CA2230275A1 - Polyamino monosuccinic acid derivative degradable chelants, uses and compositions thereof - Google Patents

Abstract

Polyamino monosuccinic acids are effective chelants for use in gas conditioning (preferably involving the polyamino monosuccinic acid in the form of a metal chelate, preferably an iron complex). Hydrogen sulfide can be removed from a fluid by contacting said fluid with an aqueous solution at a pH suitable for removing hydrogen sulfide wherein said solution contains at least one higher valence polyvalent metal chelate of at least one polyamino monosuccinic acid. NOx can be removed from a fluid by contacting the fluid with an aqueous solution of a least one lower valence state polyvalent metal chelate of at least one polyamino monosuccinic acid. The copper chelates are also useful in electroless copper plating. In electroless deposition, the invention includes a method of electroless deposition of copper upon a nonmetallic surface receptive to the deposited copper including a step of contacting the non-metallic surface with an aqueous solution comprising a soluble copper salt and at least one polyamino monosuccinic acid and plating baths appropriate for such use. Another aspect of the invention includes the use of the polyamino monosuccinic acids in laundry detergent compositions containing a detergent surfactant and builder.

Description

- CA 0223027~ 1998-02-24 POLYAMINO MONOSUCCINIC ACID DERIVATIVE DEGRADABLE
CHELANTS, USES AND COMPOSITIONS THEREOF

This invention relates to chelants, particularly uses of certain s degradable chelants.
.
Chelants or chelating agents are compounds which form coordinate covalent bonds with a metal ion to form chelates. Chelates are coordination compounds in which a central metal atom is bonded to two or 0 more other atoms in at least one other molecule (called ligand) such that at least one heterocyclic ring is formed with the metal atom as part of each ring.

Chelants are used in a variety of applications including food 1~ processing, soaps, detergents, cleaning products, personal care products, pharmaceuticals, pulp and paper processing, gas conditioning, water treatment, metalworking and metal plating solutions, textile processing solutions, fertilizers, animal feeds, herbicides, rubber and polymer chemistry, photofinishing, and oil field chemistry. Some of these activities 20 result in chelants entering the environment. For instance, agricultural uses or detergent uses may result in measurable quantities of the chelants being present in water. It is, therefore, desirable that chelants degrade after use.

Biodegradability, that is susceptibility to degradation by 2s microbes, is particularly useful because the microbes are generally naturallypresent in environments into which the chelants may be introduced.
Commonly used chelants like EDTA (ethylenediamine tetraacetic acid) are biodegradable, but at rates somewhat slower and under conditions considered by some to be less than optimum. (See, Tiedje, "Microbial Degradation of Ethylenediaminetetraacetate in Soils and Sediments,"
Applied Microbiology, Aug. 1975, pp. 327-329.) It would be desirable to have a chelant useful in areas such as those mentioned above wherein such chelant is greater than about 60 35 percent biodegradable within less than 28 days according to the OECD
301 B Modified Sturm Test or greater than about 80 percent biodegraclable CA 0223027~ 1998-02-24 W O 97/08287 PCT~US96/13939 within less than 28 days according to the Semicontinuous Activated Sludge .
Test (ASTM D 2667 89).

It has been found that certain polyamino monosuccinic acid 5 compounds are excellent chelating agents for a variety of applications.

In one aspect, the invention includes methods of electroless plating using various metals (especially copper) complexed with a mixture of chelants comprising at least polyamino monosuccinic acids, or salts 0 thereof. The invention includes a method of electroless deposition of copper upon a non-metallic surface receptive to the deposited copper including a step of conlaclillg the non-metallic surface with an aqueous solution comprising a soluble copper salt and a polyamino monosuccinic acid. Also included is a method of electroless copper plating which 5 comprises immersing a receptive surface to be plated in an alkaline, autocatalytic copper bath comprising water, a water soluble copper salt, and a polyamino monosuccinic acid complexing agent for cupric ion.
Additionally, there is an improvement in a process for plating copper on non-metallic surfaces, only selected portions of which have been pretreated 20 for the reception of electroless copper, by immersing the surface in an autocatalytic alkaline aqueous solution comprising, in proportions capable of effecting electroless deposition of copper, a water soluble copper salt, a complexing agent for cupric ion, and a reducing agent for cupric ion, the improvement comprising using as the complexing agent for cupric ion, a 2s polyamino monosuccinic acid. The invention includes a bath for the electroless plating of copper which comprises water, a water soluble copper salt, a polyamino monosuccinic acid complexing agent for cupric ions, sufficient alkali metal hydroxide to result in a pH of from 10 to 14, and a reducing agent.
Another aspect of the invention includes a method for removing iron oxide deposits or organic stains from a surface including a step of contacting the deposits or stains with a solution comprising a polyamino monosuccinic acid.
3s CA 0223027~ 1998 - 02 - 24 Yet another aspect of the invention involves gas conditioning.
In this aspect the invention includes a process of removing H2S from a fluid comprising contacting said fluid with an aqueous solution at a pH
suitable for removing H2S wherein said solution contains at least one s higher valence polyvalent metal chelate of a polyamino monosuccinic acid.
Another aspect of the gas conditioning invention includes a process of removing N0x from a fluid comprising contacting the fluid with an aqueous solution of at least one lower valence state polyvalent metal chelate of a polyamino monosuccinic acid.

The present invention is also to a laundry detergent composition comprising (a) from 1% to 80% by weight of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b) from 5% to 80% by 1S weight of at least one detergent builder; and (c) from 0.1% to 15% by weight of at least one polyamino monosuccinic acid or salt thereof.

The laundry detergent of the present invention may be a liquid laundry detergent composition comprising (a) from 10% to 50% by weight 20 of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b) from 10% to 40% by weight of at least one detergent builder; and (c) from 0.1 % to 10% by weight of at least one polyamino monosuccinic acid or salt thereof.
2s The laundry detergent of the present invention may also be a granular laundry composition comprising comprising (a) from 5% to 50%
by weight of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b) 30 from 10% to 40% by weight of at least one detergency builder; and (c) from 0.1 % to 10% by weight of at least one polyamino monosuccinic acid or salt thereof.

The above laundry compositions may be used in a process for 35 laundering fabrics comprising contacting the fabric with an aqueous solution of any of the above laundry detergent compositions.

W O 97/08287 PCT~US96/13939 In still another aspect, the present invention is to an automatic dishwashing composition comprising (a) as least one polyamino monosuccinic acid, or salt thereof; and (b~ a bleach active salt.

The present invention is also to a chelate composition comprising a chelating agent and a metal wherein the chelating agent is a polyamino monosuccinic acid and the metal is iron.

It has been unexpectedly found that polyamino monosuccinic acids are excellent for use in electroless plating of metals, in removing iron oxide stains, in removing organic stains from fabrics, in removing H2S from fluids, and in removing N0x from fluids. The compounds are also biodegradable as measured by the 301 B Modified Sturm Test or the 15 Semicontinuous Activated Sludge Test (ASTM D 2667 89).

Polyamino monosuccinic acids are compounds having at least two nitrogen atoms to which a succinic acid (or salt) moiety is attached to one of the nitrogen atoms. As used herein the term succinic acid includes 20 salts thereof. The compounds have at least 2 nitrogen atoms, and due to the commercial availability of the amine, preferably have no more than about 10 nitrogen atoms, more preferably no more than about 6, most preferably 2 nitrogen atoms. The remaining nitrogen atoms may be substituted with hydrogen, an alkyl, an alkylaryl, or an arylalkyl moiety.
2s The alkyl moiety may be linear or branched, saturated or unsaturated and generally contains from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms, and more preferably from 1 to 12 carbon atoms. The arylalkyl or alkylaryl moiety generally contains from 6 to 18 carbon atoms and preferably contains from 6 to 12 carbon atoms. The alkyl, arylalkyl, or 30 alkylaryl moieties may also be substituted with from 0 to 12 atoms other than carbon, such as oxygen, sulfur, phosphorus, nitrogen, fluorine, chlorine, bromine, iodine, hydrogen, or combinations thereof. Such substitutions include carboxyalkyl, hydroxyalkyl, sulfonoalkyl, phosphonoalkyl or alkylene hydroxamate groups.

CA 0223027~ 1998-02-24 W O 97/08287 PCT~US96/13939 Although the succinic acid moiety may be attached to any of the nitrogens, preferably the succinic acid group is attached to a terminal nitrogen atom. By terminal it is meant the first or last nitrogen which is present in the compound, irrespective of other substituents. The remaining s bonds on the nitrogen having a succinic acid group are preferably bonded to a second nitrogen through an alkyl or alkylene group and the remaining bond of the nitrogen containing the succinic acid moiety is preferentially filled by a hydrogen or an alkyl group, but most preferably hydrogen.
Generally the nitrogen atoms are linked by alkyl or alkylene groups, each of from 2 to 12 carbon atoms, preferably from 2 to 10 carbon atoms, more preferably from 2 to 8, and most preferabiy from 2 to 6 carbon atoms.
The polyamino monosuccinic acid compound preferably has at least about 6 carbon atoms and preferably has at most about 50, more preferably at most about 40, and most preferably at most about 30 carbon atoms.
In one aspect of the present invention, when it is desired for the polyamino monosuccinic acid to contain a metal ion binding moiety in addition to the carboxyl groups of the succinic acid, it is desirable to place such a functional group on a nitrogen atom to which the succinic acid moiety is not bound. For example, when the polyamino monosuccinic acid contains two nitrogen atoms which are joined by an ethylene moiety, it is preferred that the nitrogen atom which is not bound to the succinic acid moiety is substituted with at least one metal ion binding moiety. In another aspect of the present invention, depending on the molecule to be made, for ease of synthesis, the nitrogen atom or nitrogen atoms to which the succinic acid moiety is not bound are generally substituted with hydrogen.
For example, when the polyamino monosuccinic acid contains two nitrogen atoms joined by an ethylene moiety, it is preferred that the nitrogen atom which is not bound to the succinic acid moiety is substituted with two hydrogen atoms.

~ Polyamino monosuccinic acids useful in the present invention include ethylenediamine-N-monosuccinic acid, diethylenetriamine-N-monosuccinic acid, triethylenetell~nline-N-monosuccinic acid, 1,6-hexamethylenediamine-N-monosuccinic acid, 2-hydroxypropylene-1,3-diamine-N-monosuccinic acid, 1,2-propylenediamine-N-monosuccinic acid, CA 0223027~ 1998-02-24 W O 97/08287 PCTnJS96/13939 1,3-propylenediamine-N-monosuccinic acid, cis-cyclohexanediamine-N-monosuccinic acid, trans-cyclohexanediamine-N-monosuccinic acid, ethylene-bis(oxyethylenenitrilo)-N-monosuccinic acid, N-carboxymethyl-ethylenediamine-N'-monosuccinic acid, N-carboxyethyl-ethylenediamine-N'-s monosuccinic acid, N-methyl-ethylenediamine-N'-monosuccinic acid, N-methyl-ethylenediamine-N-monosuccinic acid, N-phosphonomethyl-ethylenediamine-N'-monosuccinic acid, N-sulfonomethyl-ethylenediamine-N'-monosuccinic acid, N-hydroxyethyl-ethylenediamine-N'-monosuccinic acid, N-hydroxypropyl-ethylenediamine-N'-monosuccinic acid, N-o hydroxybutyl-ethylenediamine-N'-monosuccinic acid, N-sulfonomethyl-ethylenediamine-N'-monosuccinic acid, N-2-hydroxy-3-sulfopropyl-ethylenediamine-N'-monosuccinic acid, ethylenediamine-N-methylene hydroxamate-N'-monosuccinic acid, N-carboxymethyl-diethylenetriamine-N"-monosuccinic acid, N-hydroxyethyl-diethylenetriamine-N"-monosuccinic acid, N-hydroxypropyl-diethylenetriamine-N"-monosuccinic acid, N-carboxyethyl-diethylenetriamine-N"-monosuccinic acid, N-methyl-diethylenetriamine-N"-monosuccinic acid, N-phosphonomethyl-diethylenetriamine-N"-monosuccinic acid, N-sulfonomethyl-diethylenetriamine-N "-monosuccinic acid, N-carboxymethyl- 1, 6-hexamethylenediamine-N'-monosuccinic acid, N-carboxyethyl-1,6-hexamethylenediamine-N '-monosuccinic acid, N-hydroxyethyl- 1, 6-hexamethylenediamine-N '-monosuccinic acid, N-hydroxypropyl- 1, 6-hexamethylenediamine-N'-monosuccinic acid, N-methyl-1 ,6-hexamethylenediamine-N '-monosuccinic acid, N-phosphonomethyl- 1, 6-hexamethylenediamine-N '-monosuccinic acid, N-sulfonomethyl- 1, 6-hexamethylenediamine-N'-monosuccinic acid, N-carboxymethyl-2-hydroxypropylene-1,3-diamino-N'-monosuccinic acid, N-carboxyethyl-2-hydroxypropylene- 1, 3-diamino-N '-monosuccinic acid, N-hydroxyethyl-2-hydroxypropylene-1,3-diamino-N'-monosuccinic acid, N-hydroxypropyl-2-hydroxypropylene-1,3-diamino-N'-monosuccinic acid, N-methyl-2-hydroxypropylene-1,3-diamino-N'-monosuccinic acid, N-phosphonomethyl-2-hydroxypropylene- 1, 3-diamino-N ' -monosuccinic acid, N-sulfonomethyl-2-hydroxypropylene- 1, 3-diamino-N '-monosuccinic acid, N-carboxymethyl- 1, 2-propylenediamine-N'-monosuccinic acid, N-carboxyethyl-1,2-propylenediamine-N'-monosuccinic acid, N-methyl-1,2-propylenediamine-N'-monosuccinic acid, N-hydroxyethyl-1,2-propylenediamine-N'-monosuccinic CA 0223027~ 1998-02-24 W O 97/08287 PCT~US96/13939 acid, N-hydroxypropyl-1,2-propylenediamine-N'-monosuccinic acid, N-phosphonomethyl-1 ,2-propylenediamine-N'-monosuccinic acid, N-sulfonomethyl-1,2-propylenediamine-N'-monosuccinic acid, N-carboxymethyl-1,3-propylenediamine-N'-monosuccinic acid, N-s carboxyethyl-1 ,3-propylenediamine-N '-monosuccinic acid, N-methyl-1,3-propylenediamine-N'-monosuccinic acid, N-hydroxyethyl-1,3-propylenediamine-N '-monosuccinic acid, N-hydroxypropyl- 1 ,3-propylenediamine-N'-monosuccinic acid, N-phosphonomethyl-1 ,3-propylenediamine-N'-monosuccinic acid, N-sulfonomethyl-1,3-o propylenediamine-N'-monosuccinic acid, N-carboxymethyl-cis-cyclohexanediamine-N'-monosuccinic acid, N-carboxymethyl-trans-cyclohexanediamine-N'-monosuccinic acid, N-carboxyethyl-cis-cyclohexanediamine-N'-monosuccinic acid, N-carboxyethyl-trans-cyclohexanediamine-N'-monosuccinic acid, N-methyl-cis-5 cyclohexanediamine-N'-monosuccinic acid, N-methyl-trans-cyclohexanediamine-N'-monosuccinic acid, N-hydroxyethyl-cis-cyclohexanediamine-N'-monosuccinic acid, N-hydroxyethyl-trans-cyclohexanediamine-N'-monosuccinic acid, N-hydroxypropyl-cis-cyclohexanediamine-N'-monosuccinic acid, N-hydroxypropyl-trans-20 cyclohexanediamine-N'-monosuccinic acid, N-phosphonomethyl-cis-cyclohexanediamine-N'-monosuccinic acid, N-phosphonomethyl-trans-cyclohexanediamine-N'-monosuccinic acid, N-sulfonomethyl-cis-cyclohexanediamine-N'-monosuccinic acid, N-sulfonomethyl-trans-cyclohexanediamine-N'-monosuccinic acid, N-carboxymethyl-ethylene-2s bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-carboxyethyl-ethylene-bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-methyl-ethylene-bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-hydroxyethyl-ethylene-bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-hydroxypropyl-ethylene-bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-phosphonomethyl-ethylene-30 bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-sulfonomethyl-ethylene-bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-carboxymethyl-triethylenetetramine-N"'-monosuccinic acid, N-carboxyethyl-triethylenetetramine-N"'-monosuccinic acid, N-methyl-triethylenetetramine-N"'-monosuccinic acid, N-hydroxyethyl-triethylenetetramine-N"'-3s monosuccinic acid, N-hydroxypropyl-triethylenetetramine-N'"-monosuccinic CA 0223027~ 1998-02-24 W O 97/08287 PCTnJS96/13939 acid, N-phosphonomethyl-triethylenetetramine-N"'-monosuccinic acid, and N-sulfonomethyl-triethyleneletl~rnine-N"'-monosuccinic acid.

Preferred polyamino monosuccinic acids are those that contain s two nitrogen atoms and wherein the nitrogen atom which is bound to the succinic acid moiety is substituted with hydrogen and the nitrogen atom which is not bound to the succinic acid moiety is substituted with at least one hydrogen atom.

o Polyamino monosuccinic acids can be prepared, for example, by the process of Bersworth et al. in U.S. Patent 2,761,874, the disclosure of which is incorporated herein by reference, and as disclosed in Jpn. Kokai Tokkyo Koho JP 57,116,031. In general, Bersworth et al. disclose reacting alkylene diamines and diaikylene triamines with maleic acid esters under mild conditions in an alcohol to yield polyamino monosuccinic acid esters which are then hydrolyzed to the corresponding acids. The reaction yields a mixture of the R and S isomers.

Polyamino monosuccinic acids with carboxyalkyl groups can be prepared by reacting the unsubstituted polyamino monosuccinic acids or their esters with the appropriate haloalkyl carboxylic acid or ester followed by hydrolysis of the ester. Polyamino monosuccinic acids with carboxyalkyl groups may also be prepared utilizing the reaction of the unsubstituted polyamino monosuccinic acids or their esters with the 2s appropriate aldehydes and cyanide followed by hydrolysis of the nitrile and ester to the corresponding carboxyalkyl groups. Polyamino monosuccinic acids containing a hydroxyalkyl group may be prepared by reacting the unsubstituted polyamino monosuccinic acids or their esters with the appropriate alkyl oxide followed by the hydrolysis of the ester. Polyamino monosuccinic acids containing hydroxyalkyl or alkyl groups may also be prepared by reaction of the appropriate hydroxyalkylamine or alkylamine with a maleic acid ester followed by hydrolysis of the ester or by reaction of the amine with maleic acid and an alkali metal hydroxide such as sodium hydroxide. Polyamino monosuccinic acids containing phosphonoalkyl 3s groups or sulfonoalkyl groups can be prepared by reacting the unsubstituted polyamino monosuccinic acids or their esters with the CA 0223027~ 1998-02-24 W O 97/0~287 PCTAUS96/13939 appropriate haloalkyl phosphonate or haloalkyl sulfonate, respectively foliowed by hydrolysis of the ester. Phosphonoalkyl groups may also be introduced by reacting the unsubstituted polyamino monosuccinic acids with the appropriate aldehyde and phosphorous acid. Certain sulfonoalkyl s groups may be introduced by reacting the appropriate aldehyde and a bisulfite with the unsubstituted polyamino monosuccinic acids.
Hydroxamate groups can be introduced by reacting the appropriate aminocarboxylic acid ester or anhydride with a hydroxylamine compound as described in U.S. 5,256,531.

The invention includes use of iron complexes of polyamino monosuccinic acids such as ethylenediamine-N-monosuccinic acid (EDMS) in abatement of hydrogen sulfide and other acid gases and as a source of iron in plant nutrition. Similarly other metal complexes such as the copper, 15 zinc and manganese complexes supply those trace metals in plant nutrition.
The ferrous complexes are also useful in nitrogen oxide abatement.

Iron complexes used in the present invention are conveniently formed by mixing an iron compound with an aqueous solution of the 20 monosuccinic acid (or salt). The pH values of the resulting iron chelate solutions are preferably adjusted with an alkaline material such as ammonia solution, sodium carbonate, or dilute caustic (NaOH). Water soluble iron compounds are conveniently used. Exemplary iron compounds include iron nitrate, iron sulfate, and iron chloride. The final pH values of the iron 2s chelate solutions are preferably in the range of 4 to 9, more preferably in the range of 5 to 8. When an insoluble iron source, such as iron oxide, is used, the succinic acid compounds are preferably heated with the insoluble iron source in an aqueous medium at an acidic pH. The use of ammoniated amino succinic acid solutions is particularly effective. Ammoniated amino 30 succinic acid chelants are conveniently formed by combining aqueous ammonia solutions and aqueous solutions or slurries of amino succinic ~ acids in the acid (rather than salt) form.

Polyamino monosuccinic acids are effective as chelants 3s especially for metals such as iron and copper. Effectiveness as a chelant is conveniently measured by complexing the chelant with a metal such as CA 0223027~ 1998-02-24 copper such as by mixing an aqueous solution of known concentration of the chelant with an aqueous solution containing copper (Il) ions of known concentration and measuring chelation capacity by titrating the chelant with copper in the presence of an indicator dye.
s The polyamino monosuccinic acid compounds, such as ethylenediamine-N-monosuccinic acid, are biodegradable by standardized tests, such as the OECD 301 B Modified Sturm Test or the Semicontinuous Activated Sludge Test (ASTM D 2667 89).

The polyamino monosuccinic acid compounds are preferably employed in the form of water-soluble salts, notably alkali metal salts, ammonium salts, or alkyl ammonium salts. The alkali metal salts can involve one or a mixture of alkali metal salts although the potassium or 5 sodium salts, especially the partial or complete sodium salts of the acids are preferred.

Polyamino monosuccinic acids are also useful, for instance, in food products vulnerable to metal-catalyzed spoilage or discoloration; in 20 cleaning products for removing metal ions, that may reduce the effectiveness, appearance, stability, rinsibility, bleaching effectiveness, germicidal effectiveness or other property of the cleaning agents; in personal care products like creams, lotions, deodorants and ointments to avoid metal-catalyzed oxidation and rancidity, turbidity, reduced shelf-life;
25 in pulp and paper processing to enhance or maintain bleaching effectiveness; in pipes, vessels, heat exchangers, evaporators, filters to avoid or remove scaling, in pharmaceuticals; in metal working; in textile preparation, desizing, scouring, bleaching, dyeing; in agriculture as in chelated micronutrients or herbicides; in polymerization or stabilization of 30 polymers; in the oil field such as for drilling, production, recovery, hydrogen sulfide abatement.

The chelants can be used in industrial processes whenever metal ions such as iron or copper are a nuisance and are to be prevented.
3s CA 0223027~ 1998-02-24 W O 97/08287 PCTrUS96/13939 The polyamino monosuccinic acids in the present application may be used in a variety of applications, as is disclosed for the use of disuccinic acid compounds in W0 94/05674 published May 20, 1994.
These uses include the use of succinic acid mixtures for the electroless s deposition of metals such as nickel and copper; in the polymerization of rubber; in the textile industry; in agriculture to supply micronutrients; and ingas conditioning to remove H2S, nitrous oxides (NO") and SO2.

The use of chelating agents in removal of H2S is further o exemplified by United States Patents 4,421,733; 4,614,644; 4,629,608;
4,683,076; 4,696,802; 4,774,071; 4,816,238 and 4,830,838. Gas conditioning for removal of N0X or S02 compounds is further described in United States Patents 4,732,744; 4,612,175; 4,708,854; 4,615,780;
4,126,529; 4,820,391 and 4,957,716.

The polyamino monosuccinic acids are also useful in laundry detergents, particularly laundry detergents containing a detergent surfactant and builder. The polyamino monosuccinic acids facilitate the removal of organic stains such as tea stains, grape juice stains and various food stains from fabrics during laundering operations. The stains are believed to contain metals such as copper and iron. The polyamino monosuccinic acids are very effective in chelating these metals and thus aid in the removal of the troublesome stain. The compositions comprise from 1 % to 80% by weight of a detergent surfactant, preferably from 10%
2s to 50%, selected from nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, ampholytic surfactants and mixtures thereof; from 5% to 80% by weight of a detergent builder, preferably from 10% to 50%; and from 0.1% to 15% by weight of a polyamino monosuccinic acid, preferably from 1 % to 10%, or alkali metal, alkaline earth, ammonium or substituted ammonium salt thereof, or mixtures thereof .

Nonionic surfactants that are suitable for use in the present invention include those that are disclosed in U.S. 3,929,678 (Laughlin et 3s al.), incorporated herein by reference. Included are the condensation products of ethylene oxide with aliphatic alcohols, the condensation of CA 0223027~ 1998-02-24 W O 97/08287 PCT~US96/13939 ethylene oxide with the base formed by the condensation of propylene oxide and propylene glycol or the product formed by the condensation of propylene oxide and ethylendiamine. Also included are the various polyethylene oxide condensates of alkyl phenols and various amine oxide 5 surfactants.

Anionic surfactants that are suitable for use are described in U.S. 3,929,678. These include sodium and potassium alkyl sulfates;
various salts of higher fatty acids, and alkyl-polyethoxylate sulfates.

Cationic surfactants that may be used are described in U.S.
4,228,044 (Cambre), incorporated herein by reference. Especially preferred cationic surfactants are the quaternary ammonium surfactants.

In addition, ampholytic and zwitterionic surfactants such as those taught in U.S. 3,929,678 can be used in the present invention.

Suitable builder substances are for example: wash alkalis, such as sodium carbonate and sodium silicate, or complexing agents, such 20 as phosphates, or ion exchangers, such as zeolites, and mixtures thereof.
These builder substances have as their function to eliminate the hardness ions, which come partially from the water, partially from dirt or textile material, and to support the surfactant action. In addition to the above mentioned builder substances, the builder component may further contain 2s cobuilders. In modern detergents, it is the function of cobuilders to undertake some of the functions of phosphates, for example sequestration, soil antiredeposition and primary and secondary washing action.

The builder components may contain for example 30 water-insoluble silicates, as described for example in German Laid-Open Application DE-OS No. 2,412,837, and/or phosphates. As phosphate it is possible to use pyrophosphates, triphosphates, higher polyphosphates and metaphosphates. Similarly, phosphorus-containing organic complexing agents such as alkanepolyphosphonic acids, amino- and 3s hydroxy-alkanepolyphosphonic acids and phosphonocarboxylic acids, are suitable for use as further detergent ingredients generally referred to as CA 0223027~ 1998-02-24 W O 97/08287 PCTrUS96/13939 stabilizers or phosphonates. Examples of such detergent additives are the following compounds: methanediphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane,-1,1-diphosphonic acid, 5 aminotrismethylenetriphosphonic acid, methylamino- or ethylamino-bismethylenediphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminopentamethylenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, phosphonoacetic and 0 phosphonopropionic acid, copolymers of vinylphosphonic acid and acrylic and/or maleic acid and also partially or completely neutralized salts thereof.

Further organic compounds which act as chelants that may be present in detergent formulations are polycarboxylic acids, 15 hydroxycarboxylic acids and aminocarboxylic acids which are usually used in the form of their water-soluble salts.

Examples of polycarboxylic acids are dicarboxylic acids of the general formula HOOC-(CH ) -COOH where m is 0-8, maleic acid, 20 methylenemalonic acid, citraconic acid, mesaconic acid, itaconic acid, noncyclic polycarboxylic acids having 3 or more carboxyl groups in the molecule, for example tricarballylic acid, aconitic acid, ethylenetetracarboxylic acid, 1,1,3- propanetricarboxylic acid, 1,1,3,3,5,5-pentanehexacarboxylic acid, hexanehexacarboxylic acid, cyclic 25 di- or poly-carboxylic acids (e.g. cyclopentanetetracarboxylic acid, cyclohexanehexacarboxylic acid, tetrahydrofu~antet~acarboxylic acid, phthalic acid, terephthalic acid, benzene-tricarboxylic, -tetra-carboxylic or -pentacarboxylic acid) and mellitic acid.

Examples of hydroxymonocarboxylic and hydroxypolycarboxylic acids are glycollic acid, lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, citric acid,tartaric acid and salicylic acid.

Examples of aminocarboxylic acids are glycine, glycylglycine, alanine, asparagine, glutamic acid, aminobenzoic acid, iminodiacetic acid, CA 0223027~ 1998-02-24 iminotriacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, hydroxyethylethylenediaminetriacetic acid, 2-hydroxypropylene-1,3-diaminedisuccinic acid, diethylenetriaminepentaacetic acid and higher 5 homologues which are prepared by polymerization of an N-aziridylcarboxylic acid derivative, for example of acetic acid, succinic acid or tricarballylic acid, and subsequent hydrolysis, or by condensation of polyamines having a molecular weight of from 500 to 10,000 with salts of chloroacetic or bromoacetic acid.

Preferred cobuilder substances are polymeric carboxylates.
These polymeric carboxylic acids include the carboxymethyl ethers of sugars, of starch and of cellulose. Zeolites and phosphates are also useful.

Particulariy important polymeric carboxylic acids are for example the polymers of acrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylenemalonic acid, citraconic acid, the copolymers between the aforementioned carboxylic acids, for example a copolymer of acrylic acid and maleic acid in a ration of 70:30 and having a molecular weight of 70,000, or copolymers thereof with ethylenically unsaturated compounds, such as ethylene, propylene, isobutylene, vinyl methyl ether, furan, acrolein, vinyl acetate, acrylamide, acrylonitrile methacrylic acid, crotonic acid, for example the 1:1 copolymers of maleic anhydride and methyl vinyl ether having a molecular weight of 70,000 or the copolymers 2s of maleic anhydride and ethylene and/or propylene and/or furan.

The cobuilders may further contain soil antiredeposition agents which keep the dirt detached from the fiber in suspension in the liquid and thus inhibit graying. Suitable for this purpose are water-soluble colloids usually of an organic nature for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ethercarboxylic acids or ethersulfonic acids of starch and of cellulose or salts of acid sulfates of cellulose and of starch. Even water-soluble polyamides containing acid groups are suitable for this purpose. It is also possible to use soluble starch products and starch products other than those mentioned above, for CA 0223027~ 1998-02-24 example degraded starch, aldehyde starches. Polyvinylpyrrolidone is also usable.

Bleaching agents that can be used are in particular hydrogen s peroxide and derivatives thereof or available chlorine compounds. Of the bleaching agent compounds which provide H202 in water, sodium perborate hydrates, such as NaB02.H2O2.3H20 and NaBO .H O and percarbonates such as 2 Na2C03.3H202, are of particular importance.
These compounds can be replaced in part or in full by other sources of 0 active oxygen, in particular by peroxyhydrates, such as, peroxyphosphonates, citrate perhydrates, urea, H202-providing peracid salts, for example caroates, perbenzoates or peroxyphthalates or other peroxy compounds.

Aside from those according to the invention, customary water-soluble and/or water-insoluble stabilizers for peroxy compounds can be incorporated together with the former in amounts from 0.25 to 10 percent by weight, based on the peroxy compound. Suitable water-insoluble stabilizers are the magnesium silicates MgO:SiO2 from 4:1 to 1:4, preferably from 2:1 to 1:2, in particular 1:1, in composition, usually obtained by precipitation from aqueous solutions. Other alkaline earth metals of corresponding composition are also suitably used.

To obtain a satisfactory bleaching action even in washing at 2s below 80~C, in particular in the range from 60~C to 40~C, it is advantageous to incorporate bleach activators in the detergent, advantageously in an amount from 5 to 30 percent by weight, based on the H202-providing Compound.

Activators for peroxy compounds which provide H202 in water are certain N-acyl and O-acyl compounds, in particular acetyl, propionyl or benzyl compounds, which form organic peracids with H2O2 and also carbonic and pyrocarbonic esters. Useful compounds are inter - alia:
N-diacylated and N,N'-tetraacylated amines, for example N,N,N',N'-tetraacetyl-methylenediamine or-ethylenediamine, CA 0223027~ 1998-02-24 W O 97/08287 PCTrUS96/13939 N,N-diacetylaniline and N,N-diacetyl-p-toluidine, and 1,3-diacylated hydantoins, alkyl-N-sulfonyl-carboxamides, N-acylated hydrazides, acylated triazoles or urazoles, for example monoacetylmaleohydrazide, O,N,N-trisubstituted hydroxylamines, for example 5 O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine, O-p-methoxybenzoyl-N, N-succinyl-hydroxylamine, O-p-nitrobenzoyl-N,N-succinylhydroxylamine and O,N,N-triacetylhydroxylamine, carboxylic anhydrides, for example benzoic 0 anhydride, m-chlorobenzoic anhydride, phthalic anhydride and 4-chlorophthalic anhydride, sugar esters, for example glucose pentaacetate, imidazolidine derivatives, such as 1,3 -diformyl -4,5-diacetoxyimidazolidine, 1 ,3-diacetyl-4,5-diacetoxyimidazoline and 1,3-diacetyl-4,5-dipropionyloxyimidazolidine, acylated glycolurils, for 5 example tetrapropionylglycoluril or diacetyldibenzoylglycoluril, dialkylated 2,5-diketopiperazines, for example 1,4-dipropionyl-2,5-diketopiperazine and 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine and 1,4-dipropionyl-3,6-2,5-diketopiperazine, acetylation and benzoylation products of propylenediurea or 2,2-dimethylpropylenediurea.
The bleaching agents used can also be active chlorine compounds of the inorganic or organic type. Inorganic active chlorine compounds include alkali metal hypochlorites which can be used in particular in the form of their mixed salts and adducts on orthophosphates 2s or condensed phosphates, for example on pyrophosphates and polyphosphates or on alkali metal silicates. If the detergent contains monopersulfates and chlorides, active chlorine will form in aqueous solution .

Organic active chlorine compounds are in particular the N-chlorine compounds where one or two chlorine atoms are bonded to a nitrogen atom and where preferably the third valence of the nitrogen atom leads to a negative group, in particular to a CO or SO2 group. These compounds include dichlorocyanuric and trichlorocyanuric acid and their 3s salts, chlorinated alkylguanides or alkylbiguanides, chlorinated hydantoins and chlorinated melamines.

CA 0223027~ 1998-02-24 W O 97/08287 PCTrUS96/13939 Examples of additional assistants are: suitable foam regulants, in particular if surfactants of the sulfonate or sulfate type are used, are surface-active carboxybetaines or sulfobetaines and also the s above mentioned nonionics of the alkylolamide type. Also suitable for this purpose are fatty alcohols or higher terminal diols.

Reduced foaming, which is desirable in particular for machine washing, is frequently obtained by combining various types of surfactants, 10 for example sulfates and/or sulfonates, with nonionics and/or with soaps.
In the case of soaps, the foam inhibition increases with the degree of saturation and the number of carbon atoms of the fatty acid ester; soaps of saturated C2Q-C24-fatty acids, therefore, are particularly suitable for use as foam inhibltors.
The nonsurfactant-like foam inhibitors include optionally chlorine-containing N-alkylated aminotriazines which are obtained by reacting 1 mole of cyanuric chloride with from 2 to 3 moles of a mono-and/or dialkylamine having 6 to 20, preferably 8 to 18, carbon atoms in the 20 alkyl. A similar effect is possessed by propoxylated and/or butoxylated aminotriazines, for example, products obtained by addition of from 5 to 10 moles of propylene oxide onto 1 mole of melamine and further addition of from 10 to 50 moles of butylene oxide onto this propylene oxide derivative.

2s Other suitable nonsurfactant-like foam inhibitors are water-soluble organic compounds, such as paraffins or haloparaffins having melting points below 1 00~C, aliphatic C1 8- to C40-ketones and also aliphatic carboxylic esters which, in the acid or in the alcohol moiety, possibly even both these moieties, contain not less than 18 carbon atoms 30 (for example triglycerides or fatty acid fatty alcohol esters); they can be used in particular in combinations of surfactants of the sulfate and/or sulfonate type with soaps for foam inhibition.

- The detergents may contain optical brighteners for cotton, for 3s polyamide, for polyacrylonitrile or for polyester fabrics. Examples of suitable optical brighteners are derivatives of diaminostilbenedisulfonic acid CA 0223027~ 1998-02-24 for cotton, derivatives of 1,3-diarylpyrazolines for polyamide, quaternary salts of 7-methoxy-2-benzimidazol-2'-ylbenzofuran or of derivatives form the class of the 7-[1',2',5'-triazol-1'-yl]-3-[1",2",4"-triazol-1"-y] coumarins for polyacrylonitrile. Examples of brighteners suitable for polyester are s products of the class of the substituted styryls, ethylenes, thiophenes, naphthalenedicarboxylic acids or derivatives thereof, stilbenes, coumarins and naphthalimides.

It is preferred that laundry compositions herein also contain lo enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains. Amylase and protease enzymes suitable for use in detergents are well known in the art and in commercially available liquid and granular detergents. Commercial detersive enzymes (preferably a mixture of amylase and protease) are typically used at levels of from 0.001 5 to 2 weight percent, and higher, in the present cleaning compositions.

Detergent formulations of this invention may contain minor amounts of other commonly used materials in order to enhance the effectiveness or attractiveness of the product. Exemplary of such materials 20 are soluble sodium carboxymethyl cellulose or other soil redeposition inhibitors; benzotriazole, ethylene thiourea, or other tarnish inhibitors;
perfume; fluorescers; dyes or pigments; brightening agents; enzymes;
water; alcohols; other builder additives, such as the water soluble salts of ethylenediaminetetraacetic acid, 2s N-(2-hydroxyethyl)-ethylenediaminetriacetic acid; and pH adjusters, such as sodium hydroxide and potassium hydroxide. Other optional ingredients include pH regulants, polyester soil release agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, fabric softeners especially clays and mixtures of clays with 30 various amines and quaternary ammonium compounds. In the built liquid detergent formulations of this invention, the use of hydrotropic agents may be found efficacious. Suitable hydrotropes include the water-soluble alkali metal salts of toluene sulfonic acid, benzene sulfonic acid, and xylene sulfonic acid. Potassium toluene sulfonate and sodium toluene sulfonate 35 are preferred for this use and will normally be employed in concentrates ranging up to 10 or 12 percent by weight based on the total composition.

CA 0223027~ 1998-02-24 W O 97/08287 PCT~US96/13939 It will be apparent from the foregoing that the compositions of this invention may be formulated according to any of the various commercially desirable forms. For example, the formulations of this s invention may be provided in granular form, in liquid form, in tablet form of flakes or powders.

Use of these ingredients is within the skill in the art.
Compositions are prepared using techniques within the skill in the art.

The invention will be further clarified by a consideration of the following examples, which are intended to be purely exemplary of the present invention.

EXAMPLE 1:
One mole (60.01 9) of dry ethylenediamine was mixed into 500 ml of tertiary butanol and stirred under a dry atmosphere. One mole (144.13 g) of dimethyl maleate was slowly added while keeping the temperature below 30~C and the mixture then stirred for five days. The mixing of the ethylenediamine with dimethyl maleate resulted in the formation of a white precipitate which was filtered from the solution (87.15 9, 0.427 mole).
After vacuum evaporation of the remaining liquid, additional white solid was obtained and washed with toluene. An NMR confirmed that both samples of white material were the dimethyl ester of 2-aminoethyl-N-2s aspartic acid. The solids were combined, weighed, (107.57 9, 0.527 mole), and dissoived in water. Sodium hydroxide as a 50 percent by weight solution (1.5 moles) was added to the aqueous solution of dimethyl 2-aminoethyl-N-aspartate. The resulting solution was then refluxed for three to four hours. Conversion of the resulting disodium 2-aminoethyl-N-aspartate to the acid form was accomplished by passing the solution through a cationic exchange resin (e.g., MSC-1-H obtained from The Dow Chemical Company) in the acid form. Vacuum evaporation removed the water to result in solid 2-aminoethyl-N-aspartic acid (i.e., ethylenediamine-N-monosuccinic acid). A second method for preparing the acid form of 2-3s aminoethyl-N-aspartic acid from the disodium salt was performed by addition of hydrobromic acid to the disodium 2-aminoethyl-N-aspartate CA 0223027~ 1998-02-24 W O 97/08287 PCT~US96/13939 solution until the pH fell to 4. The resulting solution was added to dry methanol which precipitated the 2-aminoethyl-N-aspartic acid. Filtration under a dry nitrogen blanket yielded solid 2-aminoethyl-N-aspartic acid (i.e., ethylenediamine-N-monosuccinic acid).
EXAMPLE 2:
In 50 ml of dry tertiary butanol, 1.75 9 (0.0236 mole) N-methylethylenediamine was dissolved and stirred under a dry atmosphere.
Dimethyl maleate (3.40 9, 0.0236 mole) was slowly added while keeping 0 the temperature of the solution below 30~C. The solution was stirred for five days followed by vacuum evaporation of the liquid. The resultant product was weighed (4.27 9, 0.0196 mole) and dissolved in water. NMR
studies revealed the presence of two geometric isomers of the product, the dimethyl ester of N'-methyl-2-aminoethyl-N-aspartate and the dimethyl ester of N-methyl-2-aminoethyl-N-aspartate. Sodium hydroxide (0.045 mole) was added and the solution was refluxed for three hours. The resulting disodium salt was converted to the acid form by passage through a cationic exchange resin (MSC-1-H) in the acid form. By collecting and concentrating appropriate fractions from the column, the two geometric isomers, N'-methyl-2-aminoethyl-N-aspartic acid (i.e., ethylenediamine-N-methyl-N'-monosuccinic acid) and N-methyl-2-aminoethyl-N-aspartic acid (i.e., ethylenediamine-N-methyl-N-monosuccinic acid), were separated.

EXAMPLE 3:
The diethyl ester of 2-aminoethyl-N-aspartic acid (23.23 9, 0.1 mole of diethyl 2-aminoethyl-N-aspartate) was dissolved in water and adjusted with sodium hydroxide to a pH above 12 in a stainless steel vessel and kept above 50~C for one hour. The solution was cooled with an ice bath.
An equal molar amount of glycolonitrile (14.33 9 of 38.9% solution, 0.1 mole) was slowly added to the solution while maintaining the temperature below 20~C and the pH above 12. After 12 hours at room temperature, the sodium hydroxide concentration was increased to 25% and the solution was refluxed for two to four hours. The acid form(s) of monocarboxymethyl 2-aminoethyl-N-aspartic acid were obtained by either 3~ adjusting the pH to 4 by the addition of HBr followed by precipitation in methanol or by passage through a cationic exchange resin (MSC-1-H) in the CA 0223027~ 1998-02-24 . w O 97/O~87 PCT~US96/13939 acid form. A product was obtained consisting of approximately 85%
ethylenediamine-N-carboxymethyl-N-monosuccinic acid and about 15%
ethylenediamine-N-carboxymethyl-N'-monosuccinic acid. ' s EXAMPLE 4:
Dimethyl ester of ethylenediamine-N-monosuccinic acid was prepared as in Example 1. A quantity of 33.29 9 (0.22 mole) methyl bromoacetate was dissolved in acetonitrile or toluene. Anhydrous sodium carbonate (36.20 9, 0.34 mole) was added to the solution. With vigorous o stirring, 45.02 9 of dimethyl ester of ethylenediamine-N-monosuccinic acid was added. The reaction mixture was refluxed for an hour and allowed to cool. The solids were removed by filtration. The solvent was removed by evaporation under a vacuum resulting in 38.9 9 of a thick, pale yellow liquid. A carbon NMR spectrum was consistent with the trimethyl ester of 5 ethylenediamine-N-carboxymethyl-N'-monosuccinic acid. Nanopure water (50 ml) and 10 M NaOH (50 ml) were mixed together and added to the 38.9 9 of liquid. The solution was stirred overnight at room temperature.
A carbon NMR was consistent with the trisodium salt of ethylenediamine-N-carboxymethyl-N'-monosuccinic acid. The solution was adjusted to pH 5 20 with HBr. Addition of the solution to a large quantity of dry methanol produced a white precipitate. Filtration of the precipitate beneath a nitrogen blanket resulted in 97.39 9 of a white powder. A carbon NMR
spectrum was consistent with ethylenediamine-N-carboxymethyl-N'-monosuccinic acid and methanol. The powder was placed into a vacuum 2s oven at 40~C. After 4 days, the material was a dry, slightly yellow powder with a weight of 37.24 9 (overall yield 73%).

EXAMPLE 5:
In 100 ml of dry tertiary butanol, 10.32 9 (0.1 mole) of dry 30 diethylenetriamine were dissolved, and the resulting solution was sparged with dry nitrogen. After cooling to 10~C, 14.41 9 (0.1 mole) dimethyl maleate was slowly added while maintaining the solution temperature below 20~C. The solution then was maintained at room temperature for three days. Although no precipitate formed, NMR analysis indicated 3s completion of the reaction by the disappearance of the methine carbons of maleate. The solvent was removed by vacuum evaporation resulting in a CA 0223027~ 1998-02-24 W O 97t08287 PCT~US96/13939 viscous, clear liquid. This liquid was dissolved in 30 milliliters of water and mixed with 30 milliliters of 10 M sodium hydroxide. The resulting solution was then refluxed for about four hours. After refluxing, the solution was passed through a cationic exchange column (MSC-1-H) in the acid form.
s Fractions from the column were collected and concentrated by vacuum evaporation of the water. A total of 13.30 9 (0.061 mole) of product was recovered and confirmed by NMR analysis to be (2-aminoethyl)-N'-2-aminoethyl-N-aspartic acid (i.e., diethylenetriamine-N-monosuccinic acid).

lo EXAMPLE 6:
About 75.1 9 of water and 64.0 9 of 50% (by weight) sodium hydroxide (0.8 mole) were placed into a stainless steel reactor equipped with a reflux condenser, thermometer, magnetic stirrer bar, and heating mantle. Maleic acid (44.5 9, 0.38 mole) was dissolved in the solution with lS five minutes of stirring. Over a 10 minute period, 2-(2-aminoethyl)-aminoethanol (42.1 9, 0.40 mole) was added. The reaction mixture was refluxed for two days and then cooled to room temperature. Half of this solution was then placed in a beaker in an ice-water bath and hydrobromic acid (65.9 9 of 49% solution, 0.4 mole) added while stirring and 20 maintaining the temperature below 25~C. The resulting solution had a pH
of 5.2 and precipitated some fumaric acid after standing for three hours.
The fumaric acid was removed by maintained at room temperature for three days. Although no precipitate formed, NMR analysis indicated completion of the reaction by the disappearance of the methine carbons of 2s maleate. The solvent was removed by vacuum evaporation resulting in a viscous, clear liquid. This liquid was dissolved in 30 milliliters of water and mixed with 30 milliliters of 10 M sodium hydroxide. The resulting solution was then refluxed for four hours. After refluxing, the solution was passed through a cationic exchange column (MSC-1-H) in the acid form. Fractions 30 from the column were collected and concentrated by vacuum evaporation of the water. A total of 13.30 9 (0.061 mole) of product was recovered and confirmed by NMR analysis to be (2-aminoethyl)-N'-2-aminoethyl-N-aspartic acid (i.e., diethylenetriamine-N-monosuccinic acid).filtration and the filtrate was stirred into 1130 9 of methanol. After 30 minutes of stirring, 3s the slurry was filtered and rinsed with 400 ml of methanol. The material was dried in a vacuum oven at 75~C for several hours. After drying, 31.5 CA 0223027~ 1998-02-24 9 (0.14 mole) of product was produced and confirmed by NMR analysis to be (2-hydroxyethyl)-N'-(2-aminoethyl)-N-aspartic acid (i.e., ethylenediamine-N-hydroxyethyl-N'-monosuccinic acid).

s EXAMPLE 7:
A 1.95 9 (0.011 mole) quantity of ethylenediamine-l\l-monosuccinic acid prepared in Example 1 was dissolved in 200 g deionized water. The pH was adjusted from 5.3 to 7.1 by addition of an aqueous ammonium hydroxide solution. Iron nitrate ~2.4 g, 0.00507 mole) was then added to lO the solution with stirring. The resulting pH of 3.1 was adjusted to about 5.0 with aqueous ammonium hydroxide, and the solution was diluted to a final volume of 500 milliliters. Fifty gram aliquots were placed in separate vessels and adjusted to pH 5.0, 6.0, 7.0, 8.0, 9.0, and 10.0 with ammonium hydroxide. After 21 days, the solutions were filtered and 5 analyzed by inductively coupled plasma spectroscopy for soluble iron. The results were as follows:

DH pPm Fe % Fe in solution 9 1.7 CA 0223027~ 1998-02-24 W O 97/08287 PCT~US96/13939 EXAMPLE 8:
A 1.02 gram (0.0058 moles) quantity of ethylenediamine-N-monosuccinic acid from Example 1 and 200 grams of deionized water were placed in a beaker. The solution was stirred with a magnetic stirrer bar and s approximately 2.4 grams of iron nitrate solution (11.8% iron) was added with stirring. The iron chelate solution (pH = 2.1) was diluted in a volumetric flask to a final volume of 500 milliliters. Fifty gram aliquots of the above solution were placed in 2 ounce bottles and the pH adjusted to 5.0, 6.0, 7.0, 8.0, 9.0 and 10.0 by the addition of a few drops of aqueous o ammonia solution. After the samples stood for 6 weeks, they were filtered and analyzed for soluble iron by inductively coupled plasma spectroscopy.
The results were as follows:

~ ppm Fe% Fe in solution 500 99.2 6 529 99.2 8 520 97.2 9 3 <1 0.9 <1 EXAMPLE 9:
A 1.35 9 (0.0061 mole) quantity of the material from Example 6 was dissolved in 200 milliliters of deionized water and stirred. Iron nitrate 2s (2.35 g, 0.0050 mole) was added to the solution which was then diluted to 500 ml. Fifty gram aliquots were placed in separate vessels and adjusted to pH values of 6.0, 7.0, 8.0, 9.0, and 10.0 with the addition of aqueous ammonium hydroxide. After 16 days, the solutions were filtered and the filtrates were analyzed by inductively coupled plasma spectroscopy for soluble iron. The results were as follows:
E~ ppm Fe% Fe in solution 3s 9 530 97 CA 0223027~ 1998-02-24 W O 97/08287 PCT~US96/13939 EXAMPLE 10:
The reduction potential of the material prepared in Example 6 was determined by making the ferric complex. The ferric complex was 0.001 molar iron and 0.0011 molar ethylenediamine-N-hydroxyethyl-N'-s monosuccinic acid in 0.1 molar NaClO4 adjusted to pH 5 with NaOH and HCI04. The half cell potentials were measured by normal pulse polarography as detailed in Electrochemical Methods, Fundamentals and Ar~Plications by A. J. Bard and L. F. Faulkner, 1980, Wiley. Correcting the results to the standard Ag/AgCI electrode gives the half cell potential of Fe 0 EDTA as -150 mV and of Fe ethylenediamine-N-hydroxyethyl-N'-monosuccinic acid as -55 mV. This redox potential indicates that the ferric complex of ethylenediamine-N-hydroxyethyl-N'-monosuccinic acid was suitable for use in certain redox applications, such as in hydrogen sulfide abatement.
EXAMPLE 11:
The reduction potential of the material prepared in Example 1 was measured by the same method as in Example 10. The half cell potential of Fe ethylenediamine-N-monosuccinic acid was -140 mV. This redox potential indicates that the ferric complex of ethylenediamine-N-monosuccinic acid was suitable for use in redox applications such as in hydrogen sulfide abatement.

EXAMPLE 12:
2s The biodegradability of the material prepared in Example 1 was measured by both the ASTM D 2667-89 (SemiContinuous Activated Sludge) test and the OECD 301 B Modified Sturm test. The ASTM D 2667-89 test exposes the organisms in sludge to about 33 ppm of the test compound each day for 28 days. After 23 hours of contact with the sludge, the remaining compound was analyzed. in order to pass the test, a minimum of 80% of a compound must be degraded during each 23 hour period for at least 7 consecutive days during the 28 day period. The ethylenediamine-N-monosuccinic acid was more than 80% degraded within the prescribed time for passing the ASTM D 2667-89 test. The OECD
3s 301 B Modified Sturm test measures the CO2 produced by the test compound or standard, which was used as the sole carbon source for the CA 0223027~ 1998-02-24 . W O 97/08287 PCT~US96/13939 microorganisms. The ethylenediamine-N-monosuccinic acid was tested at a .
20 ppm dose level. In addition to a vessel containing the test compound, a vessel containing acetate as a standard compound, and a vessel containing innoculum as a blank were used as controls. The seed innoculum was s obtained from microorganisms previously exposed to ethylenediamine-N-monosuccinic acid in a semi-continuous activated sludge test. To confirm the viability of each seed innoculum, acetic acid was used as the standard at a concentration of 20 ppm. The blank vessel was used to determine the inherent C02 evolved from each respective innoculum. Carbon dioxide o captured in the respective barium hydroxide taps was measured at various times during the 28-day test period. The results from this test indicated that the material was over 75 percent biodegraded within the prescribed time. A value of greater than 60% of the theoretical amount of C ~2 produced in this test indicates that a compound was readily biodegradable.
EXAMPLE 13:
The material prepared in Example 3 was subjected to biodegradability testing in the ASTM D 2667-89 test as described in Example 12. Results from this test show that the material was greater than 80% biodegraded 20 within the prescribed time.

EXAMPLE 14:
The material prepared in Example 1 was titrated with 0.01 M copper solution using murexide as the indicator. The material complexed 1.0 mole 2s of copper per mole of ethylenediamine-N-monosuccinic acid.

EXAMPLE 15:
The material prepared in Example 4 was titrated with 0.01 M copper solution using murexide as the indicator. Each mole of the material 30 complexed one mole of copper.

EXAMPLE 16:
The material prepared in Example 6 was titrated with 0.01 M copper solution using murexide as the indicator. Each mole of the material 35 complexed 1.0 mole of copper.

Claims (17)

WHAT IS CLAIMED IS:

1. A method of electroless deposition of copper upon a non-metallic surface receptive to the deposited copper comprising contacting the non-metallic surface with an aqueous solution comprising a soluble copper salt and at least one polyamino monosuccinic acid.

2. A laundry detergent composition comprising (a) from 1% to 80%
by weight of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b) from 5% to 80% by weight of at least one detergent builder; and (c) from 0.1% to 15% by weight of at least one polyamino monosuccinic acid or salt thereof, wherein one of the nitrogen atoms of the polyamino monosuccinic acid or salt thereof is bonded to a succinic acid and the remaining nitrogen atoms are substituted with hydrogen, a C1-C12 alkyl, or a C6-C18 arylalkyl or alkylaryl and each alkyl, arylalkyl and alkylaryl substituent may also be substituted with from 0 to 12 atoms other than carbon.

3. A liquid laundry detergent composition comprising (a) from 10%
to 50% by weight of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b) from 10% to 40% by weight of at least one detergent builder;
and (c) from 0.1 % to 10% by weight of at least one polyamino monosuccinic acid or salt thereof, wherein one of the nitrogen atoms of the polyamino monosuccinic acid or salt thereof is bonded to a succinic acid and the remaining nitrogen atoms are substituted with hydrogen, a C1-C12 alkyl, or a C6-C18 arylalkyl or alkylaryl and each alkyl, arylalkyl and alkylaryl substituent may also be substituted with from 0 to 12 atoms other than carbon.

4. A granular laundry composition comprising from 5% to 50%
by weight of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b) from 10% to 40% by weight of at least one detergency builder; and (c) from 0.1% to 10% by weight of at least one polyamino monosuccinic acid or salt thereof, wherein one of the nitrogen atoms of the polyamino monosuccinic acid or salt thereof is bonded to a succinic acid and the remaining nitrogen atoms are substituted with hydrogen, a C1-C12 alkyl, or a C6-C18 arylalkyl or alkylaryl and each alkyl, arylalkyl and alkylaryl substituent may also be substituted with from 0 to 12 atoms other than carbon.

5. An automatic dishwashing composition comprising (a) at least one polyamino monosuccinic acid or salt thereof; and (b) a bleach active salt, wherein one of the nitrogen atoms of the polyamino monosuccinic acid or salt thereof is bonded to a succinic acid and the remaining nitrogen atoms are substituted with hydrogen, a C1-C12 alkyl, or a C6-C18 arylalkyl or alkylaryl and each alkyl, arylalkyl and alkylaryl substituent may also be substituted with from 0 to 12 atoms other than carbon.

6. The composition of any one of the claims 1-5 wherein the polyamino monosuccinic acid or salt thereof has two or more nitrogen atoms wherein one of the nitrogen atoms is bonded to a succinic acid or salt thereof and the polyamino monosuccinic acid or salt thereof has from 6 to 50 carbon atoms carbon atoms which are unsubstituted or substituted with an alkyl group containing 1 to 12 carbon atoms, or an arylalkyl group containing 6 to 12 carbon atoms, or alkyaryl group containing 6 to 12 carbon atoms, wherein any of the atoms in the molecule may also be substituted with from 0 to 12 atoms other than carbon including oxygen, sulfur, phosphorus, nitrogen, fluorine, chlorine, bromine, iodine hydrogen, or various combinations of these elements

7. The composition of Claim 6 wherein the polyamino monosuccinic acid or salt thereof has from 2 to 6 nitrogen atoms with the nitrogen atoms being separated by alkylene groups of from 1 to 12 carbon atoms each.

8. The composition of Claim 7 wherein the polyamino monosuccinic acid or salt thereof has only two nitrogen atoms.

9. The composition of Claim 8 wherein the polyamino monosuccinic acid or salt thereof is selected from ethylenediamine-N-monosuccinic acid, ethylenediamine-N-methyl-N'-monosuccinic acid, ethylenediamine-N-methyl-N-monosuccinic acid, ethylenediamine-N-carboxymethyl-N'-monosuccinic acid, ethylenediamine-N-carboxymethyl-N-monosuccinic acid, 1,2-propylenediamine-N-monosuccinic acid, 1,3-propylenediamine-N-monosuccinic acid, ethylenediamine-N-hydroxyethyl-N'-monosuccinic acid, 2-hydroxypropylene-1,3-diamine-N-monosuccinic acid, or salts thereof.

10. The composition of claim 9 wherein the polyamino monosuccinic acid is ethylenediamine-N-monosuccinic acid or salt thereof.

11. The composition of any one of claims 2, 3, or 4 incorporating from 2% to 40% by weight of a bleach active salt.

12. The composition of claim 11 wherein the bleach active salt is selected from sodium perborates, sodium percarbonates, and mixtures thereof.

13 The composition of claim 12 wherein the bleach active salt is percarbonate.

14. A method for laundering fabrics comprising contacting the fabrics with an aqueous solution containing the composition of any one of claims 2, 3, or 4.

15. The composition of any one of claims 2, 3, or 4 incorporating from 0.1% to 15% by weight of at least one aminocarboxylic acid selected from glycine, iminodiacetic acid, alanine, iminotriacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, hydroxyethylethylenediaminetriacetic acid, 2-hydroxypropylene-1,3-diaminedisuccinic acid, diethylenetriaminepentaacetic acid and salts thereof.

16. A chelate composition comprising a chelating agent and a metal wherein the chelating agent is a polyamino monosuccinic acid and the metal is iron.

17. The composition of claim 16 wherein the polyamino monosuccinic acid is or salt thereof is selected from ethylenediamine-N-monosuccinic acid, ethylenediamine-N-methyl-N'-monosuccinic acid, ethylenediamine-N-methyl-N-monosuccinic acid, ethylenediamine-N-carboxymethyl-N'-monosuccinic acid, ethylenediamine-N-carboxymethyl-N-monosuccinic acid, 1,2-propylenediamine-N-monosuccinic acid, 1,3-propylenediamine-N-monosuccinic acid, ethylenediamine-N-hydroxyethyl-N'-monosuccinic acid, 2-hydroxypropylene-1,3-diamine-N-monosuccinic acid, or salts thereof.