CA1293419C - Ether carboxylate detergent builders and process for their preparation - Google Patents

Abstract

ETHER CARBOXYLATE DETERGENT BUILDERS AND
PROCESS FOR THEIR PREPARATION
ABSTRACT OF THE DISCLOSURE
Provided herein are ether carboxylate builder compositions comprising a combination of tartrate monosuccinic acid (or salts thereof) and tartrate disuccinic acid (or salts thereof). Such mixtures can be prepared by reacting water-soluble, mixed maleic acid salts with mixed tartaric acid salts. Both components of the resulting ether carboxylate mixture act as sequestering agents and are useful as detergency builders. Detergent and laundry additive compositions incorporating these ether carboxylates can be pre-pared without use of detergent builder components containing phosphorus or nitrogen.

Description

~a ~3 ETHER CARBOXYLATE DETERGENT BUILDERS AND
PROCESS FOR THEIR PREPARATION
Rodney Do Bush Daniel S. Connor Stephe~ W. H~inz~an Larry N. Mackey BACKGROUND OF THE INVEHTION
The present invention relates to ether carboxylate-containing compositions and to a process for making them. These ether locarboxylate materials are effective sequestering agents and are useful as builders in detergent compositions for householdD in-stitutional and industrial use.
The role of sequestering agents in softening water by com-plexing the "hardness" cations in water supplies is well-known.
15Sequestering agents are recognlzed aids in detergent processes because they form a soluble complex with calcium and magnesium ions which can react with soaps and other anionic surfactants and otherwise adversely affect detergency. Polyphosphates such as ; tripolyphosphates and pyrophosphates are widely used as ingredi-~` 20ents in detergent compositions in part because of their property of sequestering hardness ions. Such phosphorus-containing com-pounds as well as nitrogen-containins compounds, e.g., nitrilo-triacetates, are highly effective. However, the effect of the phosphorus content and the nitrogen content of these sequestering 25agents upon eutrophication of lakes and streams has been ques-tioned, and the use of phosphates in detergent compositions has been subject to government scrutinyp regulation or prohibition.
These circumstances have developed a need for highly effec-~` tive and efficient phosphorus-free and nitrogen-free sequestering 30agents and detergency builders. A varie~y of phosphorus-free and ~ nitrogen-free builder materials have, in fact, been prepared in `~ the form of polycarboxylate compounds. Especially preferred polycarboxylate builders from the standpoint of hardness seques-tering capacity and builder performance are the ether polycar-35boxylates.

~ P

?3f~1 A number of types of ether polycarboxylates are known in the art and, along with ~ethods for their preparation, have been disclosed in the patent literature. For example, Stubbs et al;
U.S. Patent 4,017,541; Issued April 12, 1977 disclose dicarboxy-5 alkyl ethers of the for~ula:
COOM
(~H2)n R - CH - ~ - CH
(CH20CH2)m SOOM

wherein R1 is H,-CH3 or -COOM; R2 is H or COOM; R3 is H,^C~2COOM
or -CH(COOM)(CH2)n(COOM), n is O or 1, m is 0, 1 or 2 or M is H,~CH3, -C2H5 or alkali metal. Preferred compounds of this type ; are said to include propylene glycol monosuccinyl ether and propylene glycol disuccinyl ether.
Pearson et al; U.S. Patent 3,776,850; Issued December 4, 1g73 disclose polymeric polycarboxylate builder compounds of the formula:
R R
HO - - C - C - O - -H
COOH COOH n wherein R can be hydrogen and n ranges from 2 to 4. Builder compositions of this ~ype usually contain a mixture of polymers having structures within this general formula.
Berg; U.S. Patent 3,120,207; Issued April 7, 1964 and Lam-berti et al; U.S. Patent 3,635,830; Issued January 18, 1972 both disclose oxydisuccinic acid and salts thereof. The '830 patent discloses the use of this oxydisuccinic acid material as ~ deter-gent builder.
The disclosed methods for preparing the ether carboxylates of the foregoing patents in general inwlve the alkaline earth metal catalyzed reaction of carboxylic reactants such as maleic an hydride, maleic acid, and their derivatives. For example, oxy-disuccinate builder materials as disclosed in the aforementioned U.S. Patents 3,120,207 and 3,635,830 are prepared by heating maleic anhydride or maleic acid in the presence of a molar excess 34~

of calcium hydroxide, followed by acid treatment of the resulting reaction product. Such processes employing these particular reactants~ however, have especially s10w reaction kinet~cs and furthermore result in relatively low conversions of starting material to the desired ether carboxylate reaction product. These processing disadvantages render such materials as oxydisuccinate less attractive for use as builders in detergent products to be commercially marketed in large volume.
Therefore, notwithstanding the existence of the foregoing Io types of ether carboxylate detergent builders and ether carboxy-late preparation processes, there remains a continuing need to identify additiona1 non-phosphorus, non-nitrogen sequestering agents such as ether carboxylates which can be prepared via commercially acceptable synthesis processes and which can be employed in commercially useful and practical detergent composi-tions. Accordingly, it is an object of the present invention to provide novel ether carboxylate builder compositions and compo-nents thereof, which compositions and components can serve as especially effective builder materials in both granular and liquid detergent and laundry additive compositions.
It is a further object of the present invention to provide a process for preparing ether carboxylate materials of this type via an efficient, hlgh yield reaction which utilizes simple, commer-cially available reactants.
It is a further object of the present invention to provide detergent compositions and laundry additiYe compositions employing such novel ether carboxylate compounds as sequestering builders.
SUMMARY OF THE IN~ENTION
In its composition aspects, the present invention relates to ether carboxylate detergent builder compositions comprising from about 1% to 99% by weight of a tartrate monosuccinic acid, or a salt thereof, and from about 1% to 99% by weight of a tartrate disuccinic acid~ or salt thereof. Separate claims to each of these novel builder co~position components are also presented.
Likewise claims are also presented to detergent compositions and laundry additive compositions containing 1) the ether carboxylate 3~

compositions herein or 2) the novel components of such composi-tions.
In its process aspects, the present invention relates to a process for preparing a mixture of ether carboxylates useful as detergent builder composition. Such process involves the forma-tion of an aqueous reaction mixture containing, as reactants, from about 20% to 60% by weight o~ both calcium and ~onovalent cation salts of maleic acid and tartaric acid. Such a reaction mixture corresponds to the over neutralized mixture which is formed by combining maleic and tartaric acids in a molar ratio of from about 0.5:1 to about 8:1, along with particular amounts of a source of calcium cations and a neutralizing agent comprising an hydroxide of a monovalent cation. The source of calcium cations, preferably calcium hydroxide, is added to the reaction mixture in a molar ratio of calcium to tartaric acid within the range of from about 0.1:I to 2:1 with the proviso that the moles of calcium added not exceed the total moles of maleic and tartaric acids added. The monovalent cation-containing neutralizing agent is added in an amount such that the ratio of monovalent cations to ~oles of maleic acid plus moles of tartaric acid minus moles of calcium ranges from about 2.1:1 to about 3.8:1. Such a reaction mixture is maintained at a temperature of from about 20C to 120C for a period of time sufficient to form a reaction product mixture containing both a) tartrate monosuccinic acid salt, and b) tar-trate disuccinic acid salt. The resulting reaction product mixture is thereafter treated to reduce its calcium content to the extent that the molar ratio of calcium to the tartrate succinate product compounds therein is less than about 1:10.

The drawing provides an illustration of the concentration of free calcium ion in a solu~ion into which solutions of various ; builder materials, including those of the present invention, are ;; titrated.
DETAILED DESCRIPTION OF THE INVENTION
The principal component of the ether carboxylate builder compositions of the present invention is a particular novel ~lZ~3 ~

tartrate monosuccinic acid, or salts thereof, having the struc-tural formula:

COOX CûOX COOX COOX
wherein X is H or a salt-forming cation. This tartrate mono-succinic acid or salt thereof is hereinafter designated as "TMS."
"TMS" is used to designate both the acid and salt forms of this material.
The tartrate monosuccinic acid component may be employed in the compositions herein in its free acid form, i.e. 9 wherein X in the structural formula is H. Alternatively, and preferably, this material may be partially or fully neutralized to a tartrate monosuccinate salt. Preferred salt-forming cations useful ~n forming the neutralized materials are those which yield substan-tially water-soluble salts of tartrate monosuccinic acid. Exam-ples of such preferred salt-forming cations include alkali metal (e.g., sodium, potassium, lithium), ammonium, Cl-G4 alkyl sub-stituted ammonium and Cl-C4 alkanolamine. The most pr~ferred salt-forming cations are sodium, potassium, monoethanolamine and triethanolamine.
The tar~rate monosuccinic component will generally be present in the builder compositions of this invention in an amount ranging from about lX to 99% by weight-of the composition. More pref-erably, the tartrate monosuccinate component will comprise from about 10% to g8X by weight of the builder compositions herein.
Most preferably, this component is present to the extent of from about 20X to 97X by weight of the builder composition.
The second essential component of the ether carboxylate builder compositions of this invention is the particular novel ; polycarboxylate, tartrate disuccinic acid, or a salt thereof, having the structural formula:
CH - CH - O - CH - CH - O - CH - CH
~ 2 ~ 2 COOX COOX COOX CO~X COOX C~OX
wherein X is H or a salt-forming cation. Tartrate disuccinic acid, or a salt thereof, ls hereinafter designated as "TDS."

3 ~ 3 As with the TMS component, the TDS component can be utilized in either its free acid form or in its partially or fully neu-tralized form in the builder compositions herein. Neutralizing cations are likewise those which provide TDS in the form of its substantially water-soluble salt. Examples of suitable salt-forming cations include the same cations hereinbefore described for formation of the tartrate monosuccinate material. For conve-nience both the acid and salt forms of the TDS material will hereinafter be referred to as the "tartrate disuccinate" or "TDS"
component.
The TDS component will generally be present in the builder compositions of this invention in an amount ranging from about 1%
to 99% by weight of the composition. More preferably~ the TDS
component wlll comprise from about 2X to 90% by weight of the builder compositions herein. Most preferably, TDS is present to the extent of from about 3% to 80% by weight.
The builder compositions of the present invention need only contain the tartrate monosuccinate and tartrate disuccinate components hereinbefore described and can be prepared in the form of solid or granular compositions containing these components.
Frequently however, the builder compositions herein will contain optional materials such as those used or formed during the prepa-ration of the builder compos~tions as hereinafter described. Most frequently, one such optional ingredient of the builder composi-tions herein will be water or moisture from the a~ueous reaction mixture used to prepare the builder compositions. Other possible optional ingredients include unreacted reactants such as maleates, tartrates and alkaline earth metals, e.g., ca7cium, ~in ionic, complex, or salt form) used in the preparation of the TMS and TDS
components. Likewise, the builder compositions will frequently contain some by-products of the process used for composition preparation. Such by products can include, for example, malates, malea~es, tartrates, fumarates and the like.
No ma~ter what the nature of the optional components, the builder compositions herein will generally contain no more than about 70X by weight of the composition of such optional -~L~9 3 ~

components. Since the compositions herein are to be used as detergent builders, it is especially important that such composi-tions contain especially low levels o~ alkaline earth metals such as calcium. The builder compositions of this invention should generally contain no more than about 10 Mole percent of calcium based on thè total ~oles of TMS and TDS present.
Whether or not the builder compositions herein contain significant amounts of optional ingredients, the two essential ether carboxylate components will generally be present in such compositions in a tartrate monosuccinate to tartrate disuccinate weight ratio of from about 97:3 to 20:80. More preferably, this weight ratio will range from about 95:5 to 40:60.
It has been discovered that the particular two-component builder mixtures of the present invention provide hardness, e.g.
calcium, sequestering performance which is superior to that of known ether carboxylate builder mater~als such as carboxymethyl-oxysuccinate and oxydisuccinate and wh~ch is also superior to that of conventional builder materials such as sodium tripolyphosphate.
Furthermore it has also been discovered that certain of the two-component builder compositions herein, i.e., those containing the hereinbefore described preferred ratios of TMS to TDS, can be prepared by a procedure hereinafter described with especially high conversion of reactants to desired builder materials after espe-cially short reaction time.
Both the tartrate monosuccinate, i.e., TMS, component and the tartrate disuccinate, i.e., TDS, component of the builder composi-tions herein can be synthesized by the reaction of mixed calcium and monovalent cation maleic acid salts with mixed calcium and monovalent cation tartaric acid salts. Such a reaction, in fact, produces a mixture of tartrate monosuccinate and tartrate di-succinate with the relative amounts of tartrate monosuccinate and tartrate disuccinate in such a mixture depending on the molar ratio of the maleate and tartra~e reactants used and the reaction conditions used. Accordingly, such a reaction can be used to ; 35 directly form the two-component builder compositions of this ~39~1~

invention, and this reaction thus forms the basis of the builder composition preparation process of the present invention.
The first step of the builder composition preparation process herein involves the formation of an aqueous reaction mixture containing particular amounts of a maleate reactant comprising both monovalent cation and calcium salts of maleic acid and a tartrate reactant comprising both monovalent cation and calcium salts of tartaric acid. The total amount of maleate plus tartrate reactants in the reaction mix~ure will generally range from about lo 20% to 60% by weight of the mixture, more preferably from about 40% to 55% by weight. Materials which yield these reactants in solution can be dissolved in water to form the reaction mixture used in this process.
Usually both the maleate and tartra~e reactants in requisite mixed salt form and amounts can be generated in the reaction mixture in si~u. This can be done by combining in aqueous so-lution certain amounts of maleic acid or maleic anhydride, tar-taric acid, a source of calcium cations and, as a neutralizing agent, an hydroxide of a monovalent cation in certain amounts.
The molar ratio o~ maleic acid to ~artaric acid in such solutions will generally range from about 0.5:1 to 8:1, more preferably from about 0.9:1 to 1.2:1. The ratio of maleic and tartaric acids which is used will depend upon the relatiYe amounts of tartrate monosuccinate and tartrate disuccinate desired in the builder composition to be prepared.
A source of calcium cations, which act as a catalyst for the tartrate succinate-forming reaction, is generally added to such aqueous solutions in an amount such that the ratio of catcium cations to tartaric acid range from about 0.1:~ to about 2.0:1, more preferably from about 0.8:1 to 1.5:1. However, within this ratio range, the amount of calcium added should be such ~hat the ratio of moles of calcium cations to total moles of maleic and tartaric acids in solution is less than 1. Any compound which yields calcium cations in solution can be employed as the calcium cation source. Such compounds include calcium hydroxide and water-soluble calcium salts. Catcium hydroxide is highly pre-1~39*:~
g ferred since it acts as both a calcium cation source and a neu-tralizing agent.
An hydroxide of a monovalent cation is also essentially added to the reactant mixture as a neutralizing agent. This neutraliz-ing agent is usually added in an amount such that the ratio ofmoles of monovalent cations to total moles of tartaric acid plus the moles of maleic acid minus the ~oles of calcium cations ranges from about 2.1:1 to about 3.8:1. More preferably this ratio ranges from about 2.2:1 to about 3:1. The monovalent cation-containing neutralizing agent can be any hydroxide which uponaddition to water yields monovalent neutralizing cations in solution. Such neutralizing agents include, for example, alkali metal, ammonium or substituted ammonium hydroxide. Sodium hy-droxide is highly preferred.
Enough neu~ralizing base (e.g. calcium hydroxide and mono-~ valent cation hydroxide) should be idded to the reaction mixture ; to ensure that the reaction mixture is over-neutralized. Thus thereaction mixtures of this invention will generally have a pH
within the range of from about 8.5 to 13, more preferably from about 9.5 to 12.5.
In forming the reaction mixture of the present process, it is possible to employ precursors of the essential reaction mixture components. Precursors of the tartrate and maleate mixed salt reactants in solution can take a variety of forms. For example, tartaric actd in either its D-, L- or DL- stereoisomer form is suitable for use as the precursor of the tartrate reactant. It is also possible to generate tartaric acid in situ by reaction of maleic acid and hydrogen peroxide using, for example, a tungstate catalyst. The maleate reactant can be derived from maleic acid.
Maleic acid itself can be formed in aqueous solution by the addition of maleic anhydride to water.
It iS9 of course, also possible to form the reaction mixture used in the process herein by adding the tartrate and maleate reactants in their appropriate salt forms to wa~er and ~o thereby prepare the reaction mixture without the step of in situ neu-tralization. If ~he reaction mixture is formed in this manner, 3~:~{3 amounts of the tartrate, maleate and calcium materials, as well as added neutralizing agents, should be selected so that the result-ing solution corresponds in composition to the hereinbefore described reaction mixtures formed by in situ generation of the ; 5 essential reaction mixture components As indicated hereinbefore, the preferred process o~ the present invention employing reactant molar ratios of maleate to tartrate within the range of 0.9:1 to 1.2:1 is especially advanta-geous from the reactant conversion and reaction kinetics stand-point. At reactant ratios within this range, total reactant conversion levels as high as 84% can be realized in comparison with the much lower conversion percentages reported for prepara-tion of such materials as oxydisuccinate using a maleic anhydride reactant. Without being bound by theory, the improved conversion ; 15 percentages which can be realized using the preferred process embodiments of the present invention may be in part due to the inherently greater stability of TMS in the reaction mix~ure in co~parison with oxydisuccinate (ODS) under similar conditions.
TMS under conditions used for its formation does not appear to decompose as readily as oxydisuccinate to unreactive by-products such as fumarate, thereby enhancing both TMS formation and subsequent TDS formation from TMS. It should also be noted that irrespective of conversion percentage, production of MHODS/TDS
mixtures in general can be realized in a relatively short reaction time compared with the extended reaction times which are reported to be required for preparation of other ether carboxylates such as oxydisuccinate.
It should also be noted that use of the hereinbefore de-scribed par~icular amounts of the calcium cation source is like-3~ wise believed to play a role in realizing the improved conversiun levels achieved with the process of the present invention. In direct contrast to prior art teaching regarding ether carboxylate preparation (See, for example, U.S. Pa~ent 3,635,830), the amount of calcium in the reaction mixture of the present process should be kept within the hereinbefore described concentration limits in order to avoid ~ormation of a large amount of insoluble or 12~3~

sparingly soluble calcium salts of the maleate and tartrate reactants. Utilization of these reactants in their soluble, mixed salt, e.g. sodium/calcium, form may facilitate the kinetics of the ether carboxylate-forming reaction and accordingly improve product yield.
After the aqueous reaction mixture hereinbefore described has been formed by combining the separate reactants and catalyst, or precursors thereof, in the required concentrations, the builder composition forming reaction is carried out by maintaining the lo aqueous reaction mixture at a temperature of from about 20C to 120C, preferably from about 50C to 80~C, for a period of time sufficient to form a reaction product mixture which contains the desired amounts of the tartrate monosuccinate and tartrate di-succinate components of the compositions herein. Reaction times of from about 0.5 to 10 hours, more preferably from about 1 to 4 hours will generally be suitable for realizing acceptable yields of the two essential components of the builder compositions herein.
After the ether carboxylate forming reaction has been com-pleted to the desired extent, the calcium content of the aqueous ; reaction must be reduced. Removal of calcium to effect this reduction can be carried out in a number of ways known in the art.
Frequently, calcium can be removed from the product mixture by adding thereto a calcium precipi~ating material having a greater affinity for reaction with calcium than do the tartrate mono-succinate and tartrate disuccinate reaction products. Such mate-rials can include, for example, precipitating chelating agents such as ethanehydroxyd~phosphonic acid, or salts thereof, (EHDP) or calcium precipitating materials such as alkali metal carbonate, pyrophosphate, bicarbonate and/or alkali metal silicate. The resulting calcium precipitate can thereafter be removed from the aqueous reaction product mixture by filtration. An alternate means for removing calcium from the aqueous reaction product mixture involves treatment of ~he reaction product mixture with an appropriate insoluble ion exchange resin. No matter what tech-nique is employed, calcium con~2nt of the aqueous reaction mixture ~3~1~

should be reduced to the extent that the ratio of moles of c~lcium to total moles of tartrate monosuccinate and tartrate disuccinate is less than about 1:1~, preferably less than about 1:20.
Preferably in addition to such calcium reduction processing, the reaction product mixture of the present invention may also optionally be treated to remove excess reactants or reaction by-products such as maleates, malates, tartrates and fumarates.
This can be accomplished by conventional salt separation pro-cedures using a solvent such as methanol in which these excess reactants and reaction by-produc~s are relatively soluble and in which the desired tartrate monosuccinate and tartrate disuccinate are relatively insoluble.
After the calcium content of the aqueous reaction product mixture has been reduced to the requisite levels, and, if deslred, lS after excess reactants and reaction by-products have been removed, the reaction product mixture may be concentrated by a removal of water to the desired extent. Water removal may, for example, involve substantially complete drying of the reaction product mixture, e.g., by spray drying~ so that the ether carboxylate builder mixt~re is recovered in solid, e.g., granular, form.
Alternatively, the builder composition in the form of an aqueous liquid may be utilized directly in the preparation of detergent compositions or laundry additive products of the types more fully described hereinafter.
After reduction of the calcium content in the reaction product m~xture, it is possible, if desired, to acidify the product mixture using conventional acidification or ion exchange techniques to convert the ether carboxylate produc~s therein to their free acid form. Nonmally, however, the tartrate mono-succinate and tartrate disuccinate materials of this invention can be used as builders in their water-soluble salt form, ard such ~`~ acidification is therefore not usually necessary or desirable.
It is also possible, if desired, to separate the individual components of the resulting builder mixture and recover such compounds as substantially pure TMS and TDS materials. Such component separation can be effected, for example, using ~z~

conventional liquid chromatographic techniques. For use in some types of detergent compositions, it may be desirable to use either TMS or TDS as substantially pure materials. More frequently, however, recovery of the individual TMS and TDS components as substantially pure materials is neither necessary nor particularly advantageous.
The ether carboxylate builder compositions herein, or the individual tartrate monosuccinate and tartrate disuccinate compo-nents thereof, may be employed as sequestering builders in a wide varie~y of detergent compositions or laundry additive compo-sitions. These particular builder materials are believed to be especially effective in promoting certain types of fabric cleaning in comparison with a number of structurally s~milar carboxylate builders of the prior art. Such materials also retain their lS efficacy as detergent bu1lders even in relatively low pH cleaning solutions. The specific ether carboxylate materials of this invention furthermore possess especially desirable biodegrad-ability characteristics.
Detergent compositions incorporating the ether carboxylate materials of the present invention contain as essential components from about 0.5g to about 98% of a surfactant and from about 2% to about 99.5X of the ether carboxylate compounds or mixtures of the present invention as a detergency builder.
Typical laundry detergent compositions within the scope of ~he present invention contain from about 5% to about 30X of a surfactant and from about 5X to about 80% total detergency build-er. Of this builder component from about 20% to lOOX by weight of builder component can be the ether carboxylate compounds or mixtures of the present inven~ion with the balance of the builder component being op~ional known builders.
Detergent compositions herein may also contain from about 5%
to 95% by weight of a wide variety of addition~l optional compo-nents. Such optional componen~s can include, for example, addi-tional detergent builders, chelating agents, enzym2s~ fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering ~3~
:

agents, soil removal/anti-redeposition agents, soil release agents, fabric softening agents, perfumes, colorants and opac-ifiers. A number of these additional optional components are hereinafter described in greater detail.
The detergent compositions of this invention are effective in cleaning solutions over the broad cleaning solution pH range of from about 6 to about 13. The compositions can be formulated to provide a desired cleaning solution pH by proper selection oF the acid form of appropriate salts or mixtures thereof. Preferred water-soluble salts of the builder compounds, for example, can be the alkali metal salts such as sodium, potassium, lithium and am~onium or substituted ammonium, e.g. triethanol ammonium.
Depending on the pH of the desired solution, the salts are par-tially or fully neutralized.
l~ The detergent compositions of this invention can be prepared in solid or liquid physical form.
The detergent compositions of this invention are particular7y suitable for laundry use, but are also suitable for the cleaning of hard surfaces and for dishwashing.
In a laundry method using the detergent composition of this invention, typical laundry wash water solutions comprise from about 0.1% to about 1% by weight of the detergent compositions of this ~nvention.
The ether carboxyla~e materials herein may also be employed as builders in laundry additlve compositions. Laundry additive compositions of the present invention contain as essential compo-nents from about 2% to about 99.5% of the ether carboxylate compounds or mixtures of the present invention and further con-tains from about 0.5% to 98% by weight of a laundry adjuvant selected from the group consisting of surfactants, alternate builders, enzymes, fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes9 bleaching agents, bleach precursors, buffering agents, soil removal/antideposition agents, soil release agents, fabric softening ~gents, perfumes, colorants, opacifiers and mixtures of these adjuvants. Such adjuvants, whether used in the detergent or laundry additive compositions ~L~ 3~

herein, perform their expected functions in such compositions. A
number of these adjuvants are described in greater detail as ~o 1 1 ows:
Surfactants Yarious types of surfactants can be used in the detergent or laundry additive compositions of this invention. Useful surfac-tants include anionic, nonionic, ampholytic, zwitterionic and cationic surfactants or mixtures of such materials. Detergent compositions for laundry use typically contain from about 5% to about 30% anionic surfactants, mix~ures of anionic and nonionic surfactants or cationic surfactants. Detergent compositions for use in automatic dishwashing machines typically contain from about 2X to about 6% by weight of a relatively low sudsing nonionic surfactant or mixtures thereof and, optionally, suds control agents. Particularly suitable low sudsing nonionic surfactants are the alkoxylation products of compounds containing at least one reactive hydrogen wherein, preferably, at least about 20% by weight of the alkylene oxide by weight is propylene oxide.
Examples are produc~s of the BASF-Wyandotte Corporation designated Pluroni ~, Tetronic~, Pluradot~ and block polymeric variations in which propoxylation follows ethoxylation. Preferred suds control agents include mono-and distearyl acid phosphates.
The various classes of surfactants useful in the detergent and laundry additive compositions herein are exemplified as ~ollows:
(A) Anionic soap and non-soap surfactants This ctass of surfactants includes alkali metal monocar-boxylates (soaps) such as ~he sodium, potassium, ammonium and alkylolammonium satts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 12 to about 18 carbon atoms. Suitable fatty acids can be obtained from natural sources suoh as, for ~nstance, from plant or animal esters (e.g.~ palm oil, coconu~ oil 9 babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof). The fatty acids also can be synthetically prepared (e.g.~ by the oxidation of petroleum, or by hydrogenation of ~3 carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable such as rosin and those resin acids in tall oil. Naph-thenic acids are also suitable. Sodium and potassium soaps can be made by direct saponification of the fats land oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the ; sodium and potassium salts of the mixtures of fatty acids derivedfrom coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Soaps and fatty acids also act as detergency builders in detergent compositions because they remove multivalent ions by precipitation.
Anionic surfactants also include water-soluble salts, par-ticularly the alkali metal and ethanolamine salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical. (Included in the term alkyl is the alkyl portion of alkylaryl radicals.) Examples of this group of non-soap anionic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (C~-C18 carbon atoms); alkyl ben~ene sulfonates3 in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, sodium alkyl glyceryl ether sulfonates; fatty acid monoglyceride sulfonates and sulfates; sulfuric acid esters of the reaction product of one mole of a C12 18 alcohol and about 1 to 6 moles of ethylene oxide and salts of alkyl phenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain abou~ 8 to about 12 carbon atoms.
Additional examples of non-soap an~onic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil and sodium or potassium salts of fat~y acid amide of methyl lauride in which the fatty acids, for example are derived from coconut oil.
Still other anionic surfactants include the class designated as succinamates. This class includes such surface active agents 3~

as disodium N-ootadecylsulfosuccinamate; tetrasodium N-(1,2-dicar-boxyethyl)-N-octadecylsulfosuccinamate9 the diamyl ester of sodium sulfosuccinic acid; the dihexyl ester of sodium sulfosuccinic acid and the dioctyl ester of sodium sulfosuccinic acid.
Anionic phosphate surfactants are also useful in the deter-gent or laundry additive compositions of the present invention.
These are surface active materials having substantial detergent capability in which the anionic solubilizing group connecting hydrophobic moieties is an oxy acid of phosphorus. The more common solubilizing groups are -S04H, -503H, and -C02H. Alkyl phosphate esters such as (R-0)2P02H and ROP03H2 in which R repre-scnts an alkyl chain containing from about 8 to about 20 carbon atoms are useful.
These esters can be modified by lncluding in the molecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units.
Particularly useful anionic surfactants for incorporation into the compositions herein are alkyl ether sulfates. The alkyl ether sulfates are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms.
Preferably, R has 12 to 18 carbon atoms. The alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthet-ic. Such alcohols are reacted with 0.5 to 30, and especially 1 to 6, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 to 6 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
Other suitable anionic surfactants are olefin and paraffin sulfonates having from about 12 to about 24 carbon atoms.
~B) Nonionic sur~actants Alkoxylated nonionic surfactants may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Alkoxylated nonionic surfactants include:
(1) The condensation product of aliphatic alcohols having from 8 to 22 carbon atoms, in ei~her straight chain or branched chain configuration, with from about 5 to about 20 moles of ethyl-ene oxide per mole of alcohol.

(2) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the ethylene oxide being present in amounts of from about S
to about 25 moles of ethylene oxide per ~ole of alkyl phenol. The alkyl substituent in such compounds may be derived from poly-merized propylene, diisobutylene, octene, or nonene, for example.
(3~ Materials derived from the condensatinn of ethylene oxide with a product resulting ~rom the reaction of propylene ; oxide and a compound with reactive hydrogen such as glycols and amines such as, for example, compounds containing from about 40%
2~ to about 80% polyoxyethylene by weight resulting from the reaction of ethylene oxide with a hydrophobic base constituted of the re-action product of ethylene diamine and propylene oxide.
Non-polar nonionic surfactants inc1ude the amine oxides and corresponding phosphine oxides. Useful amine oxide surfactants include those having the formula R1R2R3N_o wherein R1 is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of Rl which is an alkyl group containing from about 10 to about 18 carbon atoms and R2 and R3 are selected ; 30 from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.
Specific examples of amine oxide surfactants include: di-methyldodecylamine oxide, dimethyltetradecylamine oxide, ethyl-methyltetradecylamine oxide, cetyldimethylamine oxide, diethyl-tetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hy-droxyethyl)dodecylamine oxide, bis-(2-hydroxypropyl~methyltetra-decylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.
Additional operable nonionic surfactants ~nclude alkyl glucos1des and alkylamides of the formula O
Rl--C---NHR2 l s C10-Cl8 alkyl and R2 is -H~ -CH2 or -C H
lo (C) Zw~tterion1c Surfactants Zwitterion1c surfactants include derivàtives of al1phatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic moiety can be straight or branched chain and whereln one of the allphatic substituents conta1ns from about 8 to 24 carbon atoms and one contains an anionic water-solubilizing group.
Particularly preferred zwitter10nic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al, issued December 9, 1975 and 3,929,678, Laughlln et al, issued December 30, 1975. Ammonioamidates are also useful zwitterionic surfactants.
(D) Ampholyt k Surfactants Ampholytlc surfactants include derivat~Yes of aliphatic ^
heterocycllc secondary and tertiary amines in which the aliphatic molety can be stralght chain or branched and wherein one of the allphatlc substituents contains from about 8 to about 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solub~lizing group.
; (E) Cationic Surfactants 3~ Cationic surfactants compr~se a wide variety of compounds characterized by one or more organlc hydrophoblc groups in the cation and generally by a quatern~ry nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered ~uaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide~ Tertiary amines can have characteristlcs s~m~lar to ca~ionic sur~actants at washing so-lutions pH values less than about 8.5.

:~Z~ 19 A more complete disclosure of cationic surfactants can be found in U.S. Patent 4,2~89044, issued October 14, 1980, to Cambre.
When cationic surfactants are used in combination with anionic surfactants and certain deter3ency builders including polycarboxylates, compatibility must be considered. A type of cationic surfactant generally compatible with anionic surfactants and polycarboxylates is a C8 18 alkyl tri Cl 3 alkyl ammonium chloride or methyl sulfate.
More complete disclosures of surfactants suitable fur incor-poration in deteryent and laundry additive compositions of the present invention are in U.S. Patents 4,056,481, Tate (November 1, 1977); 4,049,586, Collier ~September 20, 1977); 4,040,988, Vincent et al (August 9, 1977); 4,035,257, Cherney (July 12, 1977);

4,033,718, Holcolm et al ~July 5, 1977); 4,019,999, Ohren et al (Apr~l 26, 1977); 4,019,998, Vincent et al ~April 26, 1977); and 3,985,669, Krummel et al (October 12, 1976).

Optional Deter~ency Builders The detergent and laundry additive compositions of the present invention can contain detergency builders in addition to the ether carboxylate compounds or mixtures described hereinbefore as essen~ial components.
Suitable additional polycarboxylate detergency builders include the ac~d form and alkali metal, ammonlum and substituted ammonium salts of citric, ascorbic, phytic, mellitic, benzene pentacarboxylic, oxydiacetic, carboxymethyloxysuccinic, carboxy-methyloxymalonic, cis-cyclohexanehexacarboxylic, cis-cyclopentane-tetracarboxylic and oxydisuccinic acids. Also suitable are poly-carboxylate polymers and copolymers described ln U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Particularly suitable are acrylic acid polymers and salts thereof and copolymers of acrylic and maleic acids and salts thereof which act as dispersants of particulate materials in wash solutions.
X

I

The polyacetal carboxylates disclosed in U.S. Patent 4,144,226 issued March 13, 1979, to Crutchfield et al and U.S.
Patent 4,146,495 issued March 27, 1979 to Crutchfield et al can be incorporated in the detergent and laundry additive compositions of the invention.
Also suitable in the detergent and laundry additive composi-tions of the invention are the 3,3-dicarboxy-4-oxa-1~6-hexane-dioates and th~ r~lated ~ompnunds disclosed in Canadian -Patent No. 1,260,009.

Suitable ether polycarboxylates also include cyclic com-pounds, particularly alicyclic compounds, such as described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Polyphosphonate detergency builders comprise a large range of organic compounds having two or more - C - PQ3M2 groups, wherein M ls hydrogen or a salt-forming radical. Suitable phos-phonates include ethane-l-hydroxy-1,1-diphosphonates, ethane-; hydroxy-1,1,2-triphosphonates and their oligomeric ester chain condensates. Suitable polyphosphonates for use in the composi-tions of the invention also include nitrogen-containing poly-phosphonates such as ethylenediaminetetrakis (methylenephosphonic) acid and diethylenetriaminepentakis (methylenephosphonic) acid and alkali metal, ammonium and substi~uted ammonium salts thereof. In ; 25 co~non with other phosphorus-containing components, the incorpo-ration of phosphonatçs may be restricted or proh~bited by govern-ment regulat1On.
As discussed hereinbefore C~ 2~ alkyl monocarboxylic acid and soluble salts thereof have a detergent builder function in addi-tion to surfactant characteristics. C8-C24 alkyl, alkenyl, alkoxy and thio-substituted alkyl d1carboxylic ac1d compounds, such as 4-pentadecene -1,2-dicarboxylic acid, salts thereof and mixtures thereof, are also useful optional detergency bu~ders.
Inorganic detergency builders useful in the detergent and 7aundry addi~ive compositions of this invention at total combined levels of from 0% to about 75% by weight, include alkali metal 3~

; -22-phosphates, sodium aluminosilicates, alkali metal silicates and alkali metal carbonates.
Phosphate detergency builders include alkali metal ortho-phosphates which remove multivalent metal cations from laundry solutions by precipitation and the polyphosphates such as pyro-phosphates, tripolyphosphates and water-soluble metaphosphates that sequester multivalent metal cations in the form of soluble complex salts or insoluble precipitating complexes. Sodium pyrophosphate and sodium tripolyphosphate are particularly suit-able in granular detergent and laundry additive compositions to the extent that governmental regulations do not restrict or prohibit the use of phosphorus-containing compounds in such compositions. Granular detergent and laundry additive composttion embodiments of the invention partlcularly adapted for use in areas where the incorporatinn of phosphorus-containing compounds is restricted contains low total phosphorus and, preferabty, essen-tially no phosphorus.
Other optional builder material include aluminosilicate ion exchange materials, e.g. zeolites. Crystalline aluminosilicate 2~ ion exchange materials useful in the practice of this invention have the formula Nazt(Alo2)ztsio2)y]H2o wherein z and y are at least about 6, the molar ratio of z to y is from about I.O to about 0.5 and x is from about IO to about 264. In a preferred embodi~ent the aluminosilicate ion exchange material has the a NaI2[(A102)I2(SiO2)I2]XH20 wherein x is from about 20 to about 30, especially about 27.
Amorphous hydrated aluminosilicate material useful herein has ; the empirical fsrmula: Naz(zAl02.ySiO2), ~ is from about 0.5 to about 2, y is I and said material has a magnesium ion exchange capacity of at leas~ about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate.
The aluminosilicate ion exchange builder materials herein are in hydrated form and çontain from about 10% to about 28X of water by weight if crystalline and potentially eYen higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water ~2 '~3~1~
-in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about O.Ol micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns. The term "particle size diameter" herein represents the average particle size diameter o~ a given ion exchange material as determined by conventional analytical techniques such as, for example, micro-lo scopic determination utilizing a scanning electron microscope.
The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaC03 water hardness/gm. of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg.eq./g. to about 352 mg. eq./g. The aluminosilicate ion ex-change materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca~/
gallon/ minute/gram of aluminosilicate (anhydrous basis)5 and generally lies within the range of from about 2 grains/gallon/
minute/gram to about 6 grains/gallon/minute/gram, based on calcium ion hardness. Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram.
The amorphous aluminosilicate ion exchange materials usually have a Mg~+ exchange capacity of at least about 50 mg. eq.
CaC03/g(12 mg. Mg++/g.) and a Mg~+ exchange rate of at least about ; 1 gr./gal./min./g./gal. Amorphous materials do not exhibit an observable diffraction pa~tern when examined by Cu radiation (1.54 Angstrom Units).
Aluminosilicate ion exchange materials useful as optional builders in the de~ergent and laundry additive composi~ions of ~his invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in struc-ture and can be naturally-occurring aluminosilicates or synthe-tically derived. A method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. ~o. 3,985,669, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designation Zeolite A, Zeolite B, and Zeolite X.
Other optional builders include alkali metal silicates.
Suitable alkali metal sitfcates have a mole ratio of SiO2: a1kali metal oxide in the range of from about 1:1 to about 4:1. The alkali metal silicate suitable herein include commercial prepa-rations of the combination of silicon dioxide and alkali metal oxide or carbonate fused together in varying proportions according to, for example, the following reaction:
mSiO2 + Na2C03~mS102:Na20 ~ CO2 The value of m, designating the molar ratio of SiO2:Na20, ranges from about 0.5 to about 4 depending on the proposed use of the sodium silicate. The term "alkali metal silicate" as used herein refers to silicate solids with any ratio of SiO2 to alkali metal oxide. Silicate solids normally possess a high alkalinity content; in additlon water of hydration is frequently present as, for example, in metasilicates which can exist having 5, 6, or 9 molecules of water. Sodium silicate solids with a SiO2:Na20 mole ratio of from about 1.5 to about 3.5, are preferred in granular laundry detergent compositions.
Silicate solids are frequently added to granular detergent or laundry additive compositions as corrosion inhibitors to provide protectlon to the metal parts of the washing machine in which the detergent or laundry additive composition is utili2ed. Silicates have also been used to provide a degree of crispness and pour-ability to detergent or laundry additive granules which is very 3~ desirable to avoid lumping and caking.
Alkali ~etal carbonates are use~ul in the granular detergent or laundry additive composftions of the invention as a source of washing solution alkalinity and because of the ab~lity of the carbonate ion to remove calcium and magnesium ions from washing solutions by precipitation.

~"~

~3~1~

Preferred granular compositions free of inorganic phosphates contain from about 8% to about 40% by weight sodium carbonate, from 0% to about 30% sodium aluminosilicate, from about 0.~% to about 10% sodium silicate solids, from about 5% to about 35% of the novel ether carboxylate compounds of this invention and ~rom about 10% to about 25% surfactant.
Preferred liquid compositions free of inorganic phosphates contain from about 8g to about 30% by weight of non-soap anionic surfactants, from about 2X to about 25X ethoxylated nonionic lo surfactants, from about 5% to about 20% of a C8 24 alkyl or alkenyl mono-or dicarboxylic acid or salt thereof and from about 2% to about 18% of the novel ether carboxylate compounds of the present invention. Some liquid formulations may also contain from about 0.5 to about 5% of a cationic or amine oxide surfactant.
Additional Optional Components 6ranular detergent or laundry additive compositions of this invention ean contain materials such as sulfates, borates, per-borates organic peroxy acid salts, peroxy bleach precursors and activators and water of hydration.
Liquid detergent or laundry additive compositions of this invention can contain water and other solvents. Low molecular weight primary or secondary alcohol exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing the surfactant but polyols containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups can be used and can provide improved enzyme stabil-ity. Examples of polyols include propylene glycol, ethylene glycol, glycerine and 1,2-propanediol. Ethanol is a particularly preferred alcohol.
The detergent or laundry additive compositions of the in-vention can also contain such materials as pro~eolytic and amyl-olytic enzymes, fabric whiteners and optical brighteners, sudsing control agents, hydrotropes such as sodium toluene, xylene or cumene sulfonate, perfumes, oolorants, opaci~iers, anti-rede-position agents and alkalinity control or buffering agents such as monoethanolamine and triethanolamine. The use of these materials is known in the detergent art.
Materlals that provide clay soil removal/anti-redeposition benefits can als~ be incorporated in the detergent and laundry additive compositions of the inYen~ion and are particularly useful in liquid compositions of the inventlon. These clay soil re-moval/anti-redeposition agents are usually included at levels of from about 0.1~ to about 10% by weight of the composition.
Cne group of preferred cla~ soil removal/anti~redeposition agents are the ethoxylated amines disclosed in European Patent Application 112,593 of James M. Vander Meer, published July 4, 1984. ~nother group of preferred clay soil removal/anti-redeposition agents are the cationic compounds disclosed in European Patent ~pplication 111,965 to ~oung S. Oh and Eugene P. Gosselink, published June 27, 1984. Other clay soil removal/anti-redeposition agents which can be used include the etho~ylated amine polymers disclosed in European Patent Application 111,984 to Eugene P. Gosselink, published June 27, 1984; the zwitterionic compounds disclosed in ~uropean Patent Application 111,976 to Donn N. Rubingh and Eugene P. Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592 to Eugene P. Gosselink, published July 4, 1984; and the amine oxides disclosed in Canadian Patent No. 1,211,113 to Daniel S. Connor.
Polyethylene glycol can also be incorporated to provide anti-redeposition and other benefits.
Soil release agents, such as disclosed in the art to reduce oily staining of polyester fabrics, are also useful in the detergent and laundry additive compositions of the present invention. U.S. Patent 3,962,152 issued June 8, 1976, to Nicol et al., discloses copolymers of ethylene terephthalate and polyethylene oxide terephthalate as soil release agents. U.S.
Patent 4,174,305 issued November 13, 1979, to Burns et al., discloses cellulose ether soil release agents. Canadian Applicatlon Serial No. 528,401 3~1~
( -27-`` by Gosselink, discloses block polyester oompounds us~ful as soil release agents in detergent and laundry additive compositions.
Especially preferred detergent compositions herein contain, in addition to a surfactant and the ether carboxylate mixture of this invention, a particular type of dispersant component. Such a dispersant component can contain the ethoxylated amine clay soil re val/anti-redeposition agents of the hereinbefore referenced European Patent ~pplication No.
EPA-112593 and/or acrylic acid polymers or acrylic/maleic acid copoly~ers. Such especially preferred detergent compositions are more completely described in the concurrently Eiled, oopending Canadian Patent Application of Collin~, Mackey and ~Spadini having Serial No. 528,401.
The detergent and laundry additive compositions herein may also optionally contain one or more iron and magnesium chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunc-tionally - substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. Without relying on theory, it is speculated that the benefit o~ these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents in compositions of the invention have one or more, preferably at least two, units, of the substructure ' --C ~ CH2 _ N - (CH2~X COOM, wherein M ~s hydrogen, alkali metal, ammonium or substituted ammon~um (e.g. ethanolamine) and x is ~rom 1 to about 3, prefer-~; ably 1. Preferably, these amino carboxylates do not contain alkyl or alkenyl groups w~th ~ore than about ~ carbon atoms. Alkylene groups can be shared by substructures. Operable amine carboxyl-ates include ethylenedi~minetetraacetates, N-hydroxyethylethyl-enediaminetriacetates, nitrilotriacetates, ethylenediamine tetra-, 3~19 f -28-propionates, diethylen~triaminepentaacetates~ and ethano~di-glycines.
Am~no phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent composi-tions. Compounds with one or more, preferably at least two, units of the substructure , N - (CHz)x - P03M 2~
wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x ~s from 1 to about 3, preferably 1, are useful and include ethylened~am~netetrak1s ~methylenephosphonates), n1tr~1O-tris (methylenephosphonates) and diethylenetriam~nepentakis (methylenephosphonates). Preferably, these am~no phosphonates do not conta~n alkyl or alkenyl groups with more than about 6 carbon atoms. Alkylene groups can be shared by substructures.
Polyfunctionally - substltuted aromatic chelating agents are also useful in ~he compositions herein. These materials comprise compounds hav~ng the general formula OH
R ~ OH

R ~ R

wherein at least one R is -SO3H or -COOH or soluble salts thereof and mixtures thereof. U.S. Patent 3,812,044 issued May 21, 1974, to Connor et al, discloses polyfunctionally substituted arom~tic chelating and sequestering agents.
Preferred compounds of this type in acid form are dihydroxydisulfobenzenes and 1,2-dihydroxy 3,5-disulfobenzene or other disulfonated catechols in particular. Alkaline ; detergent compositions can contain these materials in the form of alkali metal, = onium or substituted ammonium (e.g. mono-or triethanolamine) salts.
If utilized, optional chelating agents will generally comprise fron about 0.1% to 10~ by weight of the detergent or laundry ~1 ., i ., ' :

3~

additive co~positions herein. More preferably chelating agents will comprise from about 0.75% to 3~b by weight of such composi-tions.
The detergent and laundry additive compositions of this invention can also include a bleach system comprising an inorganic or organic peroxy bleaching agent and, in preferred compositions, an organic peroxy acid bleach precursor. Suitable inorganic peroxygen bleaches include sodium perborate mono- and tetrahy-drate9 sodium percarbonate, sodium persilicate and urea-hydrogen peroxide addition products and the clathrate 4Na2504:2H202:1NaCl.
Suitable organic bleaches include peroxylauric acid, peroxy-octanoic acid, peroxynonanoic acid, peroxydecanoic acid, diper-oxydodecanedioic acid, diperoxyazelaic acid, mono- and diper-oxyphthalic acid and mono- and diperoxyisophthalic acid. The bleachiny agent is generally present in the detergent and laundry additive compositions of this invention at a level of from about 5% to about 50X preferably from about 10% to about 25X by weight.
The detergent and laundry additive compositions of ~he invention may also contain an organic peroxy acid bleach precursor at a level of from about 0.5% to about 10%, preferably from about lX to about 6% by weight. Suitable bleach precursors are dis-closed in UK-A-2040983, and include for example, the peracetic acid bleach precursors such as tetraacetylethylenediamine, tetra-acetylmethylenediamine, tetraacetylhexylenediamine, sodium p-ace-toxybenzene sulfonate, tetraacetylglycouril, pentaacetlyglucose, octaacetyllactose, and methyl o-acetoxy benzoate. Highly pre-fcrred bleach precursors, however, have the general formula o R-C-L
wherein R is an alkyl group containing from 6 to 12 carbon atoms wherein the longest linear alkyl chain extending frDm and in-cluding the carboxyl carbon contains from 5 to 10 earbon atoms and L is a leaving group, the conjugate acid of which has a logarith-mic acidity constant in the range from 6 to 13.
The alkyl group, R, can be either linear or branched and, in preferred embodiments, it contains from 7 to 9 carbon atoms.
:

3~19 3~
( Preferred leavlng groups L have a loyarithmic acidity constant in the range from about 7 to about 119 more preferably from about 8 to about lO. Examples of leaving groups are those having the formula - a) 0 ~ (CH2)x~

\Z
lo and O
b) -N-C-R
yH2 where~n Z is H, R1 or halogen, ~1 jS an alkyl group having from 1 to 4 carbon atoms7 X is 0 or an integer of from 1 to 4 and Y is selected from S03M, 0503M, C02M, N+(Rl)30 and N+(R1~2-0- wherein M is H, alkali metal, alkaline earth metal, ammonium or substitut-ed ammonium, and 0 is halide or methosulfate.
~0The preferred leav~ng group L has the formula ~a) in which Z
:~ is H, x ~s 0 and Y is sulfonate, carboxylate or dimethylamine oxide radical. Highly preferred materials are sodium 3,5,5,-trimethylhexanoyloxybenzene sulfonate, sodium 3,5,5-trimethyl-hexanoyloxybenzoate, sodium 2-ethylhexanoyl oxybenzenesulfonate, sodium nonanoyl oxybenzene sulfonate and sodium octanoyl oxy-benzenesulfonate, the acyloxy group in each instance preferably belng p~substituted.
The bleach precursor (act~vator) here~n will normally be added in the form of particles compris1ng finely-divided bleach act~vator and a binder. The binder ~s generally selected:from nonionic surfactants such as the ethoxylated tallow alcohols, polyethylene glycols, anionic surfactants, film forming polymers, fatty acids and mixtures thereof. Highly preferred are nonionic surfactant binders, the bleach activator being admixed with the binder and extruded in the form of elongated particles through a radial extruder as described in Canad-}an Patent No. 1,170,947!
. .

~ 3 ~ 1~3 62523. Alternatively, the bleach activator particles can be prepared by spray drying.
In addition to their utility as builders in detergent and laundry additive compositions, the ether carboxylates of the present inYention may also be utilized in other contexts wherein water hardness se4uestration is required. lhus, for example, the ether carboxylate compositions herein may be employed in water softening compositions, devices and methods. These materials are also use~ul in boiler descaling compositions and methods.
The following embodiments illustrate, but are not limiting of, the builder compounds and compositions of the present in-vention. All percentages herein are by weight unless indicated otherwise.
EXAMPLE I
lS In this example, a mixture of tartrate monosuccinate (TMS) and tartrate disuccinate (TDS) is prepared by a procedure which involves the reaction of maleate salts and tartrate salts. In such a procedure, maleic anhydride (22059, 22.5 moles) is heated in 20009 o~ distilled water until dissolved. The resultant solution of maleic acid is cooled ~o 85 ~ 5C and 2250g L~
tartaric acid (15.0 moles) is added with stirrin~ at 85+ 5C until a homogeneous clear acid solution is obtained.
Separately, 11119 of calcium hydroxide (15.0 moles) is slowly added to a mixture of 44409 of 50% sodium hydroxide solution (55.5 moles) and lOOOg distilled water while stirring at a moderate rate such that only a small fraction of unwetted calcium hydroxide is upon the surface of the solution at a time. Stirring is continued until an essentially uniform base mixture is obtained.
; The base mixture is then added at a uniform rate oYer 0.5 hour to the moderately stirred acid solution which is at 70-85C.
The resulting reaction mixture is cooled with warm (ca. 60~) water in order to maintain a reac~ion temperature of 90 ~ 5C most of the time. The reaction mixture may, however, boil briefly from time to time. The object ~s to prevent major losses of water vapor and also to limit the amount of insoluble salt which crys-tallizes upon the cool reaction vessel walls. As the last 10% of 3LZ93~-19 base is added, the reaction temperature is held at 85C. The reaction mixture is quickly weighed and brought to 13,0239, i.e., 50% active, with 2009 of distilled water. (Active is defined here as total weight of organics taken as their sodium salts i.e., sodium maleate and sodium tartrate or 160 x 22.5 moles + 194 x 15.0 moles = 65109.) The reaction ~ixture is immediately heated with steam, stirred moderately in a covered reactor, and a 0.409 sample taken with time arbitrarily set at zero. The reaction mixture which is lo a white suspension, is brought to 98-100C within lO minutes.
Within 15 to 20 min~tes of time zero, the reaction mixture clears.
Samples (0.40 ~ 0.049) of the reaction solution are taken every half hour to be dissolved in 100 ml 0.1N sulfuric acid solution and immediately submitted for high pressure liquid chromatography (HPLC) analysis in order to monitor the course of the reaction.
The results of HPLC analysis of the 1.5 hour sample indicate that the reaction is to be quenched at the 2.0 hour point.
Quenching consists of cooling the reaction product mixture to 50C
within 10 minutes. The homogeneous, almost colorless quenched reaction product solution is reweighed and is made up again to 13,0209 with 3279 of distilled water to give a reaction product solution containing 50% active.
HPLC analysis indicates that the composition of the organic portion of the reaction product solution is 11.1% tartrate, 1.7%
malate, 12.6% maleate, 10.9% fumarate, 35.0% peak 2A, 19.6% peak 2B, 3.3~ peak 3A, and 5.9~ peak 3B. Peaks 2A and 2B are isomers of sodium tartrate monosuccinate (TMS) and peaks 3A and 3B are isomers of sodium tartrate disuccinate (TDS). Therefore, the HPLC
estimated yield of TMS + TDS based upon all peak areas is 63.7%.
The approximate weight ratio of TMS:TDS is 86:14. All yields are based upon HPLC refractiYe index raw data, i.e., are not corrected to mole ~. Calculated yield of this reaction based on tartrate is ~,1399.
A second reac~ion product batch of the same size is made using similar procedures. HPLC analysis indicates that the composition of this second reaction product solution is 9.8%
tartrate, 1.7% malate, 12.4% maleate, lO.lX fumarate, 35.0% peak ;~t~3~1~

2A, 18.1% peak 2B, 5.1% peak 3A, and 7.9% peak 3B Again peaks 2A
and 2B are isomers of sodium tartrate monosuccinate (TMS) and peaks 3A and 3B are isomers of sodium tartrate disuccinate (TDS).
Therefore, the HPLC-estimated yield of TMS + TDS based upon all peak areas is 66.1X. The approximate weight ratio of TMS:TDS is 8~:20. Yield is 44009 based on calculationsO
; Both reaction product batches are combined to give 26,0409 of solution which is calculated to contain 85399 o~ TMS/TDS and 30 moles of calcium ion. This solution is then diluted with 26,0409 of water. While this solution is at 26C and stirred vigorously, a 28~ solution of 7500g (30 mole) of ethanehydroxydiphosphonate disodium salt dissolved in 18,7509 o~ water is added followed by 31789 of 50% sodium hydroxide solution to give a pH of 10.5.
Stirring is continued for 18 hours; the final pH is eleven. The resulting precipitate (EHDP-calcium complex) is then removed by filtration using suction filtration equipment with a paper filter, and the filtrate is washed with 4 liters of water. The resulting superna~ant, 56 liters, is filtered again through a glass frit to remove any remaining fine particles. This clear solution is then evaporated in a steam heated vat with a compressed air stream blown above the surface to give a solution of 3~,5509.
This solution is then poured into 80 liters of vigorously stirred methanol. This is done to help separate the less soluble TMS and TDS from the more solub~e maleic and fumaric acid salts.
The stirring is continued for 15 minutes followed by a 1/2 hour settling period. Then the liquid is decanted from the gum~y solid by siphon. This solid is dissol~ed in 13,5~09 of distilled water to give 26~6859 of solution which is then poured int~ 68 liters of methanol, essentially repeating the above. The resulting solid is dissolved in 6 liters of distilled water (pH = 8.4), and the vat is heated with steam. Methanol is removed with a stream of nitrogen directed on the surface of the solution which is well stirred. This is con~inued unti1 'H-NMR analysis indkates tha~
the methanol is removed. The resulting solu~ion is 16,3809. To reduce viscosity, 2 liters of water are added, and the mixture is filtered to give 18,8879 of solution. This solution is analyzed 1;~53~

:

and found to have the following composition by high pressure liquid chromatography using a refractive inclex detector: 43.6~
TMS/TDS (8~2359 or 96.4~ recovery by workup), 2.1~ tartrate, 0.5%
malate, 0.9% maleate, and 1.1% fumarate. The TMS/TDS ratio is 78.2:21.8. The calcium ion leve1 of the solution is 0.048 weight X as determined by atomic absorption.
EXAMPLE II
A TMS/TDS reaction product mixture is prepared using proce-dures similar to those set forth in Example I except that the reactants used to form the reaction mixture are maleic anhydride, tartaric acid, sodium hydroxide and calcium hydroxide in a 1.3:1.0:3.93:0.5 molar ratio. The resulting reaction product mixture is determ~ned by high pressure liquid chromatography to contain 17.2% tartrate, 1.5% malate, 9.9% maleate, 10.3% fumarate, TMS (2A 36.2%, 2B 13.4X) and TDS (3A 503%, 3B 6.1%). The rest of the sample is a mixture of water and calcium salts.
Calcium is then removed from this mixture by a precipitation procedure using a combination of carbonate salts. In such a procedure 26.5 grams of sodium carbonate and 21.0 grams o~ sodium bicarbonate (0.25 mole of each salt) are dissolved in 204 grams of water. This solution is then added to 250 grams of the above-described reac~ion product mixture which contains 0.125 moles of calcium. The resulting mixture is placed in a 1 liter flask equipped with a thermometer and stirrer. Thls mixture is then heated to 70C and stirred for 3 hours. After cooling to 25C
while stirring is continued, this mixture is filtered through a sintered glass filter. The resulting filter cake is washed with 20m1 of water ~wice. The filtrate is adjusted to a wei~ht of 1000 grams with the addition of water and then is analyzed. The filtrate is found to contain tartrate - 1.48%i malate - 0.14~;
maleate - 1.02%; fumarate - 0.83%; TMS - (2A 3.3%, 2B 1.3%); TDS -(3A 0.5%, 3B 0.5%); and calcium - 0.009%. The maleate ~nd fumarate salts are then removed using a methanol precipitation procedure as in Example I.

~3~ 9 EXAMPLE III
Another TMS/TDS reaction product mixture is prepared by reacting tartaric acid and maleic anhydride. In this preparation 1509 (1 mole) of L-tartaric acid are placed in 86.59. of water, and this mixture is heated to give a solution. Then while this solution is cooled and stirred vigorously, a slurry of 2249. (2.8 moles) of sodium hydroxide (50% solution in water) and 74.09. (1.0 mole) of calcium hydroxide are added. The resulting milky mixture is stirred and cooled to maintain a temperature of about 75C
while 98.09. (1.0 mole) of maleic anhydride are added. This results in a slightly yellow solution.
This reaction mixture is then stirred and maintained at 75C
for 20.5 hours. During the reaction very small samples are removed and analyzed by HPLC. The following distributions of reaction products are determined in the samples tested:
Reaction Time Product Compounds 6.5 ~_20.~ hours Tartaric acid 12.7% 8.2%
Malic acid --- 0.7 Maleic acid 10.1 3.4 Fumaric acid 1.2 3.6 TMS (2A) 37.6 40.3 TMS (2B) 11.1 12.1 TDS (3A) 16.5 18.5 TDS (3B) 10.8 13.2 Total builder 7~% ~4.1%
Using the procedures described in Example II, calcium is removed from this reaction product to a level such that the ratio of moles of calcium to the total mole of TMS + TDS is less than 1:10.
EXAMPLE IV
Various ~ixtures of sodium tartrate monosuccinate (TMS) and sodium tartrate disuccinate (TDS) are prepared in accordance with the procedure of Example I. In this procedure~ various ~olar ratios of maleate and tartrate reactants are employed to give ether carboxylate reaction products having a variety of TMStTDS
ratios. Reactant ratios, product compositions and percent conver^
sion of reactants to TMS/TDS product are set forth in Table I.
;

3~.19 ABLE I
Maleate/Tartrate TMS in TDS in Conversion of R~tio of Product Produot Reactants to Equivalents (Wt X) ~Wt %) Product (%) 8.0 21 79 33 4.0 46 54 48 2.5 44 56 65 2.0 50 50 71 1.5 58 42 79 1.25 82 18 71 1.0 82 18 70 0.83 82 18 69 0.67 89 11 58 0. 50 97 3 34 The Table I data illustrate that product mixtures containing various TMS/TDS ratios can be prepared by ad~usting the relative amounts of ~aleate and tartrate starting materials. The Table I
data further illustrate that maximum conversion of reactants to desired products is achieved for the reactions wherein the male-ate/~artrate ratio varies between about 2.5:1 and 0.80:1.
EXAMPLE V
In this example, ca kium sequesterin~ performance of various builder materials, ~ncluding a TMS/TDS-containing mixture of the present inYen~ion, is measured using a Divalent Electrode titra-t~on procedure. Such a procedure is described in general in Mbtzner et al; "Organic Builder Salts (I)," Tenside Detergents, Vol. 10, 1973 Heft 3 at pages 123-124, incorporated herein by reference.
In accordance with such procedures, a 1.2 X 10 3M calcium chloride solution ~25 ml; 0.1M buffer; 35C; pH-9.55) is titrated on an automatic titrator using a 1% solution of the sodium salt of various sequestering builder materials. Uncomp1exed calcium ion concentration is detected by the change in millivolt potential of a ca kium selective eleotrode as a function of millimoles of builder added.

1~3~1~

Builder materials tested include a TMS/TDS mixture in a 78:22 weight ratioJ sodium oxydisuccinate (ODS), sodium carboxymethyl-oxysuccinate (CMOS), sodium oxydiacetate (Ol)A) and sodium tri-polyphosphate (STP). Test results are depicted graphically in the Figure wherein the molar amount of builder added is plotted along the X-axis and the change in potential at the calcium selective electrode provided by titrating the various builder solutions is plotted along the Y-axis. The proximity of any given resulting curve to the Y-axis indicates the effectiveness with which the lo builder acts to sequester free calcium ion. The proximity o~ any such curve to the X-axis indicates an enhanced ability of the builder to keep calcium ion concentration to low levets in the solution.
The curves set ~orth in the Figure indicate that the TMS/TDS
mixtures of the present invention provide superior calcium sequestration performance in comparison with other ether carboxyl-ates such as oxydisuccinate, oxydiacetate and carboxymethyloxy-succinate and even in comparison with the phosphate builder, sodium tripolyphosphate.
EXAMPLE VI
A granular detergent composition for hsusehold 7aundry use is as follows:
Component Wt. %
Sodium C14 C15 alkylsulfate 13.3 Sodium Cl3 llnear alkyl benzene sulfonate 5.7 C12-C13 alkylpolyethoxyla~e (6.5) 1.0 Sodium toluene sulfonate 1.0 TMS/TDS, sodium salt, 86/14 weight ratio of 25.0 TMS:TDS of the Example I type Sodium N-hydroxyethylethylenediaminetriacetate 200 Sodium polyacrylate (Avg. M.W. approx. 5000) 2.0 Sodium carbonate 20.3 Sodium silicate 5.8 Polyethylene glycol (Avg. M.W. approx. 8000) l.O
Sodium sulfate, water and miscellaneous Balance ~o 100%

v--~

3~i~

The components are added together with continuous mixing with sufficient extra water (about 40% total) to form an aqueous slurry which is then spray dried to form the composition.
In the composition of Exa~ple I the following substitution can be made:
a) ~or TMS/TDS:
~` 1) an equivalent amount of ~MS alone, and 2) an equivalent amount of TDS alone.
EXAMPLE YII
A liquid detergent composition for household laundry use is as follows:
Component Wt. X
Potassium C14-C15 alkyl polyethoxy (2.5) sulfate ~-3 C12-C14 alkyl d1methyl amine oxide 3.3 Po~assium toluene sulfonate S,0 Monoethanolamine 2.3 TMS/TDS triethanolamine salt, 85/15 TMS/TDS 15.0 Potassium salt of 1,2-dihydroxy-3,5-disulfo~enzene 1.5 Potassium polyacrylate ~avg. M.W. approx. 9000) 1.5 Water and miscellaneous Balance to 100%
The components are added together with continuous mixing to form the composition.
EXAMPLE VIII
A liquid detergent composition for household laundry use is prepared by mix~ng the following ingredients:
C13 alkylbenzenesulfonic acid 10.5%
Triethanolamine cocoalkyl sulfate 4.0 C14_15 alcohol ethoxy-7 12.0 C12 18 alkyl monocarboxylic acids 15.0 TMS/TDS, triethanolamine salt 85/15 TMS/TDS 5.0 Diethylenetriaminepentakis (methylenephosphonic) acid 0.8 Polyacrylic acid ~avg. M.W. approx. 5000) 0.8 Triethanolamine 4.5 Ethanol 8.6 1,2-Propanediol 3.0 Water, perfume, buffers and miscellaneousBalance to 100 1~3~
-3g-EXAMPLE IX
In the Compositions which follow, the abbreviations used have the following designations:
C12LAS : Sodium linear C12 benzene sulfonate TAS : Sodium tallow alcohol sulfonate TAEn : Hardened tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol Dobanol 45E7 : A C14 l5 pri~ary alcohol condensed with 7 lo moles of ethylene oxide TAED : Tetraacetyl ethylene diamine NOBS : Sodium nonanoyl oxybenzenesulfonate INOBS : Sodium 3,5,5 trimethyl hexanoyl oxy-benzene sulfonate Silicate : Sodium silicate having an SiO2:Na20 rat;o ~f 1:6 Sulfate : Anhydrous sodium sulfate Carbonate : Anhydrous sodium carbonate CMC : Sodium carboxymethyl cellulose Silicone : Co~prising 0.14 parts by weight of an 85:15 by weight mixture o~ silanated silica and silicone, granulated with 1.3 parts of sodium tripolyphosphate, and 0.56 parts of tallow alcohol condensed with 25 molar proportions of ethylene oxide POl : Copolymer of 3:7 maleic/acrylic acid, average molecular weight about 70,000, as sodium salt PC2 : Polyacrylic acid, average molecular weight about 4,500, as sodium salt TMS/TDS : Mixture of tartrate monosuccinate and : tartrate disuccinate in an TMS to TDS
: weight ratio of 85/15 sodium salt form Perborate : Sodium perborate tetrahydra~e o~ nominal formula NaB~2.3H20.H202 ~ 3 ~ 3 - Enzyme : Protease EDTA : Sodium ethylene diam~ne tetra acetate Brightener : Disodium 4,4'-bis(2-mDrpholino-4-anilino-s-triazin-6-ylamino) stilbene-2:2'di-sulfonate DETPMP : Diethylene triamine penta(methylene phosphonic acid), marketed by Monsanto under the Trade ~ark Oequest 2060 EDTMP : Ethylenediamine tetra (methylene phos-phonic acid), marketed by Monsànto, under the Trade mark Dequest 2041 Granular detergent compos~tions are prepared as follows. A
base powder compos~t~on ~s first prepared by mixlng all components except, where present, Dobanol~45E7, bleach, bleach activator, enzyme, suds suppresser, phosphate and carbonate in crutcher as an aqueous slurry at a temperature of about 55C and conta~nlng about 35X water. The slurry is then spray dried at a gas inlet tempera-ture of about 330~C to form base powder granules. The bleach activator, where present, is then admixed with TAE25 as b~nder and extruded in the form of elonqated particles. thrpug~ a radica1 extruder as described in ~anadian Patent No. 1,170,~947.
The bleach act~vator noodles, bleach, enzyme, suds suppressor, phosphate and carbonate are then dry-mlxed with the base powder composition and f1nally Dobanol.45E7 is sprayed into the final mixture.

j .

COMPOSITIONS
A B C D

TAE25 0.5 0-5 0.8 TAE~
Dobanol 45E7 4 - 4 2 TAED 0.5 - 3 Perborate 19 20 10 24 EDTMP 0.3 - 0.4 0.1 DETPMP - 0.4 EDTA 0.2 0.2 0.2 0.1 Magnesium (ppm) 1000 1000 7so P~2 :~ Zeolite A* - 15 14 Sodium tripolyphosphate - - - 12 Coconut Soap - - - 2 Carbonate 17 15 10 Silicate 3 2 2 7 Silicone 0.2 0.2 0.3 0.2 Enzyme 0.8 0.5 0.4 0.3 Brightener 0.2 0.2 0.2 0.2 : Sulfate, Moisture Miscellaneous - - - - - - to 100 - -*Zeolite A of 4 A pcre size.
The above compositions are zero and low phosphate detergent compositions displaying excellent bleach stability~ fabric care and detergency performance across the range of wash temperatures with particularly outstanding performance ln the c~se of Composi-35 tions A, B and C on greasy and particulate soils at low washtemperatures.

12~3~

EXAMPLE X
A liquid detergent composition suitable for use in cleanin~, : hard surfaces is prepared having the following composition:
Component Wt. %
C13 alkylbenzene sulfonic acid 5%
TMS/TDS, scdium salt 80:20 TMS/TDS 9%
Sodium Carbonate 2%
Isopropyl Alcohol 3~
Pine Oil 6%
lO Water, Fragrance, Miscellaneous Balance to 100%

Claims (20)

1. An ether carboxylate composition suitable for use as a builder in detergent formulations, said composition comprising (a) from about 1% to 99% by weight of a tartrate mono-succinate component of the structure wherein X is H or a salt-forming cation; and (b) from about 1% to 99% by weight of a tartrate disuccinate component of the structure:
wherein X is H or a salt-forming cation.

2. A composition according to Claim 1 wherein the weight ratio of tartrate monosuccinate component to tartrate disuccinate component ranges from about 97:3 to 20:80.

3. A composition according to Claim 2 wherein the tartrate monosuccinate and the tartrate disuccinate components are in the form of their fully neutralized sodium, potassium, monoethanol-amine or triethanolamine salts.

4. A composition according to Claim 3 wherein the tartrate monosuccinate component comprises from about 10% to 98% by weight of the composition; wherein the tartrate disuccinate component comprises from about 2% to 90% by weight of the composition; and wherein the weight ratio of tartrate monosuccinate to tartrate disuccinate ranges from about 95:5 to 40:60.

5. A composition according to Claim 3 wherein the compo-sition contains up to about 70% by weight of an additional compo-nent selected from the group consisting of water, malate salts, maleate salts, tartrate salts, fumarate salts, calcium salts, and combinations of said optional components.

6. A composition according to Claim 5 wherein the compo-sition contains no more than about 10 mole percent of calcium based upon total moles of the tartrate monosuccinate and tartrate disuccinate present in said composition.

7. A composition according to Claim 6 wherein the weight ratio of tartrate monosuccinate to tartrate disuccinate ranges from about 95:5 to 40:60.

8. A tartrate monosuccinic acid, or a salt thereof, of the structure:
wherein X is H or a salt-forming cation.

9. Tartrate disuccinic acid, or a salt thereof, of the structure:
wherein X is H or a salt-forming cation.

10. A process for preparing a combination of ether car-boxylates useful as a detergent builder, which method comprises (a) forming an aqueous reaction mixture comprising from about 20% to 60% by weight of both calcium and mono-valent cation salts of maleic acid and tartaric acid, said mixture corresponding to the over-neutralized mixture which is formed by combining:
(i) maleic and tartaric acids in a maleic to tartaric molar ratio of from about 0.5:1 to about 8:1;
(ii) a source of calcium cations in an amount such that the molar ratio of calcium to tartaric acid ranges from about 0.1:1 to 2.0:1 with the ratio of moles of calcium to total moles of maleic and tartaric acid being less than 1; and (iii) a neutralizing agent comprising an hydroxide of a monovalent cation in an amount such that the ratio of moles of monovalent cation to moles of maleic acid plus moles of tartaric acid minus moles of calcium ranges from about 2.1:1 to 3.8:1 and (b) maintaining said aqueous reaction mixture at a tempera-ture of from about 20°C to 120°C for a time period sufficient to form a reaction product mixture of (i) tartrate monosuccinate of the formula:
wherein X is a salt-forming cation; and (ii) tartrate disuccinate of the formula:
wherein X is a salt-forming cation; and (c) reducing the calcium content of said reaction product mixture to the extent that the molar ratio of calcium to the tartrate succinate reaction products is less than about 1:10.

11. A process according to Claim 10 wherein the reaction mixture comprises from about 40% to 55% by weight of said salts of maleic and tartaric acids.

12. A process according to Claim 11 wherein (a) the maleic acid salt is selected from sodium and potassium maleate;
(b) the tartaric acid salt is selected from sodium and potassium tartrate; and (c) the calcium cations are provided by calcium hydrox-ide; and (d) the monovalent cation-containing neutralizing agent is selected from sodium hydroxide, potassium hydroxide and ammonium hydroxide.

13. A process according to Claim 12 wherein the maleic acid salt and tartaric acid salt reactants are formed in the reaction mixture in situ.

14. A process according to Claim 12 wherein (a) the molar ratio of maleic acid to tartaric acid used in forming the reaction mixture ranges from about 0.9:1 to 1.2:1 and (b) the molar ratio of calcium cations to tartaric acid used in forming the reaction mixture ranges from about 0.8:1 to 1.5:1.

15. A process according to Claim 12 wherein the molar ratio of calcium to tartrate succinate reaction products is reduced to less than about 1:20 by addition to the reaction mixture of a precipitating agent selected from alkali metal carbonate, alkali metal bicarbonate and mixtures thereof.

16. A process according to Claim 12 wherein the aqueous reaction mixture is maintained at a temperature of from about 50°C
to 80°C for a period of from about 0.5 to 10 hours.

17. A detergent composition comprising from about 0.5% to 98% by weight of a surfactant and from about 2% to 99.5% by weight of a builder component selected from the group consisting of (a) tartrate monosuccinic acid, or salt thereof, of the structure wherein X is H or a salt-forming cation;
(b) tartrate disuccinic acid, or salt thereof, of the structure:

wherein X is H or a salt-forming cation, or (c) a combination of said tartrate monosuccinic acid or salt and said tartrate disuccinic acid or salt, in a weight ratio of tartrate monosuccinic acid or salt, to tartrate disuccinic acid or salt, of from about 97:3 to 20:80.

18. A detergent composition according to Claim 17 which contains from about 5% to 95% by weight of an additional component selected from the group consisting of additional detergent build-ers, chelating agents, enzymes, fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents, soil removal/anti-redeposi-tion agents, soil release agents, fabric softening agents, per-fumes, solvents, opacifiers and combinations of said additional components.

19. A laundry additive composition comprising (A) from about 2% to 99.5% by weight of a builder component selected from the group consisting of (i) tartrate monosuccinic acid, or salt thereof, of the structure wherein X is H or a salt-forming cation;
(ii) tartrate disuccinic acid, or salt thereof, of the structure:
wherein X is H or a salt-forming cation, or (iii) a combination of said tartrate monosuccinic acid or salt and said tartrate disuccinic acid or salt, in a weight ratio of tartrate monosuccinic acid or salt, to tartrate disuccinic acid or salt, of from about 97:3 to 20:80; and (B) from about 0.5% to 98% by weight of a laundry adjuvant selected from the group consisting of surfactants, additional detergent builders, chelating agents, en-zymes, fabric whiteners and brighteners, sudsing control agents, solvents, hydrotropes, bleaching agents, bleach precursors, buffering agents, soil removal/anti-rede-position agents, soil release agents, fabric softening agents, perfumes; colorants, opacifiers and combinations of said laundry adjuvants.

20. A laundry additive composition according to Claim 19 wherein (A) the builder component comprises a combination of sodium tartrate monosuccinate and sodium tartrate disuccinate;
and (B) the laundry adjuvant is selected from surfactants bleaching agents, bleach precursors, enzymes and com-binations of said laundry adjuvants.

APL:3493