CA1333983C - Stable liquid detergent compositions - Google Patents

Abstract

Heavy-duty liquid detergents containing sulfonate and alcohol ethoxylate sulfate anionic surfactants, ethoxylated nonionic surfactant, saturated fatty acid, citrate and tartrate succinate builders, a neutraliza-tion system comprising sodium ions and, preferably, a low level of alkanolamine, and a stabilizing system comprising propylene glycol, water and, preferably, hydrotrope or alkenyl succinate material. The compositions are isotropic liquids providing a high level of detergency performance and good chlorine bleach compatibility.

Description

~ 333983 STABLE LIQUID DETERGENT COMPOSITIONS
-Technical Field The present invention relates to heavy-duty liquid detergent compositions containing sulfonate surfactant, alcohol ethoxylate sulfate surfactant, ethoxylated nonionic surfactant, saturated fatty acid, citrate and tartrate succinate builders, a neutralization system 10 comprising sodium ions and, preferably, a low level of alkanolamine, and a stabilizing system comprising propy-lene glycol, water and, preferably, hydrotrope or alkenyl succinate material. The compositions are isotropic liquids providing a high level of detergency 15 performance and good chlorine bleach compatibility.
There has been considerable demand for liquid detergents capable of providing superior cleaning under a wide variety of laundering conditions. Such composi-tions generally require a number of ingredients which 20 tend to separate into discrete phases. Isotropic liquid detergents are desired for both consistency of perform-ance and aesthetic reasons. The compositions herein are isotropic as made (e.g., at about 70F (21.1C), and preferably remain isotropic during shipping and storage, 25 where temperatures of 55F (12.8C) or lower are often encountered. They preferably are also formulated to recover, after freezing and thawing, to an isotropic phase prior to consumer use.
Liquid detergents often contain high levels of 30 alkanolamines to enhance performance and product sta-- bility. However, alkanolamines readily react with and destroy chlorine bleaches. Consumers who add chlorine bleaches to wash solutions containing alkanolamine-based detergents consequently do not obtain optimum bleaching 35 performance. Thus, there is a continuing need for the -development of a liquid detergent capable of providing superior cleaning, bleach compatibility and product stability.
Background Art U.S. Patent 4,561,998, Wertz et al, issued Dece~ber 31, 1985, discloses detergent compositions containing anionic surfactants, quaternary ammonium, amine or amine oxide surfactants, and fatty acids, and formulated to provide a near-neutral wash pH. The compositions are 10 preferably liquid detergents which additionally contain ethoxylated nonionic surfactants and polycarboxylate builders.
U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, discloses liquid detergents containing anionic 15 surfactants, nonionic surfactants and from about 8~ to about 20% by weight of a fatty acid. The compositions have a pH of from about 6.0 to about 7.5.
U.S. Patent 4,287,082, Tolfo et al, issued September 1, 1981, discloses liquid detergents contain-20 ing saturated fatty acids, enzymes, enzyme-accessible calcium and short-chain carboxylic acid salts, prefer-ably formates.
U.S. Patent 4,507,219, Hughes, issued March 26, 1985, discloses heavy-duty liquid detergents containing 25 sulfonate and alcohol ethoxylate sulfate anionic surfactants, ethoxylated nonionic surfactant, optional quaternary ammonium, amine or amine oxide surfactants, saturated fatty acid, polycarboxylate builder, a neutralization system comprising sodium, 30 potassium and, preferably, low levels of alkanolamines, and a solvent system comprising ethanol, polyol and water. The compositions are isotropic liquids providing a high level of detergency performance and improved chlorine bleach compatibility.

1 33s983 Summary of the Invention The present invention encompasses a heavy-duty liquid detergent composition comprising, by weight:
(a) from about 5~ to about 15~, on an acid basis, 5 of a sulfonate surfactant containing a C10-C16 alkyl or alkenyl group;
~ b) from about 8% to about 18~, on an acid basis, of an alcohol ethoxylate sulfate surfactant of the formula RO(C2H4O)mSO3M, wherein R is a C10-C16 alkyl or 10 hydroxyalkyl group, m averages from about 0.5 to about 4, and M is a compatible cation;
(c) from about 0.5% to about 7% of an ethoxylated nonionic surfactant of the formula R1(OC2H4)nOH, wherein R is a ClO-Cl6 alkyl group or a C8-C12 alkyl phenyl 15 group, n averages from about 3 to about 9, and said nonionic surfactant has an HLB of from about 10 to about 13;
(d) from about 1% to about 5% of a C10-C14 satur-ated fatty acid, the weight ratio of C10-C12 fatty acid 20 to C14 fatty acid being at least 1;
(e) from about 1% to about 7%, on an acid basis, of a citrate builder material;
(f) from about 2% to about 8%, on an acid basis, of a tartrate succinate builder material selected from 5 the group consisting of:
i) HOCIH CH - O CH CH2 coox coox loox coox ~herein X is a salt-forming cation;
ii) CH - CH - O- CH CH - O - CH CH
1 2 1 ~ 2 COOX COOX COOX COOX COOX COOX
wherein X is a salt-forming cation; and iii) mixtures thereof;
(g) from about 0 to about 0.04 moles per 100 grams of composition of an alkanolamine selected from the 35 group consisting of monoethanolamine, diethanolamine and triethanolamine;

(h) sodium ions;
(i) from `2% to about 8% of a hydrotrope selected from the group consisting of the water-soluble salts of toluene sulfonate, xylene sulfonate, cumene sulfonate, 5 and mixtures thereof, or a C12-C14 alkenyl succinic acid or salt thereof, or mixtures thereof:
(j) from about 2% to about 18% of propylene glycol; and (k) from about 40% to about 60% water;
10 said composition containing from about 15% to about 30%
of (a), (b) and (c); from about 5% to about 12% of (e) and (f); from about 8% to about 20% of (d), (e) and (f);
from about 25% to about 50% of (a), (b), (c), (d), (e) and (f); from about 5~ to about 12% of (d) and (i); from 15 about 3% to about 18% of (i) and (j); and from about 45%
to about 68% of (i), (j) and (k); the weight ratio of (a) to (b) being from about 0.3 to about 1.7; the weight ratio of (e) plus (f) to (d) being at least about 1.5; and all of said components being selected to provide an 20 isotropic liquid at 70F (21.1C) having an initial pH
of from about 7.5 to about 9.0 at a concentration of about 10% by weight in water at 68F (20C).
Detailed Description of the Invention The liquid detergents of the present invention 25 contain sulfonate and alcohol ethoxylate sulfate anionic surfactants, ethoxylated nonionic surfactant, saturated fatty acid, citrate and tartrate succinate builders, a neutralization system comprising sodium ions and, preferably, a low level of alkanolamine, and a 30 stabilizing system comprising propylene glycol, water and, preferably, hydrotrope or alkenyl succinate material.
The compositions herein are formulated to provide a high level of detergency performance under a wide vari-35 ety of laundering conditions. They also providegood chlorine bleach compatibility due to the limited - amount of alkanolamine. Since the compositions contain a relatively high level of active components and little or no alkanolamine to enhance product stability, the types, levels and ratios of the components must be carefully balanced to provide isotropic liquids as made, and preferably at temperatures as low as 55F (12.8C).
Preferred compositions herein are isotropic liquids at 50F (lO~C). They preferably also recover, after freezing and thawing, to an isotropic form by 55F
lO (12.8C), more preferably by 50F (10C).
In order to meet these stability constraints, the present compositions require a neutralization system comprising sodium ions, and, optionally, potassium ions.
Complete sodium neutralization may be used, but all 15 potassium neutralization results in an unacceptably high gel point. The total level of organic and inorganic bases must also be selected to provide a sufficiently high product pH to obtain a wash pH desired for detergency performance and to minimize the level of 20 poorly-soluble free fatty acids, without the pH being so high that pH sensitive stain removal and enzyme stability are compromised.
The compositions also require a stabilizing system comprising propylene glycol and water, and, preferably, 25 a hydrotrope or alkenyl succinate material with low levels of fatty acid. The amount of propylene glycol, water and hydrotrope or succinate material must also be sufficient to prevent organic phase separation (i.e., keep free fatty acids and poorly-soluble surfactants in 30 solution).
Sulfonate Surfactant The detergent compositions herein contain from about 5% to about 15%, preferably from about 6% to about 10%, by weight (on an acid basis) of an anionic sulfon-35 ate surfactant containing a C10-Cl6 alkyl or alkenyl group. Anionic sulfonate surfactants useful herein are disclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,919,678, Laughlin et al, issued December 30, 1975, Preferred sulfonate surfactants are the water-soluble salts, particularly the alkali metal, and alka-nolammonium ~e.g., monoethanolammonium or triethanolam-monium) salts of alkylbenzene sulfonates in which the alkyl group contains from about 10 to about 15 carbon 10 atoms, in straight chain or branched chain configura-tion, e.g., those of the type described in U. S. Patents 2,220,099 and 2,477,383. Es~pecially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 15 abo~t 11 to about 13.
Also useful herein are the water-soluble salts of paraffin sulfonates, olefin sulfonates, alkyl glyceryl ether sulfonates, esters of -sulfonated fatty acids ~ containing from about 1 to 10 carbon atoms in the ester 2~ group, 2-acyloxy-alkane-1-sulfonates containing from about 2 to 9 carbon atoms in the acyl group, and ~-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group.
Mixtures of the above-described sulfonates, partic-y ith the Cll_l3 linear alkylbenzene sulfonatescan also be used.
Alcohol Ethoxylate Sulfate Surfactant The present compositions also contain an alcohol ethoxylate sulfate surfactant of the formula 30~o(c2H4o)mso3M~ wherein R is a C10-Cl6 alkyl (preferred) or hydroxyalkyl group, m averages from about 0.5 to about 4, and M is a compatible cation. This surfactant represents from about 8% to about 18%, preferably from about 9% to about 14%, by weight (on an acid basis) of 35the composition.

Preferred alcohol ethoxylate sulfate surfactants of the above formula are those wherein the R substituent is a C12 15 alkyl group and m is from about 1.5 to about 3.
Examples of such materials are C12_15 alkyl polyetho y 5 late (2.25) sulfate (C12-15 E2.25S); C14-15 2.25 12-13 1.5S; C14_15E3S; and mixtureS thereof. The sodium, potassium, monoethanolammonium, and triethanol-ammonium salts of the above are preferred.
Ethoxylated Nonionic Surfactant The compositions also contain from about 0.5% to about 7%, preferably from about 1% to about 5%, by weight of an ethoxylated nonionic surfactant of the formula Rl(OC2H4)nOH, wherein R is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, n averages from 15 about 3 to about 9, and said nonionic surfactant has an HLB (hydrophile-lipophile balance) of from about 10 to about 13. These surfactants are more fully described in U.S. Patents 4,285,841, Barrat et al, issued August 25, 1981, and 4,284,532, Leikhim et al, issued August 18, 20 1981. Particularly preferred are condensation products of C12-C14 alcohols with from about 3 to about 7 moles of ethylene oxide per mole of alcohol, e.g., c12-c,3 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
Optional Cosurfactant The compositions herein can contain from 0% to about 5%, preferably from about 0.3% to about 3%, by weight of a `cosurfactant selected from the quaternary ammonium, amine, and amine oxide surfactants defined in 30 the above cited U.S. Patent 4,507,219, Hughes Of the above, the C10-C14 alkyl trimethylammonium salts are preferred, e.g., decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, 35 myristyl trimethylammonium bromide and coconut tri-methylammonium chloride and methylsulfate.

Fatty Acid The compositions of the present invention contain from about 1% to about 8%, preferably from about 2% to about 6%, most preferably from about 3% to about 5%, by 5 weight of a saturated fatty acid containing from about 10 to about 14 carbon atoms. In addition, the weight ratio of C10-Cl2 fatty acid to C14 fatty acid should be at least 1, preferably at least 1.5, more preferably at least about 2.5.
Suitable saturated fatty acids can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil and coconut oil) or synthetic-ally prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-15 Tropsch process). Examples of suitable saturated fatty acids for use in the compositions of this invention include capric, lauric, myristic, coconut and palm kernel fatty acid. Preferred are saturated coconut fatty acids, from about 5:1 to 1:1 (preferably about 20 3:1) weight ratio mixtures of lauric and myristic acid, mixtures of the above with minor amounts (e.g., 10%-50%
of total fatty acid) of oleic acid; and palm kernel fatty acid.
Citrate Builder The ccmpositions further contain from about 1% to about 7%, preferably from about 2% to about 5%, by weight on an acid basis, of a citrate (preferably in the form of an alkali metal or alkanolammonium salt) builder material. This material is generally added to the 30 compositions herein as citric acid, but can be added in the form of a fully neutralized salt.
Tartrate Succinate Builder The compositions also contain from about 2% to about 8%, preferably from about 3% to about 6%, by 35 weight on an acid basis, of a tartrate succinate builder material selected from the group consisting of:

i) HOCH CH - O - CH CH
~ 2 COOX COOX COOX COOX
wherein X is a salt-forming cation;
ii) CH CH - O- CH - CH - O - CH CH
~ 2 ~ 2 COOX COOX COOX COOX COOX COOX
wherein X is a salt-forming cation; and iii) mixtures thereof.
The tartrate succinate compounds used herein may be generically classified as "ether carboxylates." These 10 include tartrate monosuccinates having the structural formula:
HOCH CH O CH CH

COOX COOX COOX COOX
wherein each X is a salt-forming cation (hereinafter 15 designated as "TMS".) The tartrate monosuccinate component can be added to the compositions herein in its free acid form, i.e., wherein X in the structural formula is H. Alterna-tively, and preferably, this material may be added as a 20 partially or fully neutralized tartrate monosuccinate salt. Preferred salt-forming cations useful in forming the neutralized materials are those which yield substan-tially water-soluble salts of tartrate monosuccinic acid. Examples of such preferred salt-forming cations 25 include alkali metal, e.g., sodium, potassium, lithium, ammonium, Cl-C4 alkyl substituted ammonium and Cl-C4 alkanolamine. The most preferred salt-forming cations are sodium, potassium, monoethanolamine and triethanol-amine.
The second ether carboxylate composition which can be used in this invention is a tartrate disuccinate having the structural formula:
CH- CH - O- CH CH - O - CH CH
~ 2 ~ 2 COOX COOX COOX COOX COOX COOX
35 wherein each X is a salt-forming cation (hereinafter designated as "TDS".) As with the TMS component, the TDS component can be added to the compositions herein in either its free acid form or in its partially or fully neutralized form.
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.
~ixtures of TMS and TDS can also be used; indeed, 10 mixtures are generall~ obtained in the method of manu-facture disclosed hereinafter. Typically, such mixtures comprise TMS:TDS in ratios ranging from 97:3 to 20:~0.
Preferred ratios TMS:TDS are 95:5 to 40:60. These are used at the same levels as mentioned above for the 15 single components to provide the builder compositions of this invention.
The T~S and TDS compounds used in the practice of this invention are not believed to be described in the literature, so their preparation will be described in 20 detail.
The first step of the 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 25 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 mixture will generally range from about 20%
to 60% by weight of the mixture, more preferably from 30 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 tartrate reactants in requisite mixed salt form and amounts can be generated 35 in the reaction mixture in situ. This can be done by combining in aqueous solution certain amounts of ma'eic acic or maleic anhydride, tartaric acid, a source of calcium cations and, as a neutralizing agent, an hydrox-ide of a monovalent cation in certain amounts. The molar ratio of maleic acid to tartaric 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 relative amounts of tartrate monosuccinate and tartrate disuccinate desired in the builder composition 10 to be prepared.
A source of calcium cations, which acts as a catalyst for the tartrate succinate-forming reaction, is generally added to such aqueous solutions in an amount such that the ratio of calcium cations to tartaric acid 15 ranges from about 0.1:1 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 that the ratio of moles of calcium catior.s to total moles of maleic and tartaric acids in solution is less than 1.
20 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. Calcium hydroxide is highly preferred since it acts as both a calcium cation source and a neu-25 tralizing agent.
An hydroxide of a monovalent cation is alsoessentially added to the reactant mixture as a neutralizing agent. This neutralizing agent is usually added in an amount such that the ratio of moles of 30 monovalent cations to total moles of tartaric acid plus the moles of maleic acid minus the moles 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 35 agent can be any hydroxide which upon addition to water yields monovalent neutralizing cations in solution.

~ 333983 ~ Such neutralizing agents include, for example, alkali metal, ammonium or substituted ammonium hydroxide.
Sodium hydroxide is highly preferred.
Enough neutralizing base (e.g. calcium hydroxide and monovalent cation hydroxide) should be added to the reaction mixture to ensure that the reaction mixture is over-neutralized. Thus the reaction 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 10 12.5.
In forming the reaction mixture of the present process, it is possible to employ precursors of the essential reaction mixture components. Precursors ~f the tartrate and maleate mixed salt reactants in 15 solution can take a variety of forms. For example, tartaric acid 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 zcid and 20 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 is, of course, also possible to form the reac-tion mixture used in the process herein by adding the tartrate and maleate reactants in their appropriate salt forms to water and to thereby prepare the reaction mixture without the step of in situ neutralization. If 30 the reaction mixture is formed in this manner, amounts of the tartrate, maleate and calcium materials, as well as added neutralizing agents, should be selected so that the resulting solution corresponds in composition to the hereinbefore described reaction mixtures formed by in 35 situ generation of the essential reaction mixture components.

- 13 - l 333983 ~ As indicated hereinbefore, the preferred process of the present invention employing reactant molar ratios of maleate to tartrate within the range of 0.9:1 to 1.2:1 is especially advantageous from the reactant conversion and reactior kinetics standpoint. 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 preparation of such materials as oxydisuccinate using a maleic anhy-10 dride reactant. Without being bound by theory, theimproved conversion percentages which can be realized using the preferred process embodiments of the present reaction may be in part due to the inherently greater stability of TMS in the reaction mixture in comparison 15 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 20 should also be noted that irrespective of conversion percentage, production of TMS/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 25 carboxylates such as oxydisuccinate.
It should also be noted that use of the hereinbe-fore described particular amounts of the calcium cation source is likewise believed to play a role in realizing the improved conversion levels achieved with the process 30 of the present invention. In direct contrast to prior art teaching regarding ether carboxylate preparation (See, for example, U.S. Patent 3,635,830), the amount of calcium in the reaction mixture of the present process should be kept within the hereinbefore described concen-35 tration limits in order to avoid formation of a largeamount of insoluble or sparingly soluble calcium salts 14 l 333983 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 TMS/TDS composition forming 10 reaction is carried out by maintaining the aqueous reaction mixture at a temperature of from about 20C to 120C, preferably from about 50C to 80C, for a period of time sufficient to form a reaction product mixtu~e which contains the desired amounts of the tartrate 15 monosuccinate and tartrate disuccinate compounds 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 compounds used in the builder compositions 20 herein.
Since the TMS/TDS are to be used as detergent builders, it is especially important that such composi-tions contain especially low levels of alkaline earth metals such as calcium. The builder compositions of 25 this invention should generally contain no more than about 10 mole percent of calcium based on the total moles of TMS and TDS present.
After the ether carboxylate-forming reaction has been completed to the desired extent, the calcium con-30 tent of the aqueous reaction must be reduced. Removalof 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 precipitating material having a 35 greater affinity for reaction with calcium than do the tartrate monosuccinate and tartrate disuccinate reaction - lS - l 3 3 3 9 8 3 products. Such materials can include, for example, precipitating chelating agents such as ethanehydroxydi-phosphonic acid, or salts thereof (EHDP), or calcium precipitating materials such as alkali metal carbonate, 5 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 lO treatment of the reaction product mixture with an appro-priate insoluble ion exchange resin. No matter what technique is employed, calciu~ content of the aqueous reaction mixture should be reduced to the extent that the ratio of moles of calcium to total moles of tartrate 15 monosuccinate and tartrate disuccinate is less than about 1:10, preferably less than about 1:20.
Preferably, in addition to such calcium reduction processing, the reaction product mixture of the present process may also optionally be treated to remove excess 20 reactants or reaction by-products such as maleates, malates, tartrates and fumarates. This can be accom-plished by conventional salt separation procedures using a solvent such as methanol in which these excess reac-tants and reaction by-products are relatively soluble 25 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 desired, after excess reactants and 30 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 35 the TMS/TDS mixture is recovered in solid, e.g., granular, form. Alternatively, the TMS/TDS mixture in - 16 - l 3 3 3 9 8 3 the form of an aqueous liquid may be utilized directly in the preparation of builder, detergent compositions or laundry additive products of the types more fully described hereinafter.
After reduction of the calcium content in the reaction product mixture, it is possible, if desired, to acidify the product mixture using conventional acidifi-cation or ion exchange techniques to convert the TMS/TDS
products therein to their free acid form. Normally, 10 however, the tartrate monosuccinate and tartrate disuc-cinate materials can be used as builders in their water-soluble salt form, and such acidification is therefore not usually necessary or desirable.
It is also possible, if desired, to separate the 15 individual components of the resulting builder mixture and recover such compounds as substantially pure T~S and TDS materials. Such component separation can be effected, for example, using conventional liquid chroma-tographic techniques. For use in some types of 20 detergent compositions, it may be desirable to use either T~lS or TDS as substantially pure materials. ~lore frequently, however, recovery of the individual TMS and TDS components as substantially pure materials is neither necessary nor particularly advantageous.
Reaction Sequence I
In this sequence, a mixture of tartrate monosuc-cinate (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 30 anhydride (2205g, 22.5 moles) is heated in 2000g of dis-tilled water until dissolved. The resultant solution of maleic acid is cooled to 85 + 5C and 2250g L-(+)-tartaric acid (15.0 moles~ is added with stirring at 85 + 5C until a homogeneous clear acid solution is 35 obtained.

- 17 - l 3 3 3 9 8 3 ~ Separately, llllg of calcium hydroxide (15.0 moles) is slowly acded to a mixture of 4440g 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 solutior. at a time. Stirring is con-tinued until an essentially uniform base mixture is obtained.
The base mixture is then added at a uniform rate lO over 0.5 hour to the moderately stirred acid solution which is at 70-85C. The resulting reaction mixture is cooled with warm (ca. 60C) water in order to maintain a reaction te~.perature of 90 + 5C most of the time. The reaction mixture may, however, boil briefly from time to 15 time. The object is to prevent major losses of water vapor and also to limit the amount of insoluble salt which crystallizes upon the cool reaction vessel walls.
As the last 10% of base is added, the reaction tempera-ture is held at 85C. The reaction mixture is quickly 20 weighed and brought to 13,020g, i.e., 50% active, with 200g 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 = 6510g.) The reaction mixture is immediately heated with steam, stirred moderately in a covered reactor, and a 0.40g sample taken with time arbitrarily set at zero.
The reaction mixture, which is a white suspension, is brought to 90-100C within 10 minutes. Within 15 to 20 30 minutes of time zero, the reaction mixture clears.
Samples (0.40 + 0.04g) of the reaction solution are taken every half hour to be dissolved in 100 ml 0.1~
sulfuric acid solution and immediately submitted for high pressure liquid chromatography (HPLC) analysis in 35 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 homo-5 geneous, almost colorless quenched reaction productsolution is reweighed and is made up again to 13,020g with 327g of distilled water to give a reaction product solution containing 50% active.
HPLC analysis indicates that the composition of the 10 organic portion of the reaction product solution is 11.1% tartrate, 1.7% malate, 12.6% maleate, 10.9% fumar-ate, 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 15 isomers of sodium tartrate disuccinate (TDS). There-fore, 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
refractive index raw data, i.e., are not corrected to 20 mole%. Calculated yield of this reaction based on tartrate is 4,139g.
A second reaction product batch of the same size is made using similar procedures. HPLC analysis indicates that the composition of this second reaction product 25 solution is 9.8% tartrate, 1.7% malate, 12.4% maleate, 10.1% fumarate, 35.0% peak 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 (T~S) and peaks 3A and 3B are isomers of sodium tartrate disuccinate (TDS).
30 Therefore, the HPLC-estimated yield of TMS + TDS based upon all peak areas is 66.196. The approximate weight ratio of T~SS:TDS is 80:20. Yield is 4400g based on calculations.
Both reaction product batches are combined to give 35 26,040g of solution which is calculated to contain 8539g of T~S/TDS and 30 moles of calcium ion. This solution is then diluted with 26,040g of water. While this solution is at 26C and stirred vigorously, a 28%
solution of 7500g (30 mole) of ethanehydroxydiphos-phonate disodium salt dissolved in 18,750g of water is added followed by 3178g of 50% sodium hydroxide solution 5 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 removea by filtration using suction filtration equipment with a paper filter, and the filtrate is washed with 4 liters 10 Of water. The resulting supernatant, 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 15 32,550g This solution is then poured into 80 liters of vigorously stirred methanol. This is done to help separate the less soluble T~S and TDS from the ~ore soluble maleic and fumaric acid salts. The stirring is 20 continued for 15 minutes followed by a 1/2 hour sett'ing period. Then the liquid is decanted from the gummy solid by siphon. This solid is dissolved in 13,50Cg of distilled water to give 26,685g of solution whic~ is then poured into 68 liters Gf methanol, essentially 25 repeating the above. The resulting solid is dissclved in 6 liters of distilled water (pH = 8.4), and the vat is heated with steam. ~ethanol is removed with a stream of nitrogen directed on the surface of the solution which is well stirred. This is continued until 'H-NMR
30 analysis indicates that the methanol is removed. The resulting solution is 16,380g. To reduce viscosity, 2 liters of water are added, and the mixture is filtered to give 18,887g of solution. This solution is anal~zed and found to have the following composition by high 35 pressure liquid chromatography using a refractive ir.dex detector: 43.6~ T~S/TDS (8,235g 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 level of the solution is 0.048 weight % as 5 determined by atomic absorption.
Reaction Sequence II
A TMS/TDS reaction product mixture is prepared using procedures similar to those set forth in Reaction Sequence I except that the reactants used to form the 10 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 determined by high pressure liquid chromatography to contain 17.2% tartrate, 1.5% malate, 15 9.9% maleate, 10.3% fumarate, TMS (2A 36.2%, 2B 13.4%) and TDS 3A 5.3%, 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 20 salts. In such a procedure 26.5 grams of sodium carbonate and 21.0 grams of 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 reaction product mixture which contains 0.125 25 moles of calcium. The resulting mixture is placed in a 1 liter flask equipped with a thermometer and stirrer.
This mixture is then heated to 80C and stirred for 3 hours. After cooling to 2SC while stirring is continued, this mixture is filtered through a sintered 30 glass filter. The resulting filter cake is washed with - 20ml of water twice. The filtrate is adjusted to a weight of 1000 grams with the addition of water and then is analyzed. The filtrate is found to contain tartrate - 1.48%; malate - 0.14%; maleate - 1.02%; fumarate -35 0.83%; TMS - (2A 3.3%, 2B 1.3%); TDS - (3A 0.5%, 3B
0.5%); and calciu~l - 0.009%. The maleate and fumarate -- salts are then removed using a methanol precipitation procedure as in Reaction Sequence I.
Neutralization System The present compositions can contain from about 0 5 to about 0.04 moles, preferably from about 0.01 to about 0.035 moles, more preferably from about 0.015 to about 0.03 moles, per 100 grams of composition of an alkanol-amine selected from the group consisting of monoethanol-amine, diethanolamine, triethanolamine, and mixtures 10 thereof. Low levels of the alkanolamines, particularly monoethanolamine, are preferred to enhance product stability, detergency performance, and odor. However, the amount of alkanolamine should be minimized for best chlorine bleach compatibility.
In addition, the compositions contain sodium ions, and preferably potassium ions, at a level sufficient to neutralize the anionic species and provide the desired product pH.
Stabilizing System The stabilizing system for the compositions is com-prised of propylene glycol, water and an optional hydrotrope or alkenyl succinate material.
The propylene glycol (1,2-propane diol is particu-larly preferred) represents from about 2% to about 20~, 25 preferably from about 4% to about 18~, by weight of the composition.
The compositions also contain from about 25% to about 60%, preferably from about 40% to about 55%, by weight of water.
Finally, the compositions herein contain from 0% to about 8%, preferably from about 2% to about 5%, by weight of a hydrotrope selected from the group consisting of the water-soluble salts of toluene sulfonate, xylene sulfonate, cumene sulfonate, and 35 mixtures thereof. Salts of cumene sulfonate (especially the sodium salt) are preferred.

- 22 - ~333983 The compositions also contain from 0% to about 8%, preferably from 0% to about 5%, by weight of a C12-C14 alkenyl succinic acid or salt thereof. These materials are of the general formual R-CH(COOX)CH2(COOX), wherein R is a C12-C14 alkenyl group and each X is H or a suitable cation, such as sodium, potassium, ammonium or alkanolammonium (e.g., mono-, di-, or tri-ethanolammonium). Specific examples are 2-dodecenyl succinate (preferred) and 2-tetradecenyl succinate.
The hydrotrope and succinate material together represent from 0 to about 8%, preferably from about 2%
to about 5% of the composition.
In adcition to the above, the fatty acid and hydrotrope or succinate material together should 15 represent from about 4% to about 12%, preferably from about 5% to about 12%, more preferably from about 6% to about 10%, by weight of the composition. Compositions containing less than about 5% of fatty acid require the hydrotrope or succinate material for adequate stability.
20 Higher levels of fatty acid within the specified ranges appear to modify the cloud point of the anionics in the composition in such a way that the reduced level of hydrotrope or succinate, or no hydrotrope or succinate, is required.
In addition, the propylene glycol and hydrotrope or succinate represent from about 3% to about 25%, preferably from about 3% to about 20%, more preferably about 6% to about 18%, and the propylene glycol, hydrotrope or succinate and water represent from about 30 35% to about 68%, preferably from about 35% to a~out 63%, more preferably about 45% to about 60%, by weight of the composition.
The compositions of the present invention are further constrained by the following limits, in which 35 all percentages and ratios are calculated on an acid basis where anionic materials are involved. The sulfon-ate, alcohol ethoxylate sulfate, and ethoxylated nonionic surfactants, together, represent from abGut 15%
to about 30%, preferably from about 18% to about 25%, by weight of the composition. The weight ratio of the sulfonate surfactant to the alcohol ethoxylate sulfate surfactant should also be from about 0.3 to abcut 1.7, preferably from about 0.6 to about 1.
The citrate and tartrate succinate builders together represent from about 5% to about 12% by weight 10 of the composition, and the weight ratio of these builders to fatty acid should be at least about 1, preferably at least about 1.5. In addition, the fatty acid and citrate and tartrate succinate builders together represent from about 8% to about 20%, prefer-15 ably from about 10% to about 15~, by weight of the composition. In addition, the above fatty acid, build-ers and surfactants represent a total of from about 25~
to about 50%, preferably from about 30% to about 40%, by weight of the composition.
Finally, all of the above components are selected to provide an isotropic liquid detergent at 70F
(21.1C), preferably at 55F (12.8C), more preferably at 50F (10C). The components are also selected to provide an initial pH of from about 7.5 to abcut 9.0, 25 preferably from about 7.8 to about 8.8, at a concentra-tion of 10% by weight in water at 68F (20C).
Optional Components Optional components for use in the liquid deter-gents herein include other surfactants and builders, 30 enzymes, enzyme stabilizing agents, polyacids, soil removal agents, antiredeposition agents, suds regulants, other hydrotropes, opacifiers, antioxidants, bacteri-cides, dyes, perfumes, and brighteners such as those described in the U.S. Patent 4,285,841, Barrat et al, 35 issued August 25, 1981, and in the above mentioned U.S.
Patent 4,507,219 to Hughes. Such optional components generally represent less than about 15%, preferably from about 2%
to about 10%, by weight of the composition.
The compositions herein can contain up to about 5%

5 of ethanol as an additional solubilizing agent. How-ever, the compositions do not require ethanol for phase stability, and preferably contain little or no ethanol (e.g., less than about 1% by weight) for best product odor.
The following examples illustrate the compositions of the present invention.
All parts, percentages and ratios used herein are by weight unless otherwise specified.
EXAMPLE I
The following composition is prepared by adding the components to a mixing tank in the order listed with continuous mixing. (Components in parentheses are added only as part of a premix containing other components.) % Actual Wt. Wt.% in 20 Components Assayl Added (lb) Product C14_15 alkyl polyethoxylate 2 (2.25) sulfonic acid 26.44 836.5 10.25 (Sodium cumene sulfonate) -- -- 3.28 C13 linear alkylbenzene 25 sulfonic acid 96.00 167.5 7.45 Sodium diethylenetriamine pentaacetate 41.00 14.6 0.28 1,2-Propanediol 100.00 101.0 4.68 Monoethanolamine 100.00 18.2 1.863 30 Potassium hydroxide 45.00 17.6 0.36 (Sodium hydroxide) -- -- ~4.23 C12-14 fatty acid 100.00 71.7 3.323 Citric Acid 50.00 156.0 4.63 Sodium formate 30.00 58.0 0.81 35 Calcium formate 10.00 24.0 0.11 Boric acid 100.00 20.0 0.93 Brightener 1.81137.7 0.12 (C12-13 alcohol polyethoxy-late (6.5)*) -- -- 1.93 5 Tartrate succinate** 36.205275.8 4.63 C12 alkyltrimethylammonium chloride 37.0032.5 0.56 15-18 80.0037.4 1.39 Water -- 165.0 to 100%3 10 Protease enzyre ~2.0 AU/g) -- lS.0 0.014AU/g Amylase enzyme (375 AM. U/g)-- 3.2 0.556AM.U/g Dyes 1.006 1.6 <0.01 Perfume 100.00 5.0 0.23 lBalance to 100% is water unless otherwise noted.
2Balance also includes 10.88% sodium hydroxide, 1.41% monoethanolamine and 7.85% sodium cumene sulfonate.
From more than one source.
4Balance also includes 7.55% monoethanolamine and 20 30-21% C12_13 alcohol polyethoxylate (6.5)*.
5Balance also includes 7.98% citric acid.
6Balance also includes 1.50% monoethanolamine.
*Alcohol and monoethoxylated alcohol removed.
**Prepared as in Reaction Sequence I.
***Tetraethylene pentaimine ethoxylated with 15-18 moles (avg.) of ethylene oxide at each hydrogen site on each nitrogen.
EXAMPLE II
The following composition is prepared by adding the 30 components to a mixing tank in the order listed with - continuous mixing. (Components in parentheses are added only as part of a premix containing other components.) % Actual Wt. Wt.% in Components Assay1 Added (gm) Product C14_15 alkyl polyethoxylate 2 (2.25) sul~onic acid 26.44 40.85 10.1 5 (Sodium cumene sulfonate) -- -- 3.00 C13 linear alkylbenzene sulfonic acid 98.0 8.16 7.47 Sodium diethylenetriamine pentaacetate 41.0 0.73 0.28 10 1,2-Propanediol 100.0 13.0 13.9 (Monoethanolamine) -- -- 1.69 (Sodium hydroxide) -- -- ~3.5 C12-14 fatty acid 100.0 5.0 4.67 Citric Acid 50.0 3.52 2.57 15 Sodium formate 30.0 2.9 0.81 Calcium formate 10.0 2.0 0.187 Boric acid 100.0 0.5 0.47 Brighteners 2.89 6.1 0.166 C12 13 alcohol polYethXY 3 late (6.5)* 100.0 1.16 3.27 Tartrate succinate**36.2 12.40 4.20 Soil Release Polymer**** 100.0 1.25 1.17 C12 alkyltrimethylammonium chloride 37.0 1.35 0.47 25 TEPA-E15-18 80.0 3.44 2.57 Protease enzyme (2.0 AU/g) -- 0.6 0.011 AU/g Amylase enzyme (375 AM. U/g)-- 0.08 0.280AM.U/g Perfume 100.0 0.25 0.23 Dye 100.0 0.08 <0.01 30 1,2-Propanediol 100.0 1.88 Water -- 1.75 to 100%3 Balance to 100% is water unless otherwise noted.
Balance also includes 10.88% sodium hydroxide, 1.41~ monoethanolamine and 7.85% sodium cumene sulfonate.
3From more than one source.

- 27 - l 3 3 3 9 8 3 4Balance also includes 20.2% monoethanolamine and 38-45% C12-13 alcohol polyethoxylate 16.5)*.
5Balance also includes 8.0% citric acid.
*, **, *** as in Example I.
****Poly(terephthalate propylene glycol ester) ethoxylated with about 30 moles of ethylene oxide.
EXA~PLE III
The following composition is prepared by adding the components to a mixing tank in the order listed with 10 continuous mixing. (Components in parentheses are added only as part of a premix containing other components.) % Actual Wt. Wt.% in Components Assay1 Added Igm) Product C14_15 alkyl polyethoxylate 2 (2.25) sulfonic acid48.71 24.6 11.03 1,2-Propanediol lO0.00 20.1 18.50 Sodium diethylenetriamine pentaacetate 41.00 0.7 0.26 Brightener 1.813 6.8 0.11 20 Monoethanolamine lO0.00 1.5 1.854 C12 13 a1Chl plYethXY 4 late (6.5)* 100.00 2.0 3.73 C13 linear alkylbenzene sulfonic acid 96.00 8.3 7.33 25 (Ethanol) 92.00 -- 3.67 Potassium hydroxide 45.00 3.5 1.45 (Sodium hydroxide) -- -- ~3.4 C12-14 fatty acid lO0.00 8.5 7.824 Citric Acid 50.00 2.66 2.30 30 Sodium formate 30.00 2.90 0.80 Calcium formate 10.00 1.20 0.11 C12 alkyltrimethylammonium chloride 37.0 1.62 0.55 Tartrate succinate** 36.17 19.35 6.44 35 TEPA-E15-18 80.0 2.6 1.91 - 28 - l 3 3 3 9 8 3 Hydrochloric acid 37.3 1.2 0.41 Water to 100~4 Protease enzyme (2.0 AU/g) 0.67 0.01 AU/g Amylase enzyme (375 AM. U/g) 0.16 0.55AM.U/g 5 Dye 0.07 <0.01 Perfume 100.00 0.21 0.19 Balance to 100% is water unless otherwise noted.
Balance also includes 5.13% sodium hydroxide and 16.20% ethanol.
3Balance also includes 7.55% monoethanolamine and 30-21% C12-13 alcohol polyethoxylate (6.5)*.
From more than one source.
5Balance also includes 6.05% citric acid.
*, **, *** as in Example I.
EXA~PLE IV
The following composition is prepared by adding the components to a mixing tank in the order listed with continuous mixing. (Components in parentheses are added only as part of a premix containing other components.) % Actual Wt. Wt.% in Components Assayl Added (gm) Product C14_15 alkyl polyethoxylate 2 (2.25) sulfonic acid48.71 24.2011.19 1,2-Propanediol 100.00 18.0017.09 25 Sodium diethylenetriamine pentaacetate 41.00 0.700.27 Brightener 1.813 6.600.11 Monoethanolamine100.00 1.501.90 C12 13 alChl plYethXY 4 late (6.5)* 100.00 2.003.80 C13 linear alkylbenzene sulfonic acid 96.00 8.207.48 (Ethanol) 92.00 -_3.72 Potassium hydroxide45.00 4.501.92 35 (Sodium hydroxide) -- ~~~3.14 ~ - 29 - 1 333983 C12-14 fatty acid 100.00 4.00 3.81 C12 alkenyl succinic acid 100.00 4.50 4.27 Citric Acid 50.00 2.70 2.39 Sodium formate 30.00 2.90 0.83 5 Calcium formate 10.00 1.20 0.11 C12 alkyltrimethylammonium chloride 37.00 1.60 0.56 Tartrate succinate** 36.17 19.35 6.65 15-18 80.00 2.20 1.67 10 Water to 100%
Protease enzyme (2.0 AU/g) -- 0.67 0.01 AU/g Amylase enzyme (375 AM. U/g)-- 0.16 0.57 AM.U/g Dye 100.00 0.07 <0.01 Perfume 100.00 0.22 0.21 15 Balance to 100% is water unless otherwise noted.
Balance also includes 5.13% sodium hydroxide and 16.20% ethanol.
3Balance also includes 7.55% monoethanolamine and 30-21% C12-13 alcohol polyethoxylate (6.5)*.
20 From more than one source.
5Balance also includes 6.05% citric acid *, **, *** as in Example I.
Examples I-IV are isotropic compositions as made at about 70F (21.1C) and have an initial pH of about 8.4 25 at a concentration of about 10% by weight in water at 68F (20C).
EXAMPLE V
% Wt.% in Components Assay Product C14_15 ~Xyl ~ yethoxy~te 2 (2.25) suLonic acid 36.37 12.00 Sodium cumene s--lf~Ate 45.00 2.503 Ethancl 92.00 2.253 1,2-PropAne~;~1 100.00 3.003 Brightener 2.54 0.12 - 30 - l 3 3 3 9 8 3 C12 13 ~lro~ l palyethoxylate(6.5)* 100.00 4.00 Monoethan~mine 100.00 1.853 Sodium hy~-oxide 50.00 4.133 C13 ~inear aLlcylbenzene sulfonic ~tl 96.00 4.00 Cll 8 ~inear aLlcy~benze sulfonic aci~ 97.03 4.00 C12-14 fa~y ac~d 100.00 3.50 C;t~r Aci~ 50.00 4.00 TdL ~ate succinate** 35.40 4.00 Sodium form.ate 30.00 0.89 Ca~ium format:e 10.00 0.12 C12 aLkyltri~ y~ monium ch~ori~e37.00 0.60 15-18 80.00 1.75 Wate~ 100 003 45 033 S~l r~ase polymer**** 100.00 1.30 Protease enzyme (2.0 AU/g) -- O.OlAU/g Dyes 1.006 <0.01 Perfume 100.00 0.27 Ba~noe to 100% is water unless c~therwise noted.
Balanoe also includes 12.50% sodium hydroxide, 3.03%
eth~n~ 5.46% 1,2-prop~ne~ l, and 6.11% sodium cumene 51l1f~P .
From more than one source Balanoe also inc~udes 12.71% monoe~h~nci~mine and 42.37%
C12 ~ oh~ p~yethoxylate (6.5~ *.
Balanoe also includes 3.71% itri-- acid and 2.85% sodium forma~.
6Balanoe also includes 1.50% mcnff~hAn~ m;ne.
*Alcoh~L and monoethoxy~ated alDohc~ removed.
**Prepared as in Reac~iDn Sequence I.
***Te~thylene pen~;m;ne ethoxyl~ted with 15-18 mcles (avg.) of ethylene oxide at each hydrogen site on each nitrogen.

****P~ymer ofthe formu~

O O CH O O
~ 3 li r~ r X tOCH2CH2tn~O-C- ~ -c-ocH2cHtuto-c- ~ -C-Ot~CH2CH2OtnX

wherein each X is methyl, each n averages about 38, u averages about 2.1, and the polymer contains about 63 mole % of material where u is from 0 to 2; about 14 mole % of material where u is from 3 to 5, and about 4 mole ~
of material where u is 6 or greater. The polymer also contains about 16 mole % of monotooth material and about 0.8 mole % of the cyclic trimer material.
The a~ove composition is a stable liquid as made at about 70F and remains a stable liquid at temperatures down to about 30F. When frozen at 0F, it recovers to a clear isotropic li~uid at 50F. The composition has an initial pH of about 8.55 when measured at a concen-tration of 10% by weight in water at 20C.
EXAMPLE VI
The following composition is prepared by adding the components to a mixing tank in the order listed with continuous mixing. (Components in parentheses are added only as part of a premix containing other components.) % Actual Wt. Wt.% in 25 ComponentsAssayl Added (lb) Product Sodium C14_15 alkyl polyethoxylate (2.25) 2 sulfate 29.10 667.2 7.74 (Sodium cumene sulfonate) -- -- 2.69 30 (Monoethanolamine) -- -- 1.90 Sodium C14-C15 alkyl 3 polyethoxylate 48.02 44.8 0.86 (2.25) sulfate (Ethanol) -- ~~ 0.29 35 Cll 8 linear alkylbenzene sulfonic acid 97.00 221.6 8.6 Brightener 1.37 182.5 0.10 (C12-13 alcohol polethoxy-late (6.5)*) -- __ 3.3 P.2O 100.00 625.0 25.0 1,2-Propanediol 100.00 72.5 2.90 Citric Acid 50.00 145.0 2.9 C12-l4 fatty acid 100.00 40.0 1.60 15-18 80.00 50.0 1.60 Tartrate succinate**40.72 276.4 4.50 Sodium Hydroxide 50.00 49.2 0.98 H2O 100.00 124.3 4.97 Suds suppressor 25.00 1.5 0.06 1Balance to 100% is water unless otherwise noted.
2Balance also includes 10.1% sodium hydroxide, 0.5%
monoethanolamine and 10.1% sodium cumene sulfonate 3Balance also include 5.13% sodium hydroxide and 16.20% ethanol.
4Balance also includes 26.03 monoethanolamine and 45.2% C12 13 alcohol polyethoxylate (6.5)*.
From more than one source 6Premix of cyclomethicone and a silicone suds suppressor (a commercially available silicone/silica fluid containing about 75% polydimethyl siloxane having a viscosity of 20 cs-1,500 cs at 25.0C; about 15%
siloxane resin; and about 10% silica aerogel having an average ultimate particle size of about 12 millimicrons agglomerated to an average of 1.3-1.7 microns and having a surface area of ~325 m2/g) in a weight ratio of 3:1, respectively.
*Alcohol and monoethoxylated alcohol removed.
**Prepared as in Reaction Sequence I.
***Tetraethylene pentaimine ethoxylated with 15-18 moles (avg.) of ethylene oxide at each hydrogen site on each nitrogen.

_ 33 _ l 3 3 3 9 8 3 The above composition is stable and isotropic as made about 70F (21.1C) and has an initial pH of about 8.4 at a concentration of about 10% by weight in water at 68F (20C).

WHAT IS CLAIMED IS:

Claims (11)

1. A heavy-duty liquid detergent composition compris-ing, by weight:
(a) from about 5% to about 15%, on an acid basis, of a sulfonate surfactant containing a C10-C16 alkyl or alkenyl group (b) from about 8% to about 18%, on an acid basis, of an alcohol ethoxylate sulfate surfactant of the formula RO(C2H4O)mSO3M, wherein R is a C10-C16 alkyl or hydroxyalkyl group, m averages from about 0.5 to about 4, and M is a compatible cation;
(c) from about 0.5% to about 7% of an ethoxylated nonionic surfactant of the formula R1(OC2H4)nOH, wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, n averages from about 3 to about 9, and said nonionic surfactant has an HLB of from about 10 to about 13;
(d) from about 1% to about 5% of a C10-C14 satur-ated fatty acid, the weight ratio of C10-C12 fatty acid to C14 fatty acid being at least 1;
(e) from about 1% to about 7%, on an acid basis, of a citrate builder material;
(f) from about 2% to about 8%, on an acid basis, of a tartrate succinate builder material selected from the group consisting of:
i) wherein X is a salt-forming cation;
ii) wherein X is a salt-forming cation; and iii) mixtures thereof;
(g) from about 0 to about 0.04 moles per 100 grams of composition of an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine and triethanolamine;

(h) sodium ions;
(i) from 2% to about 8% of a hydrotrope selected from the group consisting of the water-soluble salts of toluene sulfonate, xylene sulfonate, cumene sulfonate, and mixtures thereof, or a C12-C14 alkenyl succinic acid or salt thereof, or mixtures thereof;
(j) from about 2% to about 18% of propylene glycol; and (k) from about 40% to about 60% water;
said composition containing from about 15% to about 30%
of (a), (b) and (c); from about 5% to about 12% of (e) and (f); from about 8% to about 20% of (d), (e) and (f);
from about 25% to about 50% of (a), (b), (c), (d), (e) and (f); from about 5% to about 12% of (d) and (i): from about 3% to about 18% of (i) and (j) and from about 45%
to about 68% of (i), (j) and (k); the weight ratio of (a) to (b) being from about 0.3 to about 1.7; the weight ratio of (e) plus (f) to (d) being at least about 1-5; and all of said components being selected to provide an isotropic liquid at 70°F (21.1°C) having an initial pH
of from about 7.5 to about 9.0 at a concentration of about 10% by weight in water at 68°F (20°C).

2. The composition of Claim 1 wherein the sulfonate surfactant is a C11-C13 linear alkylbenzene sulfonate;
in the alcohol ethoxylate sulfate surfactant, R is a C12-C15 alkyl group and m averages from about 1.5 to about 3; and in the ethoxylated nonionic surfactant, R
is a C12-C14 alkyl group and n averages from about 3 to about 7.

3. The composition of Claim 2 comprising from about 6%
to about 10% of the sulfonate surfactant, from about 9%
to about 14% of the alcohol ethoxylate sulfate surfac-tant, and from about 1% to about 5% of the ethoxylated nonionic surfactant.

4. The composition of Claim 3 further comprising from about 0.3% to about 1.5% of a C10-C14 alkyl trimethylammonium chloride, bromide or methylsulfate.

5. The composition of Claim 1 comprising from about 2% to about 5% of the citrate builder, and from about 3% to about 6% of the tartrate succinate builder.

6. The composition of Claim 1 wherein the tartrate succinate builder has a weight ratio of i) to ii) of from about 95:5 to about 40:60.

7. The composition of Claim 1 comprising from about 2% to about 5% of cumene sulfonate.

8. The composition of Claim 3 comprising from about 2% to about 5% of the citrate builder, and from about 3% to about 6% of the tartrate succinate builder.

9. The composition of Claim 8 comprising from about 0.01 to about 0.035 moles per 100 grams of composition of the alkanolamine, which is monoethanolamine.

10. The composition of Claim 9 having an initial pH
of from about 7.8 to about 8.8 at a concentration of 10% by weight in water at 68°F (20°C).

11. The composition of Claim 10 wherein the tartrate succinate builder has a weight ratio of i) to ii) of from about 95:5 to about 40:60.