US3392121A - Built detergent compositions - Google Patents

Description

B. H. GEDGE Ill BUILT DETERGENT COMPOSITIONS Filed Sept. 23, 1964 July 9, 1968 MAYA Amvmn v \{g NTA INVENTOR.

Burion H. Gedge lIL Wcwdu ATTORNEY United States Patent 3,392,121 BUILT DETERGENT COMPOSITIONS Burton H. Gedge 1H, Wyoming, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio Continuation-impart of application Ser. No. 235,327,

Nov. 5, 1962. This application Sept. 23, 1964, Ser.

11 Claims. (Cl. 252--136) This invention relates to built detergent compositions of solid and liquid form for heavy duty laundering use, and is based on the discovery of unexpected and remarkable synergistic building actions in mixtures or blends of water soluble inorganic builder salts and one or both of two organic builder materials. This application is a continuation-in-part of copending application Ser. No. 235,-- 327, filed Nov. 5, 1962, and now abandoned.

It has been known that when certain substances are added in relatively large amounts to the active synthetic detergent component or components of washing compositions, an increase in cleaning ability or whiteness maintenance or both is obtained, even though the washing solution used may contain less of the active detergent. Substances capable of producing this effect are known as builders. Cleaning ability is the ability of a solution of the detergent composition to remove soil from cloth. Whiteness maintenance relates to the ability of a detergent solution to prevent suspended soil from depositing on the cloth during the washing operation. The term detergency as used herein is intended to embrace both cleaning ability and whiteness maintenance.

Building effects have been noted in connection with various inorganic salts, such as alkali metal carbonates, bicarbonates, borates, phosphates and silicates. The best of the inorganic builders are the water soluble polyphosphates, and in particular the water soluble pyrophosphates and tripolyphosphates. Of these, sodium tripolyphosphate is the builder most generally used in solid detergent compositions. In the formulation of liquid detergent compositions, water soluble pyrophosphates are generally preferred because of the tendency of tripolyphosphates to hydrolyze in aqueous solution during long periods of storage, forming some pyrophosphate and some orthophosphate, the latter being a less efficient builder and having among other disadvantages a detrimental effect on the softness of the fabrics being treated. In liquid formulations, also, the potassium salts of inorganic builders are sometimes used to take advantage of their greater solubility.

Useful building actions with the water soluble polyphosphates are noted in detergent compositions in which the ratio of active synthetic detergent to polyphosphate extends generally from about 1:1 to 1:10. Currently, the most widely sold built detergent compositions contain from about 1 part to about 7 parts of polyphosphate for each part of active synthetic detergent.

Building actions have also hitherto been noted in connection with certain organic salts.

The nature of the building action is not fully understood. There appears to be a connection between the ability of a builder to soften the water which is used to make up the washing solution, and the improved results in detergency obtained when the builder is used. But not all materials whichact to sequester hardness-imparting calcium and magnesium ions perform satisfactorily as builders. Further, useful building actions with the most effective builders can be noted both above and below the point at which the builder is present in the washing solution in stoichiometric proportions to the hardness in water.

1 Detergency itself is a complex phenomenon believed to involve very many factors. Among the aspects of built "ice detergency systems, with respect to which builders are thought to have useful effects, are such factors as stabilization of suspended solid soils, emulsification of soils, the surface activity of the aqueous detergent solution, the solubilization of water-insoluble materials, foaming or suds producing characteristics of the washing solutions, peptization of soil agglomerates, neutralization of acid soils, and the like, in addition to the sequestration of mineral constituents present in the washing solution. The action, therefore, of different builders varies, and no general basis has been found either in physical properties or in chemical structure upon which one can predict in advance the excellence, ranking or performance of chemical materials or mixtures thereof as detergency builders.

It should also be kept in mind that the effect of any given detergent composition when used in solution to perform a washing operation will vary with such factors as concentration, temperature, the nature of the soil, the nature of the active detergent ingredient, the amount of active ingredient in the solution, the ratio of builder to active ingredient, the hardness of the water and the like. An active ingredient having in itself a low detergency value may appear to be helped more by a given quantity of a given builder than would an active detergent ingredient having superior detersive properties.

The ratio of builder to active detergent in a detergent composition is conveniently expressed in parts by weight. Where a comparison is to be made between a builder material which is a mixture of ingredients in varying proportions, this can often best be done by selecting a suitable active ingredient o-r surfactant, selecting a formulation containing a representative ratio of surfactant to a standard building ingredient, and then making up compositions for use by substituting portions of other builder ingredients for portions of the standard builder ingredient on a molar basis. Test results obtained with the various compositions so produced will be indicative and will be affected by fewer variables than otherwise.

A basic object of the invention is the attainment of an enhanced building action with a corresponding increase in the above noted desirable qualities associated with built detergent compositions. The synergistic action in the detergent compositions to which this invention is addressed manifests itself in improvements in one or more or all of these qualities, but notably in improved whiteness maintenance.

It is an object of the invention to attain an enhanced building action, particularly in heavy-duty laundry detergent compositions which, so far as is known, is the most effective building action ever attained in such compo sitions.

It is an object of the invention to provide a synergistic builder mixture having building properties substantially greater than the additive contributions of the components thereof.

It is an object of the invention to provide detergent compositions which are effective in water solutions over a wide range of concentrations inasmuch as the conditions under which household laundry is done vary quite widely with the individual.

It is an object of the invention to provide detergent compositions in which the proportion of active ingredient can be increased, if desired, without sacrificing building action.

It is an object of the invention to provide detergent compositions which are effective for heavy duty laundering over a Wide range of temperature and in particular at temperatures in the lower part of the range.

According to this invention, these objects are obtained and an unexpected and surprising synergistic building action is displayed by mixtures of a water soluble salt of ethane-l-hydroxy-l, l-diphosphonic acid and a builder selected from the group consisting of water soluble inorganic polyphosphate builders, particularly the soluble salts of tripolyphosphates and pyrophosphates, and water soluble salts of nitrilotriacetic acid, and, preferably mixtures thereof in the proportion-s hereinafter described.

Reference is made to the accompanying drawing which is a ternary diagram illustrating the proportions (on a molar basis) in which the builder mixtures of this invention exhibit a surprising and unexpected synergistic building action as hereinafter described.

The essential organic builder salts of this invention are derivatives of ethane-l-hydroxy-l, I-diphosphonic acid which has the molecular formula CH C(OH) (PO H According to nomenclature by radicals, the acid might also be named l-hydroxyeth-ylidene diphosphonic acid.

The most readily crystallizable form of the builder compound is obtained when three of the acid hydrogens are replaced by sodium. Hence, the salt commonly prepared is the trisodium salt which gives a pH near 9.5 in distilled water. The anhydrous trisodium salt has the structure CHs-(f-OH 3Na+ P Can It crystallizes normally as the hexahydrate, which loses some water during air-drying to yield a mixture of hexaand mono-hydrate averaging 3 to 4 molecules of water of hydration. It is more stable toward hydrolysis than ordinary condensed polyphosphates, and is compatible with them.

While any alkali metal or ammonium or substituted ammonium salt form can be used in the practice of this invention, the tetrasodium salt, the trisodium salt and mixtures thereof are the preferred forms. Mixtures of the tetrasodium and trisodium salts give a pH in water solution from about 9.5 to 11.5. Each of the lesser neutralized forms such as monosodium and disodium derivatives or the free acid have comparable builder capacities to the trisodium and tetrasodium salt forms provided that additional alkali is added to adjust the pH of the washing solution to about 9 to about 12. The standard alkaline materials can be used for this purpose, such as alkali metal silicates, phosphates, borates and carbonates. Free alkali materials such as sodium and potassium hydroxides can also be used. For brevity herein, the soluble salts of ethane-l-hydroxy-l, l-diphosphonic acid will be referred to as EHDP.

The inorganic builder salts of this invention are primarily the sodium and potassium salts of tripolyphosphoric and pyrophosphoric acids. Other inorganic substances may be present in addition, such as those mentioned above. Other soluble salts of tripolyphosphoric and pyrophosphoric acids may be employed such as those utilizing other alkali metals as the cation or a cation chosen from ammonium or substituted ammonium radicals. Sodium or potassium tripolyphosphates have an advantage over sodium or potassium pyrophosphate, especially in whiteness maintenance and in the feel of fabrics washed in solutions thereof; but both are effective builders. For brevity, the inorganic water soluble polyphosphate builder salts are referred to hereinafter as STP, exemplifying sodium tripolyphosphate.

Water-soluble salts of nitrilotriacetic acid have the formula CHzC O OH NCH2O O O H CHzC O O H wherein a suitable cation is substituted for the acidic hydrogens in the above formula, the cation being sodium, potassium, other alkali metals or ammonium or substituted ammonium radicals. The trisodium salt of nitrilotriacetic acid is most generally used. The soluble salts of 4 nitrilotriacetic acid will be referred to herein for brevity as NTA.

It has been found that the builder mixtures of this invention exhibit important building properties with a very wide range of active detergent substances and mixtures thereof, and are compatible with the adjuvants normally used in detergent compositions. The detergent substances include anionic synthetic non-soap detergents, nonionic synthetic detergents, ampholytic synthetic detergents-and zwitterionic synthetic detergents and mixtures thereof. These substances are outlined more at length as follows:

(a) Anionic synthetic non-soap detergents can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical cont aining from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the synthetic detergents which form a part of the preferred compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfa-ting the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, especially those of the types described in United States Letters Patents Numbers 2,220,- 099 and 2,477,383; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium 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 about 8 to about 12 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl tauride in which the fatty acids, for example, are derived from coconut oil; and others known in the art, a number being specifically set forth in United States Letters Patent Nos. 2,486,921, 2,486,922 and 2,396,278.

(b) Nonionic synthetic detergents 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 'r-adical 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.

For example, a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with an hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility,has a molecular weight of from about 1500 to 1800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the Water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates of alkyl phenol-s, 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 said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.

(2) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydro-phobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000, are satisfactory.

(3) The condensation product of aliphatic alcohols having from 8 to 22 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from to 14 carbon atoms.

(4) Long chain tertiary amine oxides corresponding to the following general formula, R R R N- 0, wherein R is an alkyl radical of from about 8 to about 18 carbon atoms, and R and R are each methyl or ethyl radicals. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecyl amine oxide, dimethyloctylamine oxide, dimethyldecyla'mine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide.

(5 Long chain tertiary phosphine oxides corresponding to the following general formula RRR"P- O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are:

dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide, cetyldimethylphosphine oxide, stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide,

dodecyldi (hydroxymethyl) phosphine oxide, dodecyldi (Z-hydroxyethyl) phosphine oxide, tetradecylmethyl-Z-hydroxypropyl phosphine oxide, oleyldimethylphosphine oxide, and 2-hydroxydodecyldimethylphosphine oxide.

(c) Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphate, or phosphono. Examples of compounds falling within this definition are sodium-3- dodecylaminopropionate and sodium-3-dodecylaminopropane sulfonate.

(d) Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxyl, sulfo, sulfato,

' phosphato, or phosphono. Examples of compounds falling hexadecylammonio) -2-hydroxy propane-1-sulfonate which are especially preferred for their excellent cool water detergency characteristics.

The non-soap anionic, nonionic, ampholytic and Zwitterionic detergent surfactants mentioned above can be used singly or in combination in the practice of the present invention. The above examples are merely specific illustration-s of the numerous detergents which can find application within the scope of this invention.

The foregoing synthetic non-soap detergent compounds can be made into any of the several commercially desirable composition forms, for example, granular, flake, liquid and tablet forms.

Also, it will be understood that the compositions may contain adjuvants, diluents and additives, inclusive of germicidal agents, suds boosters, suds depressants, antitarnishing agents, and anti-bacterial agents, and the like without detracting from the advantageous characteristics of the mixtures.

In general, in the compositions of this invention, the essential ingredients are (a) a detergent substance as set forth above and (b) a builder mixture, as hereinafter described more at length.

The specific action of the builder mixtures of this invention will vary to some extent depending upon the ratio of active detergent to builder mixture in any given detergent composition. There will be considerable variation in the strengths of the washing solutions employed by difierent housewives, i.e., some housewives may tend to use less or more of the detergent compositions than will others. Moreover, there will be variations in temperature and in soil loads as between washing operations. Further, the degree of hardness of the water used to make up the washing solutions will also bring about apparent diflerences in the cleaning power and whiteness maintenance results. Finally, diiferent fabrics will respond in somewhat different ways to diiferent detergent com- 7 positions. The best type of detergent composition for houeshold use would in theory be a composition which accomplishes an excellent cleaning and whiteness maintenance effect under the most diverse cleaning conditions. The built detergent compositions of this invention are especially valuable in this respect.

The builder mixtures taught herein are very efficient, and, in general, can be used to permit the attainment of equal detergency with a smaller total quantity of builder in relation to the total quantity of active detergent ingredient. It may be stated that useful degrees of build ing activity may be attained in the practice of this invention with ratios of active ingredient to builder mixture of from about 1:0.5 to about 1:10.

In vew of the wide permissible variations in the ratio of active detergent substance to builder, the best way to demonstrate the synergistic action on which this application is based is to select a good detergent composition containing a widely used inorganic builder-STP- and substitute difierent quantities of EHDP or EHDP and NTA for corresponding quantities of STP on a molar basis. This was done in Example I which follows:

EXAMPLE I A solid, heavy-duty detergent composition was made up according to the following formulation, wherein the percentages are given by weight:

Percent Sodium tallow alkyl sulfate 20 Builder 50 Sodium silicate 6 Sodium sulfate Remainder A series of additional compositions were made up, differing from the above in that various quantities of EHDP or EHDP and NTA were substituted for like quantities of sodium tn'polyphosphate and for each other, on a molar basis. Thus, compositions were made up in which the builder consisted entirely of poly-phosphate, in which the builder consisted entirely of NTA and in which the builder consisted entirely of EHDP, together with intermediate compositions in which the builder mixture contained varying amounts of both EHDP and NTA substituted in molar proportions for molar equivalents of the polyphosphate, as well be evident from the drawing. In some builder mixtures EHDP and NTA completely replaced the polyphosphate. In all the mixtures of builders, at least molar percent of EHDP was present.

These several compositions were tested as follows:

Naturally soiled garments and also whiteness cloths were Washed with the above detergent formulations for ten minutes in an agitator-type washing machine. The water solution had a pH of about and was at 130 F., the water hardness was 7 gr./gal. and the product concentration in the water was 0.10%. After washing, the garments and whiteness cloths were visually compared with similar pieces, sirnilarly soiled, and washed in like detergent formulations differing only in the composition of the builder.

It will be understood that because of the dilference in molecular weight of EHDP, NTA and STP there occurred a progressive small variation in the weight percentage as more and more EHDP or EHDP and NTA was substituted for STP in a molar basis; but all other conditions remained the same. Thus the tests gave a direct comparison between EHDP, NTA, STP and various mixtures of these substances (i.e., EHDP+STP; EHDP-i-NTA; and EHDP+STP+NTA) on a mole-formole basis.

The visual comparison of the washed materials was made by a group of five people for each test who were unfamiliar with the purpose of the test and who formed their judgments independently. Separate comparisons were made for cleaning and for whiteness maintenance. The combined data from the visual judgments were recorded on a scale such that zero represented the cleaning ability or whiteness maintenance of the composition containing STP as the sole builder, and higher values represented the cleaning ability or whiteness maintenance of superior detergent formulations using mixtures of EHDP-i-STP, EHDP-l-NTA or EHDP+NTA+STP. Significant and consistent higher score values demonstrate clearly superiority in the respective areas of cleaning ability and/or whiteness maintenance, each area being a measure of detergency building.

The results of the tests outlined and other tests permitted the drawing of certain conclusions which were used to establish the proportions of builder components of the builder mixtures of this invention as set forth in the triangular diagram of the drawing. The triangular diagram is of the conventional type with each corner representing 100% of the builder component indicated thereon. The lines on the diagram each represent 10 molar percent. The boundaries of the areas of superior builder performance are defined by the following points:

A85% STP; EHDP B-10% NTA; 85% STP; 5% EHDP C84% NTA; 5% EHDP; 11% STP D% EHDP; 80% NTA E80% EHDP; 20% NTA F10% STP; 90% EHDP G-75% STP; 10% NTA; 15% EHDP H-l5% NTA; 75% STP; 10% EHDP I5% EHDP; 44% NTA; 51% STP J10% EHDP; 80% NTA; 10% STP K30% EHDP; 70% NTA L% EHDP; 30% NTA M% EHDP; 10% STP; 10% NTA N30% EHDP; 50% STP; 20% NTA O-20% EHDP; 50% STP; 30% NTA P-20% EHDP; 40% STP; 40% NTA Q30% EHDP; 20% STP; 50% NTA R40% EHDP; 10% STP; 50% NTA S50% EHDP- 10% STP; 40% NTA T50% EHDP; 20% STP; 30% NTA U40% EHDP; 40% STP; 20% NTA Conclusions were as follows:

(1) Any of the three combinations of builder substances (EHDP-l-NTA, EHDP+STP, EHDP+NTA+STP) within the area ABCDEF on the triangular diagram of the drawing gave results superior to EHDP, STP or NTA used alone.

(2) It was found that the superior building results obtained with such combination requires the presence of at least 5 molar percent of EHDP showing that EHDP is a key component in these builder combinations.

(3) As to the binary combinations of EHDP and STP, superior building results were found in the molar ranges of 90% to 15% EHDP and 10% to STP. Especially preferred molar ranges are 85% to 40% EHDP and 15 to 60% STP. The optimum combination is 60% EHDP and 40% STP on a molar basis.

(4) As to the binary combinations of EHDP and NTA, superior building results were found in the molar ranges of 80% to 20% EHDP and 20% to 80% NTA. Especially preferred molar ranges are 70% to 30% EHDP and 30% to 70% NTA. The optimum combination is 50% EHDP and 50% NTA on a molar basis.

(5) An especially preferred range which gives building results not only superior to those afforded by any of the individual components when used alone, but also building results at least equal to any mixtures of STP and EHDP, includes ternary builder mixtures containing EHDP, NTA and STP and binary builder mixtures of EHDP and NTA in the molar proportions within area GHUKLM on the triangular diagram of the drawing. This superiority was particularly demonstrated where the washing was carried on in water having a hardness of 7 grains per gallon and in the area of whiteness maintenance.

(6) Optimum results were obtained in 7 grain water with a builder mixture consisting of STP, NTA and EHDP within area NOPQRSTU on the triangular diagram of the drawing.

It is an advantage of many of the various building mixtures herein disclosed that they may contain substantial quantities of STP which at present is considerably less expensive than the other components.

An increase in the hardness of the water used to make up the washing solution affects the activity of the various builder mixtures described herein. But optimum results can still be attained with harder waters by a shift in the percentages of ingredients, and more particularly by an increase in the relative amount of EHDP as respects the other components or component. For example, where the water used to make up'the washing solution has a hardness of 21 grains per gallon, optimum results can be achieved through the use of a ternary builder mixture containing from 40 to 60% EHDP, the balance of the mixture being made up of STP- and NTA preferably in about equi-molar proportions. By the same token, improved results in waters harder than 7 grain can be achieved Within the ranges set forth above by working toward the upper values of EHDP content or by somewhat increasing the EHDP content at the expense of NTA and STP, or either of them.

It will be understood that the ratio of builder to active ingredient or ingredients can be varied within the range given above for the obtaining of particular results.

It will be understood by the skilled worker in the art that detergent compositions, including the compositions of this invention, will ordinarily contain various ingredients for special purposes. Thus, they can contain suds builders, suds depressants, anti-corrosion agents, antiredeposition agents, dyes, fluorescers, perfumes and the like, without interfering with the basic characteristic of this invention. In the manufacture of liquid detergents, water or alcohol vehicles or mixtures of the two, together with solubilizing agents and the like, as known in the art, can be used. These form no limitation on the invention, but are intended to be includable within the terms of claims calling for compositions consisting essentially of active ingredients and builder mixtures in accordance with the teachings herein.

The detergent compositions of this invention are preferably used to provide a pH in aqueous washing solution within a pH range of about 9 to about 12; the optimum building effects are obtained within this range. Washing temperatures usually range from about 80 F. to about 200 F. Fabrics are preferably rinsed and dried after washing.

Other exemplary compositions are as follows:

EXAMPLE II Percent Sodium dodecylbenzene sulfonate, derived from a polypropylene which is predominantly tetra- This composition gives exceptional results, in both cleaning and whiteness maintenance, especially in water of 7 grain hardness. It provides a pH in washing solution of about 10.

EXAMPLE 111 Percent Sodium dodecylbenzene sulfonate, derived from a polypropylene which is predominantly tetrapropylene 17.3 Builder mixture consisting of equal parts of sodium tripolyphosphate and EHDP on a molar basis 43.5 Sodium silicate 5.9 Sodium sulfate 19.6 Monoethanolamide of coconut oil fatty acids 2.1 Perfume 1.6 Moisture 10.0

Such a composition provides a pH in water solution of about and gives superior heavy duty performance as compared with compositions in which the sole builder was either EHDP or STP. Even further improvement in performance, particularly in cool water, can be obtained by replacing the sodium dodecyl benzene sulfonate with an equal amount of 3-(N,N-dimethyl-N-hexadecylammonio)-propane l-sulfonate or 3-(N,N dimethyl-N- hexadecylammonio) -2-hydroxypropane-l-sulfonate.

Similar good results can be obtained by using as the builder mixture of the composition of Example III, 35.3% of a builder mixture consisting of EHDP and 80% NTA on a molar basis and raising the level of sodium sulfate to 29.6%, and replacing the sodium dodecyl benzene sulfonate with an equal amount of the condensation product of a mole of tallow fatty alcohol and 10 moles of ethylene oxide or sodium 3-dodecyl amino-propane sulfonate.

10 EXAMPLEIV Percent Sodium dodecylbenzene sulfonate (as in Example '11) Sodium toluene sulfonate 2.0

Builder mixture consisting of sodium tripolyphosphate and 20% EHDP on a molar basis 47.4 Sodium sulfate 14.9 Trichlorocarbanilide 0.5 Sodium silicate 6.0 Monomethanolamide of coconut oil fatty acids 1.6 Perfume 1.6 Moisture 6.0

When evaluated in a comparative evaluation test, such a formulation exhibits superior cleaning ability and improved whiteness maintenance when compared to similar formulae in which sodium tripolyphosphate is the sole builder. It provides a pH in washing solution of about 10.

Even superior results are obtained in the composition of Example IV by using as the builder mixture 47.4% of a mixture of 40% EHDP+30% NTA+30% STP or 30% EHDP+40% NTA+30% STP on a molar basis. The sodium salt of linear dodecylbenzene sulfonate can also be used to advantage.

In the above example builder mixtures were used Which consisted, resepectively, of 40%, 50% and 60% EHDP, with the remainder in each case consisting of about equal percentages of STP and NTA on a molar basis. Such compositions provide a pH in washing solution of about 10 and work exceptionally well as regards cleaning and whiteness maintenance in relatively hard water, i.e., water having a hardness of 21 grains or greater, While also giving a good account of themselves in softer waters. Product usage will, of course, be increased as water hardness increases.

As an example of a liquid composition having good cleaning and whiteness maintenance properties which can be made in accordance with the invention and provides a pH of about 10, the following is given:

EXAMPLEVI Percent Sodium dodecylbenzene sulfonate (as in Example II) 9.0 Potassium alkylglyceryl ether sulfonate, the alkyl being derived from a mixture of lauryl and myristyl alcohol 4.0 Potassium pyrophosphate 11. NTA (as potassium salt) 3.75 EHDP (as potassium salt) 3.15 Monoethanolamide of coconut oil fatty acids 3.0 Potassium toluene sulfonate 8.5 Ethanol 4.0 Sodium silicate 4.5 Water, fiuorescers, etc. Balance A similar good heavy duty liquid composition can be obtained by substituting for the 18% total builder in the above formula 18% of the following builder mixtures:

A. Equal parts (on a molar basis) of potassium pyrophosphate and EHDP;

B. 40% NTA and 60% EHDP on a molar basis.

1 1 l 2 In the following examples the A columns represent duty laundering system. Moreover, a builder mixture of conventional built compositions; the B columns represent equal molar portions of EHDP and =NTA can advantagecompositions in which the builders of the A composiously be employed in a washing solution containing sotions are replaced on an equal molar basis with builder dium tallow alkyl sulfate and STP in 1:3 ratio by weight,

mixtures of this invention and which provide a pH of 10: 5 e mi e of EHIDP and NBA being added in an amount by Weight equal to that of the STP in solution.

VII VH1 IX Modifications may be made in the invention without departing from the spirit of it. The invention having been A B A B A B described in certain exemplary embodiments, what is Sodium tetrapropylene claimed as new and desired to be secured by Letters benzene sulionate 35 35 17 17 10 10 Pate t Sodium tallow alcohol n 1 sulfate 0 0 1. A builder mixture composition conslsting essentially 2'15 g g 50 20 50 so of o umpyrop osp a e NTA 11.98 13.95 8.73 (a) the trisodium salt of ethane-l-hydroxy-l,l-drphos- EHDP 3.18 7.4 5. 55 honic acid and Sodium silicate 6 6 6 6 6 6 p Monoethauolamide of (b) a builder selected from the group consiting of sotiiini uiiitfffiiii::fsaf'iai." B31. B a. "sari-in. sodium tripolyphosphate and sodium py p p the trisodium salt of nitrolotriacetic acid, and mix- The builder mixtures of the B compositions had the thereof following molar proportions: in which the molar proportions of the components of said VIIB50% STP+sodium pyrophosphate, 40% NTA, builder mixture are within the area ABCDEF on the tri- 10% EHDP; 1 angular diagram of the drawing, said composition provid- VIIIB40% STP, 40% NTA, 20% EHDP; ing in water solution a pH in the range of about 9 to IX-B60% STP, NTA, 15% EHDP. about 12.

In the laundering of naturaly soiled fabrics, continued 25 2. A built detergent composition consisting essentially use of compositions VII-B, VIII-B and IX-B will .proof sodium tallow alkyl sulfate and the builder mixture vide cleaning and whiteness maintenance superior to cornof claim 1 in which the ratio of alkyl sulfate to builder positions VII-A, VIII-A and IX-A, even though the B mixture is substantially 1:05 to 1:10 by weight. compositions contain, respectively, about 3%, about 9% 3. The composition claimed in claim 1 wherein the and about 6% less builder by weight. builder mixture contains subtantially equal proportions Additional examples of detergent compositions emof said tripolyphosphate salt and said salt of nitrilotriacetic ploying the builder mixtures of this invention are shown acid making up about 60 to 40 percent of the mixture, in the table below, wherein the .pH of the compositions With ingredient (a) making up about 40 to 60 percent in water solution is about 10, and the numbers are perthereof, all on a molar basis. centages by weight. These examples demonstrate some 4. A builder mixture composition consisting essentially of the builder-active detergent combinations which can f be made. These are then preferably formulated with the (a) the trisodium salt of ethane-l-hydroxy-l,l-diphosvarious other materials normally found in complete dephonic acid,

tergent products such as antiredeposition agents, sodium dium trip lyphosphate, and silicate, perfume, suds depressants and the like. The total the trisodium salt of nit-rolotriacetic acid actlve P builder can Vary wldely- In normal general and in which the molar proportions of the components of P p detergents this total amounts to 5090% of the said builder mixture are within the area GHIJKLM on complete product. In th soall d l g t y Products the triangular diagram of the drawing, said composition and in liquids, the sum is often considerably less, the providing in water solution a pH in the range of about balance usually being a diluent such as water. 9 to about 12.

X XI XII XIII XIV XV XVI XVII XVIII XIX XX Builder mixture of 40% EHDP plus 30% NTA plus 30% STP on a mo ar Dodecylmethyl sulfoxide 15 Dodecyldimethyl phosphiue oxide 25 -20 condlensation product of one mole of dodeeauol and 6 moles of ethylene 2 oxi e t 15 5 Condensation product of one mole of tridecyl phenol and 10 moles of ethylene oxide 20 3-(N,N-dimethyl-N hexadecyl ammonio) propane-1-sulfonate .t 35 3-(N,N-dimethyl-N dodecylammonio) 2-hydroxy propane l-sulfonate 15 15 Disodium dodecyl fl-irm'no dipropionate Sodium 3-dodecylamiuoprop ane sull'onate. (N,Ndimethyl-N dodecyl ammonio) acetat Reaction product of dodecylamiue with sod th uate (U 1 Patent 2,658,072) 10 Excellent detergent compositions can also be prepared 5. The composition claimed in claim 4 wherein the by using in each of the above Examples X-XX a builder molar proportions of the components of said builder mixmixture of EHDP+'-5()% NTAtmolar percentages) ture are within the area NOPQRSTU on the triangular or a builder mixture of 50% EHDP+50% STP (molar diagram of the drawing.

percentages) instead of the recited ternary builder mix- 6. A built detergent composition consisting essentiall ture. of sodium tallow alkyl sulfate and the builder mixture Any of the builder mixtures diclosed herein, especially of claim 4 in which the ratio of alkyl sulfate to builder those in each of the examples, can be used beneficially mixture is substantially -1:0.5 to 1:10 by weight. as an additive to washing solutions containing an organic 7. A built detergent composition consisting essentially synthetic detergent with little or none of conventional of sodium tallow alkyl sulfate and the builder mixture builders. For example, a builder mixture of 40% of claim 5 in which the ratio of alkyl sulfate to builder EHDP+30% NTA +30% STP (molar percentages), mixture is substantially 1:0.5 to [1:110 by weight.

can be added to a washing solution of sodium linear do- 8. A builder mixture composition consisting essentially decyl benzene sulfonate to provide an outstanding heavy 7 5 of 13 (a) the trisodium salt of ethane-1-hydroxy1,1-diphosphonic acid, and (b) sodium tripolyphosphate,

in which the molar proportions of the components of said builder mixture are 90% to 15% component (a) and to 85% component (b), said composition providing in water solution a pH in the range of about 9 to about 12.

9. The composition claimed in claim 8 wherein the said molar proportions are 85% to 40% component (a) and to 60% component (b).

10. A builder mixture composition consisting essentially of (a) the trisodium salt of ethane-l-hydroxyl,l-diphosphonic acid, and

(b) the trisodium salt of nitrilotriacetic acid in which the molar proportions of the components of said builder mixture are 80% to component (a) and t 20% to 80% component (b), said composition providing in Water solution a pH in the range of about 9 to about 11. The composition claimed in claim 10 wherein the said molar proportions are 70% to component (a) and 30% to component (b).

References Cited UNITED STATES PATENTS 3,151,084 9/1964 Schiltz et a1. 252-137 3,159,5 8'1 "12/1964 Diehl 252-152 3,122,417 2/1964 Blaser et a1. 26046 1.310

FOREIGN PATENTS 1,072,346 '12/ 1964 Germany.

889,670 2/ 1962 Great Britain. 1,082,235 5/ 1960 Germany.

927,617 5/1963 Great Britain. 1,107,207 5/ 1961 Germany.

925,373 5/1963 Great Britain.

LEON D. 'ROSDOL, Primary Examiner.

20 ALBERT T. MYERS, JULIUS GREENWALD, MAYER WEINBLATT, Examiners.

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