US3368978A - Builder compositions and detergent compositions using same - Google Patents

Description

United States Patent 3,368,978 BUILDER COMPOSITIGNS AND DETERGENT COMPOSITIONS USING SAME Riyad R. Irani, St. Louis, Mo., assignor to Monsanto Company, St. Louis, Mo, a corporation of Delaware N0 Drawing. Filed Dec. 28, 1964, Ser. No. 421,603

19 Claims. (Cl. 252-137) I ABSTRACT OF THE DISCILOSURE A heavy duty detergent composition consisting essentially of a surface active agent selected from the group consisting of anionic, nonionic, and amphoteric synthetic detergents and mixtures thereof and, as a builder, a composition consisting essentially of (a) from about 3% by weight to about 16% by weight of certain organic sequestering agents, (b) from about 30% by weight to about 80% by weight of sodium tripolyphosphate, and (c) from about 15% by weight to about 55% by weight of an alkali metal salt, said percents by weight being based upon the total weight of the builder composition; the weight ratio of the surface active agent to the builder composition in the detergent composition being from about 2:3 to about 1:5.

This invention relates to builder compositions which impart improved cleaning efficiency to detergents. More particularly it rel-ates to improved heavy duty detergent compositions employing novel builder compositions.

Heavy duty detergents are one of the general types of detergents on the market and are particularly suited for diflicult laundering problems, such as cleansing of heavily soiled clothes. They are normally comprised of an active, that is, a surface active agent of the anionic, nonionic or amphoteric type or mixtures of these and a polyphosphate as a builder to increase the cleansing efficiency of the active. Sodium tripolyphosphate is the most commonly used polyphosphate builder for heavy duty detergents; however, sodium tripolyphosphate suffers several serious handicaps. For example, sodium tripolyphosphate is known to be hydrolytically unstable and degrades in aqueous solutions. As another example, certain algae in bodies of water, are believed to be aided in their growth by the degraded products of tripolyphosphate. Excessive algae growth in streams, lakes and the like, have created problems, as for example, by detracting from the appearance of the water and limiting activities thereon, and it is sometimes necessary to use costly chemical treatment or physical removal treatments. Because of problems, such as the foregoing, considerable research effort has been directed toward finding a builder which would impart equal or better cleaning efiiciency to an active for heavy duty synthetic detergent applications and would reduce, minimize or obviate the handicaps of sodium tripolyphosphate. A number of builders and builder compositions have been proposed or tried in the past; however, those which exhibit good building action are relatively expensive and thus would add appreciably to the cost of the heavy duty detergent if employed as a replacement for sodium tripolyphosphate. Thus, sodium tripolyphosphate is believed to be unrivaled as a builder for heavy duty detergent, especially on a price-performance basis.

As can be appreciated, therefore, an economical builder 3,368,978 Patented Feb. 13, 1968 composition which imparts a better cleaning efliciency to detergents than the commonly used builder, sodium tripolyphosphate, and which reduces, minimizes or obviates the handicaps of sodium tripolyphosphate would be a significant advancement in the art.

It is therefore an object of this invention to provide a builder composition which imp-arts improved cleaning efiiciency to detergents.

It is another object of this invention to provide an improved heavy duty detergent composition employing a novel builder composition.

It is a further object of this invention to provide an improved heavy duty composition containing a novel builder composition which imparts a better cleaning efiiciency to detergents than the commonly used, builder, sodium tripolyphosphate.

It is still another object of this invention to provide an economical builder composition for heavy duty detergents which reduces, minimizes or obviates the handicaps of the commonly used builder, sodium tripolyphosphate.

These and still further objects of the present invention will become readily apparent to one skilled in the art from the following detailed description.

The present invention, comprising (a) an organic sequestering agent, (b) sodium tripolyphosphate and (c) an inorganic alkali metal salt, provides compositions useful for imparting improved builder action to synthetic surface active agents of the anionic, nonionic and amphoteric types and mixtures of the actives when the foregoing components of the builder composition are combined in proper amounts; all of which will be more fully discussed hereinafter. The builder composition of this invention when compared to the commonly used heavy duty detergent builder, sodium tripolyphosphate, has been found to exhibit not only superior performance and at present prices superior performance on a price-performance basis, but also to reduce, minimize or obviate many of the limitations of sodium tripolyphosphate. Organic sequestering agents and the inorganic alkali metal salts used in this invention are hydrolytically stable, and do not degrade in aqueous solutions. Since in the practice of this invention the organic sequestering agent and inorganic alkali metal salt can be used in amounts up to by weight of the builder, the promotion of algae growth that is attributed to the use of sodium tripolyphosphate as a builder can be reduced. As can be appreciated, a composition comprised of the foregoing components which include as a substitute for a portion of sodium tripolyphosphate a relatively inexpensive alkali metal salt and with the components exhibiting a synergistic action to yield a builder which gives performance superior to sodium tripolyphosphate is believed to be totally unexpected.

The organic sequestering agents useful in practicing this invention are the amino polycarboxylic acids, the amino -tri (lower alkylidenephosphonic) acids, the alkylene diphosphonic acids, the water soluble salts of the foregoing acids and mixtures thereof.

Amino polycarboxylic acids are represented by thev where R is a member selected from the group consisting of the radicals where R is a member selected from the group consisting of hydrogen, lower alkyl (1-4 carbon atoms), hydroxy substituted lower alkyl, phenyl and hydroxy substituted phenyl, and R is a member selected from the group consisting of hydrogen lower alkyl (l4 carbon atoms), and hydroxy substituted lower alkyl.

Compounds illustrative of the amino polycarboxylic acids include nitrilo triacetic acid, ethylenediamine tetraacetic acid, diethylenetriamine penta-acetic acid, 1:2:diaminocyclohexane tetra-acetic acid, hydroxyethyl amino diacetic acid, hydroxyethyl ethylene diamine triacetic acid, orthohydroxyl phenyl ethylene diamine triacetic acid, anthranilic-N-N-diacetic acid, tris (hydroxymethyl) diethylene triamine diacetic acid, c-dibutyl-nitrilo triacetic acid and c-cyclohexenyl-nitrilo triacetic acid.

Amino tri (lower alkylidenephosphonic acids) are represented by the general structure amino amino amino amino amino amino amino amino (methylenephosphonic acid) (ethylidenephosphonic acid) (isopropylidenephosphonic acid) (butylidenephosphonic acid) (propylidenephosphonic acid) tri (tert-arnylidenephosphonic acid) tri (isoamylidenephosphonic acid) tri (sec butylidenephosphonic acid) Alkylene diphosphonic acids are represented by the general structure where X is a member selected from the group consisting of hydrogen and lower alkyl group (1-4 carbon atoms), Y is either hydrogen, hydroxyl, a halogen, especially chlorine, bromine and fluorine, or lower alkyl group (1-4 carbon atoms), and n is an integer from 1 to 6.

Compounds illustrative of alkylene diphosphonic acids include:

methylenediphosphonic acid ethylidenediphosphonic acid 1 hydroxyl, ethylidenediphosphonic acid hexamethylenediphosphonic acid isopropylidenediphosphonic acid butylidenediphosphonic acid hydroxylmethylenediphosphonic acid 1 hydroxyl, propylenediphosphonic acid amylidenediphosphonic acid tri(Z-hydroxy, 3 methyl, 4 bromo 4 hexylidene) diphosphonic acid pentamethylenediphosphonic acid penta (propylidene) diphosphonic acid tetra (l-hydroxyethylidene) diphosphonic acid hexa (3-hexylidene) diphosphonic acid tri (Z-hydroxy, 3 amylidene) diphosphonic acid tetra (2- amylidene) diphosphonic acid di (2 methyl, 3 hexylidene) diphosphonic acid tetra (4 octylidene) diphosphonic acid penta (2 propylidene) diphosphonic acid tri (Z-hydroxy, 3 methyl, 4 chloro, 4 butylidene) diphosphonic acid It is to be understood that although the sodium salts of the amino tri(lower alkylidenephosphonic acids), alkylenediphosphonic acids, and aminopolycarboxylic acids are preferred, other water soluble salts such as potassium, lithium, and the like, as well as mixtures of the alkali metal salts may be substituted therefor. In addition, the ammonium salts, as well as amine salts, may be used to practice this invention.

Compounds illustrative of these salts include the following:

Aminopolycarboxylates monopotassium nitrilotriacetate pentasodium diethylenetriamine penta-acetate diammonium ethylenediaminetetra-acetate dirnethylamino diethylenetriaminetetra-acetate trilithium nitrilotriacetate disodium diethylenetriamine penta-acetate tripotassium ethylenediarninetetra-acetate diethylamino nitrilotriacetate pentapotassium diethylenetriarnine penta-acetate monosodium nitrilotriacetate tetrasodiurn ethylenediaminetetra-acetate Amino tri (lower alkylidenephosphonates) disodium amino tri (methylphosphonate) dipotassium amino tri (methylphosphonate) diammonium amino tri (methylphosphonate) pentasodium amino tri (methylphosphonate) dilithium amino tn' (ethylidenephosphonate) diammonium amino tri (ethylidenephosphonate) pentasodium amino tri (isopropylidenephosphonate) pentapotassium amino tri (butylidenephosphonate) diammonium amino tri (isopropylidenephosphonate) disodium amino tri (butylidenephosphonate) diethylamine amino tri (methylphosphonate) dimethylamine amino tri (ethylidenephosphonate) Alkylenediplzosphonates monolithium methylenediphosphonate dipotassium methylenediphosphonate diethylamine methylenediphosphonate triammonium methylenediphosphonate tetrasodium methylenediphosphonate trisodium 1 hydroxy ethylidenediphosphonate trisodium tri (2 hydroxy, 3 amylidene) diphosphonate monopotassium ethylidenediphosphonate dimethylamine ethylenediphosphonate tripotassium amylidenediphosphonate tetrasodium butylidenediphosphonate diammonium isopropylidenephosphonate monosodium amylidenediphosphonate tripotassium ethylidenediphosphonate The builder composition of this invention may be used with any of the anionic, nonionic or amphoteric type synthetic surface active agents and mixtures of these surface active agents.

Anionic synthetic surface active agents, that is nonsoap detergents, are generally described as those compounds which contain hydrophilic and lyophilic groups in their molecular structure and ionize in an aqueous medium to give anions containing both the lyophilic group and hydrophilic group. The alkyl aryl sulfonates, the alkane sulfates and sulfated oxyethylated alkyl phenols are illustrative of the anionic type of surface active compounds.

The alkyl aryl sulfonates are a class of synthetic anionic surface active agents represented by the general formula where R, is hydrogen or a straight or branched chain hydrocarbon group of from 1 to 4 carbon atoms; R is a straight or branched chain hydrocarbon radical having from about 1 to about 24 carbon atoms, at least one R having at least 8 carbon atoms; n is from 1 to 3; n is from 1 to 2; Ar is a phenyl or a naphthyl radical and M is either hydrogen, an alkali metal, such as sodium, potassiumth and the like; ammonium, or an organic amine such as entanol amine, diethanol amine, triethanol amine and hexylamine and the like. R,, can be for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and the like. R can be, for example, methyl, ethyl, hexyl, octyl, tertoctyl, iso-octyl, nonyl, decyl, dodecyl, octadecyl and the like.

Compounds illustrative of the alkyl aryl sulfonates include sodium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, ammonium methyl dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, sodium octadecylbenzene sulfonate, sodium nonylbenzene sulfonate, sodium dodecylnaphthalene sulfonate, sodium heptadecylbenzene sulfonate, potassium eico-sosyl naphthalene sulfonate, ethylamine undecylnaphthalene sulfonate and sodium docosylnaphthalene sulfonate.

The alkyl sulfates are a class of synthetic anionic surface active agents represented by the general formula where M is either hydrogen, an alkali metal, such as sodium, potassium and the like, ammonium or an organic amine, such as ethanolamine, diethanolamine, triethanolamine, ethylenediamine and diethylenetriamine, and the like; and R is a straight or branched chain saturated hydrocarbon radical, such as octyl, decyl, dodecyl, tetradecyl and hexadecyl, as well as the mixed alkyl radicals derived from fatty oils, such as coconut oil, tallow, cottonseed oil and fish oil. R usually has from 8 to 18 carbon atoms.

Compounds illustrative of alkyl sulfate class of anionic surface active agents include sodium octadecyl sulfate, sodium hexadecyl sulfate, sodium dodecyl sulfate, sodium nonyl sulfate, ammonium decyl sulfate, potassium tetradecyl sulfate, diethanolamino octyl sulfate, triethanolamine octadecyl sulfate and ammonium nonyl sulfate.

The sulfated oxyethylated alkylphenols are a class of synthetic anionic surface active agents represented by the general formula where R is a straight or branched chain saturated hydrocarbon group having from about 8 to about 18 carbon atoms, such as a straight or branched group, such as octyl, nonyl, decyl, dodecyl and the like; A is either oxygen, sulfur, a carbonamide group, thiocarbonamide group, a carboxylic group or thiocarboxylic ester group, x is an integer from 3 to 8 and M is either hydrogen, or an alkali metal such as sodium, potassium and the like, or ammonium, or an organic amine, such as ethanolamine, diethanolamine, triethanolamine, ethylene diamine and the like.

Compounds illustrative of the sulfated oxyethylated alkyl phenol class of anionic surface active agents include ammonium nonylphenoxy tetraethylenoxy sulfate, sodium dodecylphenoxy tn'ethyleneoxy sulfate, et-hanolamine decylphenoxy tetraethyleneoxy sulfate and potassium octylphenoxy triethyleneoxy sulfate.

Nonionic surface active compounds can be broadly described as compounds which do not ionize but acquire hydrophilic characteristics from an oxygenated side chain such as polyoxyethylene and the lyophilic part of the molecule may come from fatty acids, phenol, alcohols, amides or amines. The compounds are usually made by reacting an alkylene oxide such as ethylene oxide, butylene oxide, propylene oxide and the like, with fatty acids, a straight or branched chain alcohol, phenols, thiophenols, amides and amines to form polyoxyalkylene glycol ethers and esters, polyoxyalkylene alkyl phenol and polyoxyalkylene thiophenols, and polyoxyalkylene amides and the like. It is generally preferred to react from' about 3 to about 30 moles of alkylene oxide per mole of the fatty acids, alcohols, phenols, thiophenols, amides or amines.

Illustrative of these synthetic nonionic surface active agents are the products obtained from the reaction of alkylene oxide with an aliphatic alcohol having from 8 to 18 carbon atoms, such as oxtyl, nonyl, decyl, octadecyl, dodecyl, tetradecyl and the like; with an alkyl phenol in which the alkyl group contains between 4 and 20 carbon atoms, such as butyl, dibutyl, amyl, actyl, dodecyl, tetradecyl and the like; and with an alkyl amine in which the alkyl group contains between 1 to 8 carbon atoms.

Compounds illustrative of synthetic nonionic surface active agents include the products obtained from condensing ethylene oxide or propylene oxide with the following: propylene glycol, ethylene diamine, diethylene glycol, dodecyl phenol, nonyl phenol, tetradecyl alcohol, N-octadecyl diethanolamide, and N-dodecyl monoethanolamide.

Amphoteric surface active compounds can be broadly described as compounds which have both an anionic and cationic group in their structure. Illustrative of the amphoteric compounds are the amido alkane sulfonates which are represented by the general formula where M is either hydrogen, an alkali metal, such as sodium, potassium, and the like or ammonium, n is an integer from 1 to 5, R is an alkyl radical with from 8 to 18 carbon atoms, and R is a member selected from the group consisting of hydrogen, alkyl, aryl or alicyclic radicals.

For example, the C-aliphatic substituted, N-aliphatic substituted, amido alkyl sulfonates are illustrative of the amido alkane sulfonates. Compounds illustrative of these include; sodium C-pentadecyl, N-methyl amido ethyl sulfonate; sodium C-tridecyl, N-methyl amido ethyl sulfonate; ammonium C-decyl, N-dodecyl amido pentyl sulfonate; potassium C-hexadecyl, N-propyl amido prop-yl sulfonate; and potassium C-tridecyl N-hexyl amido methyl sulfonate.

In addition the C-aliphatic substituted, N-aryl substituted, amido alkyl sulfonates are illustrative of the amido alkane sulfonates. Compounds illustrative of these include: sodium C-dodecyl N-benzene amido methyl sulfonate; potassium C-octyl N-naphthalene amido propyl sulfonate; sodium C-hexadecyl N-benzene amido pentyl sulfonate and ammonium C-tetradecyl N-naphthalene amido methyl sulfonate.

Also, the C-aliphatic substituted, N-cycloalkyl substituted, amino alkyl sulfonates are illustrative of the amido alkane sulfonates. Compounds illustrative of these include: sodium C-dodecyl, N-cyclopropyl amido methyl sulfonate; potassium C-tetradecyl, N-cyclohexyl amido ethyl sulfonate; ammonium C decyl, N-cyclopropyl amido 7 butyl sulfonate and sodium C-octyl, N-cyclohexyl amido methyl sulfonate and the like.

Detergent composition, employing an anionic, nonionic, amphoteric type synthetic surface active agent and mixtures of these and the builder composition of this invention in weight ratios of active to builder of from about 2:3 to about 1:5, give excellent cleaning efficiency when used in aqueous solutions in conventional weight concentrations of about 0.2% or below. It has been found that the ranges or parts by weight of the components in the builder composition of this invention are important and the following ranges in parts by weight in the builder should be followed: (a) from about 3 parts to about 16 parts of an organic sequestering agent, (b) from about 30 parts to about 80 parts by Weight of sodium tripolyphosphate and (c) from about 15 parts to about 55 parts of an alkali metal inorganic salt selected from the group consisting of sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate and mixtures thereof.

The invention is not to be limited to any particular method of preparing a detergent containing the builder composition of the present invention and the surface active agent as described herein. The builder composition can be crutched in the active in form of a slurry and the active agent as described herein. The builder composition can be crutched in the active in form of a slurry and the active and builder dried together by any conventional means of drying, such as spray drying. The active and builder can both be dissolved in an aqueous solution and dried together, such as by drum drying and the like, to form the detergent composition. In addition, the active and builder composition can be mixed together each in the solid form by any conventional means of mixing solids such as mills, ribbon mixers and the like. Still another means of mixing the active and builder compositions is to dry one or two of the components of the builder composition along with the active by any of the before mentioned drying methods and mix the remaining component or components to the resulting solid.

An additional method of using the builder and active to achieve the desired cleaning results is to add each component of the detergent, the active and the three components of the builder, to form an aqueous solution of desired concentration. In any event the builder is intended to be used in conjunction with the active at the time the resulting detergent composition is used as a cleaning agent. In addition, the sodium tripolyphosphate can be incorporated into the detergent by using sodium trimetaphosphate and sodium hydroxide which reacts in the crutching step to form sodium tripolyphosphate. A suitable method for the use of sodium trimetaphosphate and sodiom hydroxide is shown in Example IV.

A detergent composition in accordance with this invention need only contain a surface active agent of classes described and a builder composition as hereinbefore described. However, incorporating additional additives, such as antiredeposition agents, brightening agents, corrosion inhibitors, perfume and the like, is contemplated as being within this invention. These additives are generally used in amounts of up to about by weight of the detergent composition. Compounds such as sodium carboxymethyl cellulose and methyl cellulose are generally classified as antiredeposition agents and are normally found in amounts of below about 2% by Weight in the detergent composition. Some heavy duty detergent compositions contain from about 1 to about 7% by Weight of a corrosion inhibitor such as sodium silicate. Other additives for special purposes such as brightening agents, perfume and the like are normally below about 1% by Weight in the detergent composition.

To illustrate the invention the following examples are presented. All parts and percentages are by weight unless otherwise indicated.

EXAMPLE I Ten detergent com ositions were prepared. by admix- 8 ing 20 parts by weight of sodium dodecylbenzene sulfonate and parts by Weight of various builders. The various builder ingredients in weight percentages are given below.

TABLEI Ingredients, Percent Builder 1--- 50 Builder 2..- 75 Builder 3 50 Builder 4- 50 Builder 5.-- 25 Builder 6... Builder 7 50 Builder 87..

Builder 9- 94 Builder 10 Legend: STP--Sodium tripolyphosphate; A'IltlP-Pentasodium salt of amino tri (methylenephosphonic acid); EDIA-Disodium salt of ethylene diamine tetraacetic acid; NIA-Trisodiurn salt of nitrilotriacetic acid; N 32804-S0di11l11 sulfate.

EXAMPLE II detergent (using as a builder, sodium tripolyphosphate above) and the indicated detergent compositions were compared using as a basis, an industry standard, Duponol WA (sodium lauryl sulfate) in 50 p.p.m. hardness. In each test the cleaning efiiciency of the control detergent (using as a builder, sodium tripolyphosphate alone) was rated as 100. The Comparative Cleaning Efficiency given in the following tabulated results indicates the cleaning efliciency of the indicated detergent compositions using the indicated builder prepared in Example I as compared to the control detergent as a basis.

1 Control.Detergent composition comprising 20? by weight sodium dodocylbenzeno sulfonate and 80% by weight sodium iripolyphosphato.

The results of the above tests dramatically illustrate that a builder composition comprising an organic sequestering agent, sodium tripolyphosphate and an alkali metal salt when used in proper amounts, imparts an excellent cleaning efficiency to detergents which is totally unexpected. In addition, the results show that the building properties of the builder composition of this invention are superior to sodium tripolyphosphate.

More particularly, the detergent compositions using builder compositions l, 2, 3 and 4, illustrative of the builder compositions of this invention, exhibited appreciably better cleaning efiiciency than the control deter- 9 gent composition using sodium tripolyphosphate as is shown by the results of Tests A, B, Cand D.

The results of these tests further show that the improved cleaning cfiiciency imparted to the detergents by the builder composition of this invention would not be predicted. More particularly, the results show that sodium sulfate either alone or in combination with sodium tripolyphosphate does not exhibit building properties equal to sodium tripolyphosphate alone. For example, the detergents using builders 6, 7 and 8 had less cleaning efiiciency in Test C than the control detergent using sodium tripolyphosphate as a builder. Builders 6 and 7, using sodium sulfate and sodium tripolyphosphate together, were from 92% to 99% as effective as a builder as sodium tripolyphosphate. Further, sodium sulfate alone in only 65% as effective as a biulder as sodium tripolyphosphate alone, as is illustrated by the cleaning effectiveness of the detergent using Builder 8 in Test C. also, the builder compositions with an organic sequestering agent in combination with either sodium sulfate or sodium tripolyphosphate does not have building properties equal to sodium tripolyphosphate. For example in Test E, Builder 10, a combination of pentasodium amino tri (methylene phosphonate) and sodium sulfate, was only 78% as effective as a detergent builder as sodium tripolyphosphate alone. Similarly, in Test D, Builder 9, with pentasodium amino tri (methylene phosphonate) and sodium tripolyphosphate, was only 97% as effective as a detergent builder as sodium tripolyphosphate. From the results of the tests of Builders 6, 7, 8, 9 and 10, one would predict that a builder comprising an organic sequestering agent, sodium tripolyphosphate and sodium sulfate would be inferior to sodium tripolyphosphate alone. It is therefore completely unexpected that a builder appreciably superior to sodium tripolyphosphate is produced by combining the three components of this invention in proper amounts.

In addition, the results of these tests show that it is necessary to have the proper proportions of an organic sequestering agent, sodium tripolyphosphate and an inorganic alkali metal salt in the builder to achieve the improved building efiiciency. For example, the results of Test B show that Builder was only 95% as efficient as a builder as sodium tripolyphosphate while Builders 1 and 2 were 104% and 105% as efiicient as sodium tripolyphosphate. Therefore, to achieve the benefits of increased builder efficiency it is necessary to control the amounts of each component Within the ranges specified herein. More particularly, it is necessary to have a weight percentage range of an organic sequestering agent in the builder from about 3% to about 16%, a weight percentage range of sodium tripolyphosphate in the builder fromabout 30% to about 80%, and a weight percentage range of an inorganic alkali metal inorganic salt in the builder from about to about 55%.

EXAMPLE III Ingredients: Parts Active-Sodium dodecyl sulfate 20 Builder 1 20 Percent 1 Com osi'tion of builder:

- l odium-tripolphosphate 75 Tris-odium nitrilo triacetate Sodium sulfate The above detergent gives good cleaning results when used in concentrations of about 0.2% by weight in aqueous solutions in conventional automatic washing machines for laundering clothes and the like.

Other comparable detergent compositions can be prepared in the same manner as described above by replacing trisodium nitrilo triacetate with similar amounts of other organic sequestering agents useful in practicing this invention and in like manner, that is, using similar amounts, other alkali metal alkyl sulfates can :be substituted for sodium dodecyl sulfate. For example, disodium ethylene diamine tetra-acetate, pentasodium amino tri (methylene phosphonate), tetrasodium methylene diphosphonate and pentasodium diethylenetriamine pentaacetate can be substituted for trisodium nitrilo triacetate in the foregoing builder composition and sodium octadecyl sulfate, sodium hexadecyl sulfate, potassium nonyl sulfate potassium decyl sulfate can be substituted for sodium dodecyl sulfate, and the resulting detergent compositions give good results when used for laundering clothes under the same conditions as the detergent compositions of this example.

EXAMPLE IV Four thousand parts of water, 1800 parts of sodium dodecylbenzene sulfonate, 1200 parts of sodium dodecyl sulfate, 2000 parts of sodium sulfate, 5200 parts of sodium trimetaphosphate, 400 parts of tetrasodium methylene diphosphonate and 60 parts of sodium carboxymethyl cellulose are charged into a conventional mixing vessel to form a slurry and the resulting slurry is heated to C. 2720 parts of 50% aqueous sodium hydroxide solution is charged into the slurry. The heat from the reaction evaporates most of the free water in addition to converting the sodium trimetaphosphate into sodium tripolyphosphate. After completing the drying by using heated air, a heavy duty detergent is formed having the following composition.

Additive-Sodum carboxymethyl cellulose 0.6

The above detergent gives good cleaning results in home clothes laundering applications using conventional automatic Washing machines when used in concentrations of about 0.2% by weight in aqueous solutions.

Other comparable detergent compositions can be prepared in the same manner as described above by replacing tetrasodium methylene diphosphonate with similar amounts of other organic sequestering agents useful in practicing this invention. For example, similar amounts of disodium ethylene diamino tetra-acetate, trisodium nitrilo triacetate, pentasodium diethylenetriamine pentaacetate, pentasodium amino tri(methylene phosphonate), dipotassium amino trimethylene phosphonate and dipotassium methylene diphosphonate can be substituted for tetrasodium methylene diphosphonate in the foregoing builder composition and the resulting detergent composition gives good results when used for home clothes laundering under the same conditions as the detergent composition of this example.

EXAMPLE V A builder composition comprisng 680 parts sodium tripolyphosphate, 40 parts nitrilotriacetic acid, 30 parts sodium carbonate and 370 parts sodium sulfate is prepared by admixing the four anhydrous compounds in a conventional ribbon mixer.

1120 parts of the above builder composition, 280 parts sodium dodecylbenzene sulfonate and 1600 parts water are charged into a conventional detergent crutcher. The resulting mixture is stirred and heated by steam to above 85 C. The slurry is pumped to a conventional spray drying tower where it is heat dried to form a heavy duty detergent.

The resulting detergent composition performs well cleaning clothes in home laundry application when used in conventional automatic washing machines in concentrations of about 0.2% by weight in aqueous solutions.

EXAMPLE VI A detergent composition is prepared by admixing in a convent onal ribbon mixer 300 parts sodium c-pentadecyl N-methyl amido ethyl sulfonate, 750 parts sodium tripolyphosphate, 105 parts pentasodium amino tri(methylene phosphonate) and 345 parts sodium sulfate. Admixing of the four anhydrous components results in a heavy duty detergent of the following composition.

Ingredients: Parts Active 33 Builder 1 67 1 Composition of builder:

Sodium tripolyphosphate 62.5 Pentasodium amino tri (methylene phosphonate) 8.75 Sodium sulfate 28.75

The above detergent composition gives good cleaning results in conventional automatic washing machines when used in concentrations of about 0.2% by weight in aqueous solution for laundering soiled clothes.

Other comparable detergent compositions can be prepared in the same manner as described by substituting similar amounts of other amphoteric surface active agents useful in practicing this invention. For example, similar amounts of potassium c-tridecyl N-methyl amido ethyl sulfonate, sodium c-tetradecyl amido ethyl sulfonate, sodium tridecyl amino ethyl sulfonate, sodium c-tetradecyl N-cyclohexyl amino ethyl sulfonate can be substituted for sodium c-pentadecyl, N-methyl amido ethyl sulfonate and the resulting detergent composition gives good results when used in the same manner as the detergent composition of this example.

EXAMPLES VII TO XV The following detergent compositions are prepared by admixing the anhydrous components in the proportions given in a conventional ribbon mixer. These detergents readily remove soil from clothes when used in concentrations of about 0.2% in aqueous solutions in automatic washing machines.

EXAMPLE VII Active-The product produced from condensing 10 moles of ethylene oxide per 1 mole of nonylphenol 30 Builder 1 7O 1 Composition of builder Percent Sodium tripolyphosphate Sodium sulfate Ethylene diamine tetrac Potassium carbonate 12 EXAMPLE IX Ingredients: Percentages ActiveThe sulfated product derived from sulfating the condensation product of 8 moles of ethylene oxide per one mole of dodecyl phenol 20 Builder 1 8O 1 Composition of builder: Percent Sodium tripolyphosphate 35 Trisodium nitrilotriacetate 15 Sodium sulfate 50 EXAMPLE X Active-Sodium dodecylbenzene sulfonate 20 Builder 1 8 1 Composition of builder: Percegt Sodium tripolyphosphate n9 Trisodium 1 hydroxy ethylidene diphosphonute a Trisodium nitrilotriacetate Sodium sulfate 40 EXAMPLE XI Active 1 30 Builder 2 '70 Composition of active: Percent Sodin mdodecylbenzene sultonate 20 Sodium dodecyl naphthalene sulfonate 20 Potassium nonyl sulfate 20 Product obtained from condensing moles o ethylene oxide per 1 mole of dicthylene glycol-" Potassium e-tetradecyl, N cyclohecyl amido ethyl sulfonate 20 2 Composition of builder: Percerit Sodium tripolyphosphate o0 Disodium ethylene diamine tetrwacetate 8 Tetra sodium methylene diphosphonate 6 Sodium sulfate 36 EXAMPLE XII Active Builder 2 73 Additives 3 2 1 Composition of active: Percent Sodium dodecylbenzene sulfonate 40 Product obtained from reacting 10 moles of ethylene oxide per 1 mole of N-dodecyl monoethanol amide 20 Sodium dodecyl sulfate Sodium hexadecyl sulfate 10 2 Composition of builder Percent Sodium tripolyphosphate 7O 'Ietrasodium amino tri (ethylidenephosphonate) 12 Potassium sulfate 1S Composition of additives Percent Sodium carhoxymethyl cellulose 1.00 Corrosion inhibitor 0.75 Perfume 0.25

EXAMPLE XIII ActiveSodium dodecylbenzene sulfonate Builder 1 Composition of builder: Percent Sodium tripolyphosphate 60 Pentasodium diethylenetriamine pentacetate 10 Sodium sulfate 30 EXAMPLE XIV ActiveThe sodium salt of the sulfuric acid esters of the reaction product of 1 mole lauryl alcohol per 3 moles of ethylene oxide 20 Builder 1 80 1 Composition of builder: Percent Sodium tripolyphosphate 60 Trisodium nitrilotriacetate 10 Sodium carbonate 30 EXAMPLE XV ActiveThe product obtained from the reaction of 5 moles of propylene oxide and 1 mole of ethylene diamine 25 Builder 1 1 Composition of builder: Percent Sodium tripolyphosphate 75 13 in said builder composition of an organic sequestering agent selected from the group consisting of amino tri(lower alkylidenephosphonic acids) of the formula where X and Y are selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 4 carbon atoms, alkylenephosphonic acids of the formula where X is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 4 carbon atoms, Y is selected from the group consisting of hydrogen, hydroxyl, halogen and lower alkyl groups containing from 1 to 4 carbon atoms, and n is an integer from 1 to 6, amino polycarboxylic acids of the formula OHZOOOI'I NOH2CO OH where R is selected from the group consisting of C-COOH C COOH H2? (3H2 H2C\ /CH2 Hz CHzCOOH wherein R is selected from the group consisting of hydrogen, lower alkyl groups containing from 1 to 4 carbon atoms, hydroxy substituted lower alkyl groups containing from 1 to 4 carbon atoms, phenyl and hydroxy substituted phenyl, and R is selected from the group consisting of hydrogen, lower alkyl groups containing from 1 to 4 carbon atoms and hydroxy substituted lower alkyl groups containing from 1 to 4 carbon atoms, the water soluble salts selected from the group consisting of alkali metal, ammonium and amine salts of said acids and mixtures thereof, (b) from about 30% by weight to about 80% by weight in said builder composition of sodium tripolyphosphate and (c) from about 15% by weight to about 55% by weight in said builder composition of an alkali metal salt selected from the group consisting of sodium sulfate, sodium carbonate potassium sulfate, potassium carbonate and mixtures thereof, and the weight ratio of said active to said builder composition is from about 2:3 to about 1:5 respectively.

2. The detergent composition of claim 1, wherein the organic sequestering agent is a sodium salt of said amino tri (methylenephosphonic acid).

3. A heavy duty detergent composition according to claim 1, wherein said organic sequestering agent is selected from the group consisting of said amino tri(lower alkylidenephosphonic acids), said water soluble salts of said acids and mixtures thereof.

4. A heavy duty detergent composition according to claim 4, wherein said organic sequestering agent is selected from the group consisting of said alkylenephosphonic acids, said water soluble salts of said acids and mixtures thereof.

5. The detergent composition of claim 1, wherein the organic sequestering agent is a sodium salt of said methylene diphosphonic acid.

6. The detergent composition of claim 1 wherein the organic sequestering agent is a sodium salt of 1 hydroxy ethylidene diphosphonic acid.

7. A heavy duty detergent composition according to claim 4, wherein said organic sequestering agent is selected from the group consisting of amino polycarboxylic acids, said water soluble salts of said acids and mixtures thereof.

8. The detergent composition of claim 1, wherein the organic sequestering agent is a sodium salt of said ethylene diamine tetra-acetic acid.

9. The detergent composition of claim 1, wherein the organic sequestering agent is a sodium salt of nitrilo triacetic acid.

10. A heavy duty detergent composition consisting essentially of, as an active, sodium tetradecyl benzene sulfonate; and a three component synergistic builder con sisting essentially of (a) from about 5% by weight to about 16% by weight in said builder composition of trisodium nitriloacetate, (b) from about 30% by weight to about by weight in said builder composition of sodium tripolyphosphate and (c) from about 15% by weight to about 55% by weight in said builder composition of sodium sulfate and the weight ratio of said active to said builder composition is from about 2:3 to about 1:5 respectively.

11. A heavy duty detergent composition consisting essentially of, as an active, sodium tetradecyl sulfate; and a three component synergistic builder composition consisting essentially of (a) from about 3% by weight to about 16% by weight in said builder composition of trisodium nitriloacetate, (b) from about 30% by weight to about 80% by weight in said builder composition of sodium tripolyphosphate and (c) from about 15 by weight to about 55% by weight in said builder composition of sodium sulfate; and the weight ratio of said active to said builder composition is from about 2:3 to about 1:5 respectively.

12. A heavy duty detergent composition consisting essentially of as an active containing from about 5 parts by weight to about parts by weight of sodium tetradecyl benzene sulfonate and from about 5 parts by weight to about 95 parts by weight of sodium tetradecyl sulfate; and a three component synergistic builder, a composition consisting essentially of (a) from about 3% by weight to about 16% by weight in said builder composition of trisodium nitriloacetate, (b) from about 30% by weight to about 80% by weight in said builder composition of sodium tripolyphosphate and (c) from about 15% by weight to about 55 by weight in said builder composition of sodium sulfate; and the weight ratio of said active to said builder composition is from about 2:3 to about 1:5 respectively.

13. A heavy duty detergent composition consisting essentially of as an active, an alkyl polyoxyethylene ether wherein said alkyl group contains from 8 to 18 carbon atoms and a three component synergistic builder, a composition consisting essentially of (a) from about 3% by weight to about 16% by weight in said builder composition of tn'sodium nitriloacetate, (b) from about 30% by weight to about 80% by weight in said builder composition of sodium tripolyphosphate and (c) from about 15% by weight to about 55% by weight in said builder composition of sodium sulfate; and the weight ratio of said active to said builder composition is from about 2:3 to about 1:5 respectively.

14. A heavy duty detergent composition consisting essentially of as an active, an alkyl phenol polyoxyethylene ether wherein said alkyl group contains from 4 to 20 carbon atoms; and a three component synergistic builder, a composition consisting essentially of (a) from about 3% by weight to about 16% by weight in said builder composition of trisodium nitriloacetate, (b) from about 30% by weight to about 80% by weight in said builder composition of sodium tripolyphosphate and (c) from about 15% by weight to about 55% by weight in said builder composition of sodium sulfate; and the weight ratio of said active to said builder composition is from about 2:3 to about 1:5 respectively.

15. The detergent composition of claim 9, wherein the active is an anionic synthetic detergent selected from the group consisting of alkyl aryl sulfonates, alkyl sulfates, alkyl phenol polyoxyethylene ether sulfates and mixtures thereof.

16. The detergent composition of claim 15, wherein the anionic synthetic detergent is an alkyl aryl sulfonate.

17. The detergent composition of claim 15, wherein the anionic synthetic detergent is an alkyl sulfate.

18. The detergent composition of claim 9, wherein the active is an alkyl polyoxyethylene ether.

19. The detergent composition of claim 9, wherein the active is an alkyl polyoxyethylene ether.

References Cited UNITED STATES PATENTS 2,765,279 10/1956 Nusslein 252-1l7 3,159,581 12/1964 Diehl 252152 3,234,124 2/1966 Irani 260500 3,256,370 6/1966 Fitch et al. 260-500 3,278,446 10/1966 Irani 252-152 FOREIGN PATENTS 1,045,373 12/1958 Germany. 1,102,329 3/1961 Germany.

818,151 8/1959 Great Britain.

846,499 8/1960 Great Britain.

100,519 4/ 1941 Sweden.

754,708 8/1956 Great Britain.

OTHER REFERENCES The Versenes, Bernsworth Chemical Co., Technical Bulletin No. 2, Section I, pp. 5 and 6; Section II, pp. 7-l3.

LEON D. ROSDOL, Primary Examiner.

S. D. SCHNEIDER, Assistant Examiner.