US3459670A - Builders for synthetic detergents - Google Patents

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United States Patent 3 459 670 BUILDERS FOR SFNTiIETlC DETERGENTS Richard P. Carter, Jr., Chesterfield, Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation 3,459,670 Patented Aug. 5, 1969 proved builder for synthetic organic anionic, nonionic and/ or amphoteric surface active compounds which are suitable for use as detergents in aqueous solutions.

Another object of this invention is to provide an improved washing composition of a synthetic organic anionic,

g gg sgg July 1, 1966, set. 562,127 5 nonionic and/or amphoteric surface active compound and Int. CL Clld 1 o4 an improved builder. ,s C 252.49 17 l i A still further object of this invention is to provide an improved liquid washing concentrate composition of a syirfthetic organic anionlic, tonionic andotr) alriphoteric su ace active compoun an an improve n1 er. ABSTRACT OF THE DISCLOSURE Other objects will become apparent from the following A composition useful as a detergent in an aqueous solud t il d description, tion includes a surface active compound and as The detergent builders of the persent invention are the a builder a eycloalkane Polycarboxylic acid of a Water cycloalkane polycarboxylic acids or water soluble salts soluble salt thereof. thereof, said acids having the following formula:

This invention relates to builders for synthetic detergents and, more particularly, to the use of cycloalkane C O polycarboxylic acids and/or their salts as builders for synthetic organic anionic, nonionic and/or amphoteric surface active compounds which are suitable as detergents in R R aqueous Solutions wherein x is an integer from 0 to 3 and R is hydrogen or The use of builders in detergent compositions is well a carbxoyfic acid group. with frotn 3 to 6 groups rel} known today wlth one class in particular, the polyphosresented by R being carboxylic acid groups phatcs, being used extensively. Builders, of course, are Such cycloalkane polycarboxylic acids include the used to improve detergency levels of the detergent comlowing: positions and due to the complex nature of detergency, that is, the various and numerous factors which are ineyeloprepanelrlz'trfcerboxylfe f volved, there has been no general basis found with cYcloPwPane'12,3'mm'lmxylm f respect to either the physical properties or chemical strucacld ture of compounds from which the behavior of a detergent e boxyhe builder could be predicted. In general, detergent builders cyclopemane'liz3'mcarboxyhc Y are believed to affect to various degrees such factors in cyelopentane'IZQAACUaCaYbOXYPC a the detergency system as stabilization of solid soil suspencyclohexane'1234'mtmcarbuym acid sions, emulsification of soil particles, the surface activity Preferred compounds are cyclohexane-l,2,3,4-tetracarof the aqueous detergent solution, solubilization of waterboxylic acid and cyclopentane1,2,3,4-tetracarboxylic acid. insoluble materials, foaming or suds producing charac- 40 The water soluble salts of the cycloalkane polycarteristics of the washing solutions, peptization or deflocboxylic acids are preferred (solubility in water at 25 C. culation of soil agglomerates, neutralization of acid soil Of at least 0.5), especially the alkaline salts (Salts which and sequestration of metallic ions such as mineral hardexhibit 3 R of from about 8 to about in F at a ness constituents which are often present in the washeoneemmtlon of 1% and -Lf m Particular: the ing solution. As can be appreciated from the foregoing, sodmn? Salts, although other alkah metal e such as only a few compounds have been found which can be Potas smm hthmm and the as well as mlxmres classed as effective detergent builders. alkali metal salts, may be substituted therefor. In addition, The mere fact that a compound is found to be an effecg w 'fi Reg-sig g i i ir an eammes ,wrc e 11 ecaracerisicso five deiergem builder y does not necesiamy the alkali metal salts may be used to practice the invenrender its use advantageous in detergent compositions. fiom In Particular amine salts prepared from low molecw The detergent builder, among other things, should b lar weight amines i.e. having a molecular weight below emPat 1b1e the vaneus addltlves weventlonany about 300 and more particularly the alkyl amines alkylene ffflmd 1n detergent Pomposflmns, be hydrolytlcflny Stable amines and alkanol amines containing not more than 2 since such compositions are often used in hot, alkaline amine groups such as ethylamine diethylamine propylaqueous solutions, be compatible with various bleaching amine propylenediamine hexylamine 2-ethyl hexylamine agents of the oxygen and chlorine type and should not N-butylethanolamine triethanolamine and the like are the to any appreciable degree corrode or ther i ff t h preferred amine salts. Since most of the synthetic determetal parts of h hi or equipment i hi h the gent compositions are used in alkaline aqueous systems washing process is being conducted. To one degree or the field bullders may be used by e i the P if another the known builder materials, either of the inorrequlred, f the detergen composit on or the r sulting ganic or Organic type have certain limitations and disad aqueous solution to the desired alkaline pH condition. In vantages such as those previously mentioned and thus imof the foregoing 15 Preferred that.the PH of the proved builders are continually sought which would obdetergent.composmon or the gqueous {nedmmbe Such as viate or minimize the limitations and disadvantages of the to i an gr z solutlon havmg at least prior artbuflder materials. a p 0 (pre era y a ut to about 12) when the Therefore it is an object of this invention to provide d-etergent iomposlnon 18 used m amounts to glve effeca tive cleansing action. an improved builder for synthetic organic surface active h builders f the present invention are not only compoundseffective detergent builders but also exhibit many and Another object of this invention is to provide an improved builder for synthetic organic anionic, nonionic and various advantageous properties which include being hydroylytically stable, that IS, resistant to decomposition or degradation under high temperature and/or pH condition, relatively inert or non-corrosive to metal parts, such as zinc, copper, aluminum and the like often found in washing equipment or machines, and stable toward bleaching agents such as oxygen and/or chlorine bleaches as well as not materially interfering with the functioning of such agents.

As previously mentioned, the builder may be used with any of the conventional detergent classes as synthetic non-soap anionic, nonionic and/or amphoteric surface active compounds which are suitable as cleansing agents. Anionic surface active compounds can be broadly described as compounds which contain hydrophilic or lyophilic groups in their molecular structure and which ionize in an aqueous medium to give anions containing the lyophilic group. These compounds include the sulfated or sulfonated alkyl, aryl and alkyl aryl hydrocarbons and alkali metal salts thereof, for example, sodium salts of long chain alkyl sulfates, sodium salts of alkyl naphthalene sulfonic acids, sodium salts of sulfonated abietenes, sodium salts of alkyl benzene sulfonic acids particularly those in which the alkyl group contains from 8-24 carbon atoms; sodium salts of sulfonated mineral oils and sodium salts of sulfosuccinic acid esters such as sodium dioctyl sulfosuccinate.

Advantageous anionic surfactants include the higher alkyl aryl sulfonic acids and their alkali metal and alkaline earth metal salts such as for example sodium dodecyl benzene sulfonate, sodium tridecyl sulfonate, magnesium dodecyl benzene sulfonate, potassium tetradecyl benzene sulfonate, ammonium dodecyl toluene sulfonate, lithium pentadecyl benzene sulfonate, sodium dioctyl benzene sulfonate, disodium dodecyl benzene disulfonate, disodium di-isopropyl naphthalene disulfonate and the like as well as the alkali metal salts of fatty alcohol esters of sulfuric and sulfonic acids, the alkali metal salts of alkyl aryl (sulfothioic acid) ethers and the alkyl thiosulfuric acid, etc. Preferred anionic organic surface active agents are, as noted hereinbefore, sodium salts of alkyl benzene sulfonic acids and particularly preferred sodium salts of alkyl benzene sulfonic acids are those in which the alkyl group or radical contains 10 to 18 carbon atoms in a straight (i.e., unbranched) chain.

Nonionic surface active compounds can be broadly described as compounds which do not ionize but usually acquire hydrophilic characteristics from an oxygenated side chain, such as polyoxyethylene, while the lyophilic part of the molecule may come from fatty acids, phenols, alcohols, amides or amines. Examples of nonionic surfactants include products formed by condensing one or more alkylene oxides of 2 to 4 carbon atoms, such as ethylene oxide or propylene oxide, preferably ethylene oxide alone or with other alkylene oxides, with a relatively hydrophobic compound such as a fatty alcohol, fatty acid, sterol, a fatty glyceride, a fatty amine, an aryl amine, a fatty mercaptan, tall oil, etc. Nonionic surface active agents also include those products produced by condensing one or more relatively lower alkyl alcohol amines (such as methauolamine, ethanolamine, propanolamine, etc.) with a fatty acid such as lauric acid, cetyl acid, tall oil fatty acid, abietic acid, etc. to produce the corresponding amide.

Still other nonionic surface active compounds include the amine oxides and phosphine oxides and preferably the unsymmetrical tIialkyl-amine oxides and -phosphine oxides wherein two of the alkyl groups are lower alkyl groups (1 to 4 carbon atoms) and the third alkyl group is a higher alkyl group (8 to 18 carbon atoms). Examples include dimethyldodecylamine oxide, dimethyl dodecylphosphine oxide, dimethyl tetradecyl amine oxide, dimethyltetradecyl phosphine oxide, diethylhexadecylamine oxide, diethylhexadecylphosphine oxide and the like.

Particularly -advantageous nonionic surface active agents are condensation products of a hydrophobic compound having at least 1 active hydrogen atom and a lower alkylene oxide (for example the condensation product of an aliphatic alcohol containing from about 8 to about 18 carbon atoms) and from about 3 to about 30 mols of ethylene oxide per mol of the alcohol, or the condensation product of an alkyl phenol containing from about 8 to about 18 carbon atoms in the alkyl group and from about 3 to about 30 mols of ethylene oxide per mol of alkyl phenol. Other advantageous nonionic detergents include condensation products of ethylene oxide with a hydrophobic compound formed by condensing propylene oxide with propylene glycol.

Amphoteric surface active compounds can be broadly described as compounds which have both anionic and cationic groups in the same molecule. Such compounds may be grouped into classes corresponding to the nature of the anionic-forming group, which is usually carboxy, sulfo and sulfate. Examples of such compounds include sodium N-coco beta amino propionate, sodium N-tallow beta amino dipropionate, sodium N-lauryl beta iminodipropionate and the like.

Other typical examples of these categories of the anionic, nonionic and/or amphoteric surface active agents are described in Schwartz and Perry Surface Active Agents Interscience Publishers, New York (1949) and the Journal of American Oil Chemists Society, volume 34, No. 4, pages 170-216 (April 1957) which are incorporated herein by reference.

The amount of builder necessary to be used with the surface active compound (active) may vary depending upon, inter alia, the end use, type of active employed, pH conditions and the like. In general, the builders can be employed in detergent compositions in any desired proportions. The optimum active/builder ratio depends upon the particular active employed and the end use for which the detergent composition is intended but most generally will fall within the range of active/builder weight ratio of about 10:1 to 1:10 and preferably about 4:1 to 1:4.

Often the builders of the present invention can be employed advantageously in conjunction with other detergent builders (supplementary builders) which include the conventional alkali metal polyphosphates, i.e., the tripolyphosphates and pyrophosphates, (sodium tripolyphosphate, tetrasodium pyrophosphate, tetrapotassium phosphate, disodium pyrophosphate and the like), the amino polycarboxylic acids and salts such as the sodium, potassium and ammonium salts of nitrilotriacetic acid (trisodium nitrilotriacetate), the sodium, potassium and ammonium salts of amino tri(methylene phosphonic acid) as well as the free acid, and the diphosphonic acids and salts (methylene diphosphonic acid and l-hydroxy, ethylidene diphosphonic acid) as disclosed and described in Canadian Patent718,385 issued Sept. 21, 1965 which is incorporated herein by reference. Generally speaking, a weight ratio of cycloalkane polycarboxylic acid builder and the foregoing described builder or builder mixtures of from about 1:10 to 10:1 have been found to be particularly effective as a detergent builder composition.

As a liquid washing concentrate composition useful for virtually all washing and cleaning situations including laundering and dishwashing, the detergent compositions of the present invention (active and builder) are particularly advantageous, Such concentrate compositions are either water or water-alcohol based of either the solution or emulsion type and can contain hydrotropes such as the water soluble alkali metal salts (particularly sodium and potassium) of toluenesulfonate, benzene sulfonate and xylenesulfonate in an amount of from O to about 12% by weight or a polyelectrolyte (ethylene-maleic anhydride copolymers and methyl vinyl ether-maleic anhydride copolymers) as stabilizing components in an amount of from 0 to about 8% by weight. In addition, the water or water-alcohol mixture is usually in an amount of from about 20% to about by weight of the concentrate composition.

The detergent compositions of the present invention can be prepared in any of the several commercially desirable composition forms such as, bar, granular, flake, liquid and tablet form.

The resulting detergentcomposition, that is, the active and builder, of the present invention is generally effective when used in aqueous systems in conventional amounts which are generally about 0.2% concentration or below.

The invention is not to be limited to any particular method of preparing the detergent compositions containing the builder and the surfactant. The builder may be mechanically mixed in, crutched in the surfactant in the form of a slurry, or dissolved in a solution of the surfactant. In addition, the builder may be admixed with the surfactant in any of the forms in which the surfactant is manufactured in, as well as being added simultaneously or separately to an aqueous solution. In any event, the builder is intended to be used with the surfactant at the time of application as a cleansing agent.

In order to illustrate the invention, a builder of the present invention was compared under carefully controlled conditions with sodium tripolyphosphate for building properties in hot water. The conditions of the test were; hardness, 300 ppm; total detergent concentration, 0.2%; temperature, 60 C.; pH, 9.5. The tests were made in a Launder-Ometer machine on standard soiled fabric specimens.

The following detergent compositions were used in the test with the percentages being by weight in the aqueous washing solution:

Percent Sodium dodecylbenzene sulfonate 0.04 Builder 1 0.05 Sodium silicate 0.02 Sodium carboxymethylcellulose 0.00065 Cyclopenttme-1,2,3,4-tetracurhoxyllc acid was adjusted to pH with NaOH.

TABLE 1 Builder: Percent soil removal (1) Cyclopentane-l,2,3,4-tetracarboxylic acid 36 (2) Sodium tripolyphosphate 35 (3) No building present 17 The above results indicate that a builder of the instant invention compares very favorably with sodium tripolyphosphate, a widely used builder. Therefore, it can be appreciated that the new builders of this invention exhibit building properties comparable or better to conventional widely-used builders and can be used advantageously in many applications were the conventional builders are not suitable.

As previously mentioned, the builders of the present invention exhibit the highly advantageous property of being stable in the presence of chlorine bleaches (chlorine-releasing agents) without materially interfering with the functioning of these agents. The chlorine-releasing agents which are suitable for use are those water-soluble organic and inorganic compounds which are believed to have oxidizing power by virtue of containing availablechlorine" which can react in aqueous solution to form hypochlorous acid or the hypochlorite ion. Such organic compounds include the alkyl hydochlorites and especially the lower alkyl hypochlorites, such as ethyl hypochlorite, propyl hypochlorite, n-butyl hypochlorite and tert-butyl hypochlorite; the N-chlorinated heterocyclic compounds and especially the five and six membered N-chlorinated heterocyclic compounds, such as, hydantoin, N-chlorosuccinimide and the trazines, such as, the cyanuric acids and salts which include trichloroisocyanuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate, and potassium dichloroisocyanurate, polychlorocyanurate complexes are disclosed and described in United States Patents 3,035,054; 3,035,056; 3,035,057; 3,150,132 and 3,072,654 such as [(mono-trichloro) tetra- (monopotassium dichloro) pentaisocyanurate] as well as melamine, ammeline and ammelide; and the N-chloro aromatic and substituted aromatic sulfonamides, such as, sodium benzene sulfochloroamide, sodium nitrobenzene sulfochloroamide and sodium p-toluenesulfonchloroamide. Such inorganic compounds include the alkali metal chlorine containing compounds, such as, sodium hypochlorite, sodium chlorite and lithium hypochlorite, the alkaline earth metal chlorine containing compounds, such as calcium hypochlorite and barium hypochlorite, and the chlorinated trisodium phosphates, a class of compounds which consist of physico-chemical combination in unitary crystalline form of trisodium phosphate and sodium hypochlorite. The chlorinated trisodium phosphates are known and are described along with their methods of preparation, in United States Patent 1,555,474 or 1,965,304.

The term active or available chlorine is commonly used in the hypochlorite bleaching and sterilizing art to refer to atomic or nascent chlorine. Such chlorine differs from normally occurring chlorine in that the latter occurs in molecular form and each molecule contains two atoms of chlorine. When employed for bleaching purposes the active or available" chlorine has twice the oxidizing or bleaching activity of molecular chlorine based on the weight (molecular) of the normally occurring molecular chlorine. Thus, the terms active or available chlorine are generally expressed as twice the amount in terms of percent of the chlorine present in a molecule of material.

Due to the many and varied chlorine-releasing agents which vary in molecular weight and available chlorine over a wide range and the fact that the amounts of the chlorine-releasing agent used in many applications are based on the available chlorine content, the amounts suitable for use herein unless otherwise indicated will be based on percent available chlorine per total weight of the particular composition. By knowing the molecular weight of the particular chlorine-releasing agent, its available chlorine, and the available chlorine desired expressed in percent available chlorine per total weight of the particular composition, the necessary amounts on a weight 'basis can be determined readily.

Although the amount of chlorine-releasing agent in the detergent composition can vary considerably, it is preferred that an amount of from about 0.1% to about 25% available chlorine be used. Moreover, for most end use applications the usual available chlorine may vary from about 0.001% to about 0.05% available chlorine per weight of aqueous solution.

In order to illustrate the relative stability of various organic builders which are effective in the alkaline pH region, i.e., about 8-12, and a builder representative of the instant invention in aqueous solutions containing chlorine-releasing agents, the following tests and comparisons were made with the indicated results. The tests were carried out in relatively concentrated solutions containing 3% by weight of both builder and sodium hypochlorite at pH 10 and 25 C. The measurements were made of percent original available chlorine remaining after 3 hours with the hypochlorite determined iodometrically by the thiosulfate titration.

The following table indicates the results of the above comparisons:

TABLE 2 Original hypochlorite Builder: remaining percent (1) Disodium ethylene diamine tetra acetate-2H O .7 (2) Trisodium nitrilotriacetate-H O .7 (3) Cyclopentane-1,2,3,4-tetracarboxylic acid- 97.2

As can be observed from the above table the organic builders (1) and (2) would not be considered suiable in many applications for use with a chlorine-releasing agent since less than 1% original hypochlorite remained after 3 hours in the presence of the builders. However, with a builder of the instant invention, (3), more than 95% of the hypochlorite remained after 3 hours in the presence of the builder. This dramatically illustrates the unique and totally unexpected compatibility between a builder representative of the instant invention and a chlorinereleasing agent.

As previously mentioned, the builders of the present invention exhibit the highly advantageous property of being relatively inert or noncorrosive to metal parts, such as those containing zinc, copper and/or aluminum, often found in washing equipment or machines.

In order to compare the corrosive properties of organic builders such as nitrilotriacetic acid with builders of the present invention the following tests were carried out. Into an aqueous solution containing the builder in a 1% by weight concentration (pH adjusted to with NaOI-I) are immersed several clean preweighed aluminum and (1" x 2" x 56 coupons. The immersion test is carried out by dipping the coupons into the solution for 30 seconds and then raising such out of the solution for 30 seconds with the process being repeated for about 84 hours. The following table reports the loss in weight expressed as percent weight loss Weight before-weight after X 100 weight-before TABLE 3 Percent Builder Metal weight loss (1) Nitrilotriacetic acid Al 0.87 (2) Cyclopentane-1,2,3,4-tetracatboxylic acid Al 0.0 (3) N itrilotralcetic acid Cu 1. 78 (4) Cyclopentane-a, 1,2,3,4-tetracarboxylic ac1d Cu 0.07

As can be observed from the above table, the sodium salt of nitrilotriacetic acid was quite corrosive to both aluminum and copper whereas a builder representative of the present invention (cyclopentane-1,2,3,4-tetracarboxylic acid, sodium salt) was not corrosive to any appreciable degree towards copper or aluminum under the foregoing test conditions.

While a detergent composition in accordance with this invention need contain only a detergent active of the class described and a cycloalkane polycarboxylic acid or salt builder, it will be appreciated that the incorporation in the composition of additional ingredients commonly used with cleansing agents, such as perfume, antiredeposition agents (e.g., carboxymethylcellulose), brightening agents (e.g., fluorescent dyes) and the like, are contemplated as being within the invention.

The following detergent compositions, in which the percentages are by weight, are presented as being illustrative of the present invention:

Percent Sodium dodecyl benzene sulfonate Cyclobutane-l,2,3-tricarboxylic acid (sodium salt;

pH-10) 50 Sodium carboxymethylcellulose 1 Sodium silicate 10 Sodium sulfate 19 Percent Nonionic condensate (dodecyl alcohol-ethylene oxide on a 1:10 molar ratio basis) 10 Tetrapotassium pyrophosphate 10 Cyclopcntane-1,2,3,4-tetracarboxylic acid (potassium salt; pH-10) or Cyclohexane-1,2,3,4-tetracarboxylic acid (potassium salt; pH-10) 19 Sodium carboxymethylcellulose 1 Water 60 8 III Percent Sodium N-coco beta amino propionate 20 Cyclobutane-1,2,3-tricarboxylic acid (ammonium salt;

pH-9) or Cyclohexane-1,2,3,4,5,6-hexacarboxylic acid (triethanol amine salt; pH-9) 50 Sodium carboxymethylcellulose 1 Sodium sulfate 29 Percent Sodium dodecylbenzene sulfonate 20 Cyclopentane 1,2,3,4 tetracarboxylic acid (sodium salt; pH-l0) 25 Builder 25 Sodium carboxymethylcellulose 1 Sodium silicate 10 Sodium sulfate 19 Builder:

(1) Pentasodium amino tri(methylenephosphonate) (2) Trisodium l-hydroxy, ethylidene diphosphonate (3) Trisodium nitrilotriacetate (4) 50:50 weight ratio of trisodium nitrilotriacetate and trisodium l-hydroxy, ethylidene diphosphonate (5) 75:25 weight ratio of sodium tripolyphosphate and trisodium nitrilotriacetate (6) 75:25 weight ratio of sodium tripolyphosphate and trisodium l-hydroxy, ethylidene diphosphonate.

All of the foregoing detergent compositions are effective as washing compositions for cleaning materials such as textiles, hard surfaces such as dishes and walls and the like when used in concentrations of about 0.2% in water.

For dishwashing compositions, the following additives within the range specified when incorporated with a chlorine-releasing agent give an effective formulation.

The following dry composition (parts by weight) is especially adapted for use as a machine dishwashing compound when used in amounts to give about 15 to 25 p.p.m. available chlorine in water.

1-40 percent by weight.

0-30 percent by weight.

What is claimed is:

1. A washing composition consisting essentially of a synthetic organic detergent selected from the group consisting of non-soap anionic, nonionic, and amphoteric surface active compounds and, as a builder, a compound selected from the group consisting of cycloalkane polycarboxylic acids having the formula:

wherein x is an integer from to 3, and R is selected from the group consisting of hydrogen and carboxylic acid groups with from 3 to 6'groups represented by R being carboxylic acid groups, and water soluble salts thereof having a solubility in water at 250 C. of at least 0.5% by weight, said detergent and said builder being present in said washing composition in a weight ratio of from 1:10 to :1.

2. A washing composition according to claim 1, wherein said water soluble salt is selected from the group consisting of alkali metal salts, ammonium salts, and amine salts of amines having a molecular weight below about 300 and containing not more than 2 amine groups, and said composition providing in aqueous solution a pH of from about 9 to about 12.

3. A washing composition according to claim 2, wherein said water soluble salt is a sodium salt.

4. A washing composition according to claim 3, wherein said synthetic organic detergent is a non-soap anionic surface active compound.

5. A washing composition according to claim 4, wherein said non-soap anionic surface active compound is a sodium salt of an alkyl'benzene sulfonic acid in which the alkyl group contains from 10 to 18 carbon atoms.

6. A washing composition according to claim 2, additionally containing a supplemental builder selected from the group consisting of alkali metal polyphosphates, amino polycarboxylates, amino tri(methylenephosphonates), diphosphonates and mixtures thereof, said cycloalkane polycarboxylate builder and said supplemental builder being present in said washing composition in a weight ratio of from 1:10 to 10: 1.

7. A washing composition according to claim 6, wherein said supplemental builder is sodium tripolyphosphate.

8. A composition according to claim 6, wherein said supplemental builder is sodium nitrilotriacetate.

9. A composition according to claim 6, wherein said supplemental builder is sodium l-hydroxy, ethylidene diphosphonate.

10. A washing composition according to claim 2, additionally containing a chlorine-releasing agent in an amount of from about 0.1% to about 25% available chlorine per weight of said composition.

11. A washing composition according to claim 6, additionally containing a chlorine-releasing agent in an amount of from about 0.1% to about 25% available chlorine per weight of said composition.

12. A washing composition according to claim 2, additionally containing water in an amount of from about 20% to about by weight of said composition.

13. A washing composition according to claim 6, additionally containing water in an amount of from about 20% to about 80% by weight of said composition.

14. A washing composition according to claim 2, wherein said builder is a water soluble salt of cyclopentane-l,2,3,4-tetracarboxylic acid.

15. A washing composition according to claim 6, wherein said builder is a water soluble salt of cyclopentane-l,2,3,4-tetracarboxylic acid.

16. A washing composition according to claim 10, wherein said builder is a water soluble salt of cyclopentane-l,2,3,4-tetracarboxylic acid.

17. A washing composition according to claim 12, wherein said builder is a water soluble salt of cyclopentane-l,2,3,4-tetracarboxylic acid.

References Cited UNITED STATES PATENTS 3,218,353 11/1965 Volkenburgh et al. 260-514 MAYER WEINBLATT, Primary Examiner US. Cl. X.R.

22 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 459,670 Dated August 5, 1969 Inventofls) Richard Carter, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

fil olumn 2, line 42, the figure reading "0.5" should read 0.5%

Column 9, line 22, the figures "2500" should read 25C SIGNED AND SEALED AUG 251970 (SEAL) Attest:

WILLIAM E. sum, .18- A ueating omoor I C-omissioner of Patents