US2861954A - Polyphosphate compositions containing soap and 2-mercaptothiazoline - Google Patents

Description

United States Patent 2,861,954 I POLYPHOSPHATE COMPOSITIONS CONTAINING SOAP AND Z-MERCAPT'DTHIAZOLINE Edgar E. Ruff, Bergeniield, N. .L, assignor to Lever Brothers Company, New YorlqN. Y., a corporation of Maine No Drawing. Application January 9, 1956 Serial No. 557,854 13 Claims. (Cl. 252-110) This invenion relates to detergent compositions containing tarnish inhibitors and more particularly to spraydried tripolyphosphate compositions containing a soap and Z-mercaptothiazoline as synergistic tarnish inhibitors.

Tripolyphosphate compositions are now widely used for detergent and other purposes. Aqueous solutions of such compositions when at certain pH values tend to tarnish German silver (a nickel-Zinc-copper alloy) to a variety of shades from yellow to bluish black, especially if the solutions are at elevated temperatures and are allowed to remain in contact with the metal for several minutes. Since German silver is frequently used for household articles commonly washed in tripolyphosphatebuilt detergent compositions, it is evident that this is a serious problem.

In developing a spray-dried tripolyphosphate detergent composition containing an organic anionic non-soap detergent or an organic nonionic non-soap detergent it was found that Z-mercaptothiazoline was an effective tarnish inhibitor for such compositions. However, it was also found that when such spray-dried tripolyphosphate compositions contain from about 10% to about 20% of an alkali metal carbonate that Z-mercaptothiazoline no longer was effective as a tarnish inhibitor. This is clearly shown by the six examples presented below in Table I wherein the amounts of the components in the tripolyphosphate detergent compositions are expressed in percent by weight of the total composition at the time of mixing the components together with the exception of the Z-mercaptothiazoline tarnish inhibitor, the percent thereof being based upon the weight of the tripolyphosphate present in the compositions. In thefollowing six examples Pluronic L64 is an organic nonionic non-soap detergent compound having the empirical formula HO(C H O) (C H O) (C H O) H prepared by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol where b is an integer selected from the group consisting of 26 to 30 and a plus is an integer such that the molecule contains from 40% to 50% of ethylene oxide and Oronite Dispersant NIW is an organic nonionic non-soap detergent which is a polypropylene alkyl phenol averaging tetradecyl in the alkyl radical condensed with ethylene oxide to an average of 9 ethylene oxide groups.

TABLE I Example No 1 2 3 4 5 6 Pluronic L-04 8. 75 8. 75 8.75 8. 75 8. 75 8. 75 Oronite Dispersant NIW 1.25 1. 25 1. 25 1.25 1. 25 1. 25 Pentasodium Tripclyphosphateun 35. 0O 35. 00 35. 00 35. 00 35. 00 35. 00 Sodium Car-boxymethyl Hydroxyethyl Cellulose. 0. 50 0. 5O 0. 50 0. 50 0. 50 0. 50 Water 10.00 10.00 10.00 10.00 10.00 10.00 Sodium Sulfate. 44. 50 40. 75 37.00 33. 25 29. 50 24. 50 Sodium Carbonate. 0.00 3. 75 7. 50 11.25 15.00 20.00

Total 100. 00 100. 00 100. 00 100. 00 100.00 100. 00

Z-Mereaptothiazoline (based on tripolyphosphate)... 0.06 0.06 0.06 0 06 0.06 0.06 Tarnish Grade No. l 2 3 5 5 5 The tarnishing action of each of the above tripolyphosphate detergent compositions on German silver was tested by the following procedure. Five grams of the tripolyphosphate detergent composition was dissolved in somewhat less than one quart of Water at a temperature under 17-0" F. More water was then added to give a total volume of one quart. 300 ml. of the solution was placed in a beaker, and the temperature adjusted to F.- F. A strip of German silver metal, six inches by one inch which had been cleaned with a metal polish and rinsed and dried, was partially immersed in the solution and allowed to remain for one-half hour at 160 F.-170 F. The metal strip was then removed and dried with a cloth. The strip was visually examined for tarnish and the tarnish graded as follows.

Grade N 0. Degree of Tarnish No tarnish.

Interface stain only.

Barely noticeable tarnish.

Slight tarnish.

Moderate tarnish.

Considerable (heavy) tarnish. Severe, as when inhibitor is absent.

This test procedure was employed throughout the remaining examples herein set forth.

From Example 1 above it can be readily seen that a tripolyphosphate detergent composition containing at least one organic non-soap detergent and containing 2- mercaptothiazoline produces only interface stain upon German silver when the composition does not contain any alkali metal carbonate. As the amount of alkali metal carbonate is increased and the amount of alkali metal sulfate supplemental builder correspondingly decreased it canbe seen that the 2-mercaptothiazoline loses its effectiveness as a tarnish inhibitor and becomes ineffective when the alkali metal carbonate content is in the range from about 10% to about 20%. The compositions of Examples l--6 were prepared as mechanical mixes rather than as spray-dried products in order that the proportions of sodium carbonate would not be altered by possible decomposition upon spray drying. It will be appreciated, however, that the results noted above also apply to spray-dried products.

In accordance with the instant invention it wasfound that spray-dried tripolyphosphate detergent compositions containing at least one organic non-soap detergent and from about 10% to about 20% of an alkali metal carbonate could be provided with greatly improved tarnishing properties upon German silver when such compositions contain Z-mercaptothiazoline and soap as synergistic tarnish inhibitors. The spray-dried detergent compositions of the present invention which will inhibit the formation of tarnish upon German silver therefore comprise by weight from about 20% to about 50% of an alkali metal tripolyphosphate, fromabout 5% to about 15% total of at least one organic non-soap detergent selected from the group consisting of organic anionic nonsoap detergents and organic nonionic non-soap detergents, from about 10% to about 20% of an alkali metal carbonate, about 10% of an alkali metal silicate, from about 0.03% to about 0.06% of 2-mercaptothiazoline based on the weight of tripolyphosphate, from about 1.4% to about 3.0% of a soap based on the weight of tripol'yphosphate, said soap being selected from the group consisting of alkali metal salts of fatty acids having an acyl-group of from 8 to 22 carbon atoms, and the balance water and supplemental builders. These components and percentages thereof are expressed at the time of mixing the components together and prior to spray drying. p

Any water-solublealkali metal tripolyphosph ate may be employed, examples thereof being pentasodium tripolyphosphate and pentapotassium tripolyphosphate. From about 20% to about 50%, and preferably about 35%, by weight of the alkali metal tripolyphosphate is present in the detergent composition as the heavy duty component thereof. From about to about 15% total, and preferably about total, by weight of at least one organic non-soap detergent is employed in the composition. organic anionic non-soap detergents or organic nonionic non-soap detergents. It was found that the synergistic tarnish inhibitors were ineffective with organic cationic non-soap detergents and hence such detergents are excluded from the detergent compositions.

The organic anionic non-soap detergents include by way of example the alkylaryl sulfonates, a class of anionic detergents well known in the art under this name. One example thereof is the sulfonated phenyl polypropylene alkanes, characterized by the branched chain structure of polypropylene and a tertiary alkyl carbon at the benzene ring, and having the following general structure:

where M is hydrogen, an alkali metal or an organic amine cation, and R and R are alkyl, of the type formula C H and at least one R is a polypropylene group, the whole alkyl group containing preferably 12 to 15 carbon atoms. These are known compounds, whose preparation and properties are set forth in U. S. Patent No. 2,477,383 to Lewis, issued July 26, 1949; they are available in commerce under the trade names Oronite, Ultrawet, and Neolene.

N-onionic detergents include, for example, alkyl oxyether and ester and thioether and ester detergents having the following general formula:

where R is a straight or branched chain saturated or unsaturated hydrocarbon group having from 8 to 18 carbon atoms or an aralkyl group having a straight or branched chain saturated or unsaturated hydrocarbon group of from 8 to 18 carbon atoms attached to the aryl nucleus, and attached to A through the aryl nucleus, A is selected from the group consisting of ethereal oxygen and sulfur, carboxylic ester and thiocarboxylic ester groups and x is a number from 8 to 20. R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, myristyl, cetyl or stearyl group, or an alkylaryl group such as octylbenzene, nonylbenzene, decylbenzene, stearylbenzene, etc.

When R is alkyl it will be evident that the detergent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid of high molecular weight, by condensation with ethylene oxide. Typical of this class of alkyl ether are the condensation products of oleyl or dodecyl alcohol or mercaptan with from 8 to 17 moles of ethylene oxide, such as Emulfor On, Nonic 2l8.and Sterox SE and SK. Typical alkyl esters are G1226 Renex (polyoxyethylene ester of tall oil acids), Sterox CD and Neutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol).

When R is aralkyl, the detergent can an alkyl phenol or thiophenol. V

The ethoxynated alkyl phenols and thiophenols have the following general formula:

be derived from where R is a straight or branched chain saturated or unsaturated hydrocarbon group having at least 8 carbon The organic non-soap detergents may be either 4 atoms up to approximately 18 carbon atoms, A is oxygen of sulfur and x is a number from 8 to 20. R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group. Typical V, are the condensation products of octyl and nonyl phenol and thiophenol with from 8 to 17 moles of ethylene oxide,

available commercially under the trade names NIW, Antarox A-400, Igepal CA and CO, Triton X-100,Neutronyx 600, and Tergitol NFX.

The alkali metal carbonate may be by way of example sodium carbonate or potassium carbonate, from about 10% to about 20%, and preferably 15% by weight thereof being employed in the detergent composition.

The alkali metal silicate may be sodium or potassium silicate, for example, the amount thereof being about 10%.

As noted above one of the synergistic tarnish inhibitors is 2-mercaptothiazoline. From about 0.03% to about 0.06% thereof based on the weight of tripolyphosphate is employed in the spray-dried detergent composition.

The other synergistic tarnish inhibitor is a soap, from about 1.4% to about 3.0% thereof based on the weight of tripolyphosphate being employed in the detergent composition. The soap is an alkali metal salt of one or more of the higher saturated or unsaturated fatty acids having an acyl group of from 8 to 22 carbon atoms and may include, for example, the alkali metal salts, such as the sodium salts of myristic acid, palmitic acid, tallow fatty acid, and coconut oil fatty acid.

The balance of the spray-dried detergent composition is made up of water and supplemental builders. The supplemental builders may include alkali metal and alkaline'earth metal sulfates, chlorides, and borates, such as sodium tetraborate, sodium sulfate, calcium sulfate, calcium chloride, sodium chloride, and sodium borate. The builders should be water-soluble.

In addition to or instead of the above mentioned supplemental inorganic salts, organic material, such as starch, polyethylene glycols, polyvinyl alcohols and salts of carboxymethylcellulose and carboxymethyl hydroxyethyl.

cellulose and perfumes and dyes can be used in minor proportions as builders.

The tripolyphosphate detergent compositions may be prepared by the conventional method of blending the ingredients thereof in an aqueous solution or slurry and then drying the resulting mixture in a spray dryer at elevated temperatures. -It was found that with drumdried tripolyphosphate detergent compositions that the synergistic tarnish inhibitors were not necessary in order to prevent the formation of tarnish by such compositions upon German silver. Accordingly, drum-dried tripolyphosphate detergent compositions are excluded from this invention.

The invention will be further explained by the following discussion. Drum-dried tripolyphosphate detergent compositions do not need the presence of the synergistic tarnish inhibitors, since the components of such compositions do not decompose upon drum drying. Accordingly, the 10% of alkali metal silicate added to the mixture of the composition prior to drum drying remains present inthe same amount in the drum-dried product and is sufiicient by itself in this amount to inhibit the formation of tarnish upon German silver by the tripolyphosphate. This, however, is not true of spray-dried tripolyphosphate detergent compositions.

In the conventional spray drying of tripolyphosphate detergent compositions there is a decomposition of a portion of the alkali metal tripolyphosphate into such products as alkali metal pyrophosphate. For example, a mixture of the tripolyphosphate detergent composition in Example 9 without the synergistic tarnish inhibitors upon spray drying contained about 10% of tetrasodium pyrophosphate as determined by wet analysis. There is also a decomposition of a portion of the alkali metal silicate into silica floc by the acidic breakdown products of the alkali metal tripolyphosphate, thereby reducingthe silicate content to about 68%. Accordingly, there is an insulficient amount of silicate present in the spray-dried product to inhibit the formation of tarnish Moreover, the presence of pyrophosphate in the spray-dried product resulting from the decomposition of tripolyphosphate in creases the tarnishing effect of the spray-dried product, since alkali metal silicate is much less elfective as a tarnish inhibitor against pyrophosphates than against tripolyphosphates.

The of alkali metal silicate would be efiective as a tarnish inhibitor in tripolyphosphate detergent compositions containing from 10% to 20% of alkali metal carbonate if there were no decomposition of the tripolyphosphate and silicate upon spray drying. Since there is such decomposition, it is necessary in accordance with the invention to employ the synergistic tarnish inhibitors therein.

The compositions of the invention will be further illustrated in connection with the following examples. Spraydried tripolyphosphate detergent compositions were prepared having the following percentage compositions by weight, at the time of mixing the components together and prior to spray drying. In Examples 9 and 10 the fluorescent dye was the disodium salt of 4,4-bis| [4-phenylamino 6 [bis(2 hydroxyethyl) lamino s triazine 2- ylaminol|-2,2' stilbene disulfonic acid.

Example 7 PART A Percent Sodium dodecylbenzene sulfonate 10 Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Sodium sulfate 19.48 2 mercaptothiazoline 1 0.02

Total 100 2-mercaptothiazo1ine (based on tripolyphosphate) 0.06%.

PART B Percent Sodium dodecylbenzene sulfonate 10 Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15 Sodium carboxymethyl hydroxyethyl cel1ulose 0.5 Water 10 Sodium sulfate 18.48 2 mercaptothiazoline 1 0.02 Sodium tallow soap 2 1.00

Total 100 Z-mercaptothiazoline (based on tripolyphosphate) 0.06%.

2 Sodium tallow soap (based on tripolyphosphate) 2.9%.

Example 8 PART A q Percent Sodium hardened-tallow alcohol sulfate c 10 Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15 Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Sodium sulfate 19.48 Z-mercaptothiazoline 1 0.02

Total 100 2-mercaptothiazoline (based on tripolyphosphate) 0.06%.

6 PART B Percent Sodium hardened-tallow alcohol sulfate 10 Pentasodium tripolypho-sphate 35 Sodium silicate 10 Sodium carbonate 15 Sodium carhoxymethyl hydroxyethyl cellulose 0.5 Water 10 Sodium sulfate 18.48 Z-mercaptothiazoline 1 0.02 Sodium tallow soap 2 1.00

Total 2=mercaptothiazoline (based on tripolyphosphate) 0.06%. Sod1um tallow soap (based on tripolyplhosphate) 2.9%.

Example 9 PART A Percent Pluronic L-64 8.75 Oronite dispersant NIW 1.25 Pentasodium tripolypho-sphate 35 Sodium silicate 10 Sodium carbonate 15 Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Fluorescent dye 0.03 Sodium sulfate 19.47

Total 100 Z-mercaptothiazoline (based on tripolyphosphate) 0.03

PART B Percent Pluronic L-64 8.75 Oronite dispersant NIW 1.25 Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15 Sodium carboxymethyl hydro-Xyethyl cellulose 0.5 Water 10 Fluorescent dye 0.03 Sodium sulfate 19.47

Total 100 Z-mercaptothiazoline (based on tripolyphosphate) 0.03 Sodium tallow soap (based on tripolyphosphate) 1.4

Example 10 PART A Percent Pluronic L64 8.75 Oronite dispersant NIW 1.2 5 Pentasodium tripolyphosphate 35 Sodium silicate 10 Sodium carbonate 15 Sodium carboxymethyl hydroxyethyl cellulose 0.5 Water 10 Fluorescent dye 0.03 Sodium sulfate 19.47

Total .a... 100

2-mercaptothiazoline (based on tripolyphosphate) 0.06

7 8 R B tages thereof. Accordingly, it will be understood that Percent the invention is to be limited only within the scope of the Pluronlc L-64 8.75 a d d l ppen e calms. Oronlte dlspersant NIW 1.25 I claim: zggzi i gig ig 1. A spray-dried detergent composition consisting es- Sodium carbOnat-e 15 sentlallypf from about 20% to about 50% of an alkali Sodium carbox ggz zg g g O 5 metal trlpolyphosphate which 1n aqueous solution tar- Water y y y 3 y mshes German s1lver, from about 5% to about total g ug 0 03 of at least one organic non-soap detergent selected from S 19'47 10 the group consistmg of organic anionic non-soap deter- 0 mm Su ac gents and organic nonionic non-soap detergents, from about 10% to about of an alkali metal carbonate, Total 100 about 10% of an alkali metal silicate, from about 0.03% zmercaptothiazofine (based on m 01 he to about 006% of Z-mercaptothiazoline based on the h t p yp S 15 weight of tripolyphosphate, and from about 1.4% to S 3. 6) f '1 006 about 3.0% of a water-soluble alkali metal soap based 0 i ta ow Soap (based on mpolyphos' on the weight of tripolyphosphate, said soap being sep a e) lected from the group consisting of the alkali metal salts The conditions set forth in Table II below were emof fatty acids having an acyl group of from 8 to 22 carployed in the spray-drying of the compositions in Exambon atoms; the amounts of said thiazoline and soap being P sufficient to inhibit the tarnishing and the components of TABLE II Example No 7A 7B 8A 13 0A 9B 10A 10B Percent Water in Slurry 29 29 33 33 35 35 20 20 Slurry Temperature F). 185 185 185 185 160 160 185 185 Total Mixing Time (minutes) 30 30 30 30 30 Mixing Time After Phosphate Ad ion (minutes) 10 10 10 10 l0 10 Tower Air Inlet Temperature F.) 540 540 540 540 400-450 400450 500-600 520 Examples 9A and 9B were prepared by adding 2-merthe composition being expressed by weight at the time captothiazoline (and soap) in solution to a solution of of mixing thereof and prior to spray drying. the product, which was spray-dried without Z-mercapto- 2. A spray-dried detergent composition as set forth thiazoline or other synergist. These examples differ in in claim 1 wherein the amount of alkali metal tripolythis respect fromthe others which were spray-dried after phosphate is about 3 addition of Z-mercaptothiazoline (and soap) to the 3. A spray-dried detergent composition as set forth crutcher slurry. in claim 1 wherein the alkali metal tripolyphosphate is The tarnishing action of each of the spray-dried deterpen a di m rip yp p gent compositions in Examples 7-10 upon German silver 4. A spray-dried detergent composition as set forth was tested in accordance with the above described test in Claim 1 containing about 10% total of at least one procedure. The following results were noted. Organic p detergent- 5.'A spray-dried detergent composition as set forth in claim 1 wherein the organic non-soap detergent is so- Example 5351 Degree ofTamjsh dium dodecylbenzene sulfonate.

6. A spray-dried detergent composltlon as set forth in claim 1 wherein the organic non-soap detergents are a 3 Slight tar shmixture of (l) a compound having the empirical formula 2 ittfittttttsil 2 )acsnfi nwzm w P p by 2 Barely noticeable tarnish. 5O densing ethylene oxide with a hydrophobic base formed liarrushby the condensation of propylene oxide with propylene 5 Considerable (heavy) tarnish. glycol where b is an integer selected from the group con- 1 Interface Siam sisting of 26 to 30 and a plus c is an integer such that the molecule contains from 40% to of ethylene The compositions in part A of each of Examples 7 10 oxide, and polypropylene alkyl p o averaging contained an alkali metal tripolyphosphate, at least one totfadeoyl in the alkyl Tadloal Condonsod Wlth ethylene organic anionic or nonionic non-soap detergent, an alkali OXide to an average of 9 ethylene OXld? p metal carbonate, an alkali metal silicate, supplemental A p ydetergent composltlon as sot forth builders and one of the synergistic tarnish inhibitors, in'olaim 1 containing about 15% of an alkali metal namely Z-mercaptothiazoline. In these compositions 2- bollatomercaptothiazoline alone was ineffective as a tarnish in- A p ydetergent composition as set forth hibitor, since the compositions tarnished German silver in Claim 1 wherein the alkali metal carbonate is Sodium to a degree of tarnish ranging from slight tarnish to con- Carbonatesiderable tarnish. The compositions in part B of each of A p ydetergent composition as Set forth Examples 7 -10 were as noted above with the exception in claim 1 wherein the Water-soluble alkali metal soap is that an alkali metal soap was also added thereto so-that Sodium tallOW P- each of these compositions contained the synergistic tar- A p ydotofgont Composition Consisting nish inhibitors, namely, 2-mrcaptothiazoline and an alsentially of from about 20% to about 50% of pentasokali metal soap. The compositions in part B showed a dium tripolyphosphate Which in aqueous solution tarvery noticeable improvement over the corresponding comnishes German silver, from about 5% to about 15% of positions in part A, thereby demonstrating the remark sodium dodecylbenzene sulfonate, from about 10% to able effectiveness of the synergistic tarnish inhibitors. about 20% of sodium carbonate, about 10% of sodium Various modifications and changes may be made in the silicate, from about 0.03% to about 0.06% of Z-mercapcompositions of this invention Without departing from tothiazoline based on the weight of tripolyphosphate, and the spirit of the invention or sacrificing any of the advanfrom about 1.4% to about 3.0% of sodium tallow soap K is.

9 based on the weight of tripolyphosphate; the amounts of said thiazoline and soap being sutficient to inhibit the tarnishing and the components of the composition being expressed by Weight at the time of mixing thereof and prior to spray drying.

11. A spray-dried detergent composition consisting essentially of about 35% of pentasodium tripolyphosphate which in aqueous solution tarnishes German silver, about 10% of sodium dodecylbenzene sulfonate, about 15% of sodium carbonate, about 10% of sodium silicate, from about 0.03% to about 0.06% of Z-mercaptothiazoline based on the Weight of tripolyphosphate, and from about 1.4% to about 3.0% of sodium tallow soap based on the Weight of tripolyphosphate; the amounts of said thiazoline and soap being sufiicient to inhibit the tarnishing and the components of the composition being expressed by Weight at the time of mixing thereof and prior to spray drying.

12. A spray-dried detergent composition consisting essentially of from about 20% to about 50% of pentasodium tripolyphosphate which in aqueous solution tarnishes German silver; from about to about 15% total of a mixture of (1) a compound having the empirical formula HO(C H O) (C H -O) (C H O) H prepared by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol where b is an integer selected from the group consisting of 26 to 30 and a plus c is an integer such that the molecule contains from 40% to 50% of ethylene oxide, and (2) a polypropylene alkyl phenol averaging tetradecyl in the alkyl radical condensed with ethylene oxide to an average of 9 ethylene oxide groups; from about 10% to about 20% of sodium carbonate; about 10% of sodium silicate; from about 0.03% to about 0.06% of 2-mercaptothiazoline based on the weight of tripolyphosphate; and from about 1.4% to about 3.0% of sodium tallow soap based on the weight of tripolyphosphate; the amounts of said thiazoline and soap being suflicient to inhibit the tarnishing and the components of the composition being expressed by Weight at the time of mixing thereof and prior to spray drying.

13. A spray-dried detergent composition consisting essentially of about 35% of pentasodium tripolyphosphate which in aqueous solution tarnishes German silver; about 10% total of a mixture of (1) a compound having the empirical formula HO(C H O) (C H O);,(C H O) H prepared by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide With propylene glycol Where b is an integer selected from the group consisting of 26 to 30 and a plus c is an integer such that the molecule contains from to of ethylene oxide, and (2) a polypropylene alkyl phenol averaging tetradecyl in the alkyl radical condensed with ethylene oxide to an average of 9 ethylene oxide groups; about 15% of sodium carbonate; about 10% sodium sill cate; from about 0.03% to about 0.06% of Z-mercaptothiazoline based on the Weight of tripolyphosphate; and from about 1.4% to about 3.0% of sodium tallow soap based on the weight of tripolyphosphate; the amounts of said thiazoline and soap being sufiicient to inhibit the tarnishing and the components of the composition being expressed by weight at the time of mixing thereof and prior to spray drying.

References Cited in the tile of this patent UNITED STATES PATENTS 2,486,922 Strain Nov. 1, 1949 2,618,603 Schaeffer Nov. 18, 1952 2,622,068 Hizer Dec. 16, 1952 FOREIGN PATENTS 156,852 Australia June 3, 1954 157,971 Australia Aug. 2, 1954

Claims (1)

1. A SPRAY-DRIED DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 20% TO ABOUT 50% OF AN ALKALI METAL TRIPOLYPHOSPHATE WHICH IN AQUEOUS SOLUTION TARNISHES GERMAN SILVER, FROM ABOUT 5% TO ABOUT 15% TOTAL OF AT LEAST ONE ORGANIC NON-SOAP DETERGENT SELECTED FROM THE GROUP CONSISTING OF ORGANIC ANIONIC NON-SOAP DETERGENTS AND ORGANIC NONIONIC NON-SOAP DETERGENTS, FROM ABOUT 10% TO ABOUT 20% OF AN ALKALI METAL CARBONATE, ABOUT 10% TO AN ALKALI METAL SILICATE, FROM ABOUT 0.03% TO ABOUT 0.06% OF 2-MERCAPTOTHIAZOLINE BASED ON THE WEIGHT OF TRIPOLYPHOSPHATE, AND FROM ABOUT 1.4% TO ABOUT 3.0% OF A WATER-SOLUBLE ALKALI METAL SOAP BASED ON THE WEIGHT OF TRIPOLYPHOSPHATE, SAID SOAP BEING SELECTED FROM ACIDS HAVING AN ACYL GROUP OF FROM 8 TO 22 CAROF FATTY ACIDS HAVING AN ACYL GROUP OF FROM 8 TO 22 CARBON ATOMS; THE AMOUNTS OF SAID THIAZOLINE AND SOAP BEING SUFFICIENT TO INHINIT THE TARNISHING AND THE COMPONENTS OF THE COMPOSITION BEING EXPRESSED BY WEIGHT AT THE TIME OF MIXING THEROF AND PRIOR TO SPRAY DRYING.