CA1048365A - Abrasive detergent composition - Google Patents

Abstract

ABRASIVE DETERGENT COMPOSITION

ABSTRACT

Granular detergent compositions containing a minor amount of abrasive are disclosed. Such compositions provide easier and faster cleaning especially in dishwashing operations.

Description

3~5 Backyround Tne instant invention relates to granular detergent compositions containing a minor amount of abrasive which are especially useful where high sur~actant levels are required along with a minor amount of abrasive as in the was~hing of dishes.
The use of abrasives in scouring cleansers is well known in the art. Scouring cleansers contain a major amount of fine abrasive and when used in the dishwashing process provide abrading power to make the removal of cooked ~ r on foods on kitchenware easier and more convenient. The use of such scouring cleansers, however, requires that two ;
products be available for dishwashing: one product being required for removal of non-sticking soils and a second product for scouring purposes.
Accordingly, it is an object of the present invention to provide granular dishwashing compositions containing a minor amount of abrasive which are highly effective in removing soils from kitchenware and providing sufficient abrading power to loosen soil adhering to surface to be cleaned without scratching said surfaces. ;

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It has been discovered that detergent compositions of the desired type can be realised by incorporating into a granular dishwashing composition a minor amount of abrasive having a U.S. Tyler sieve size in the range ~rom thru 20 mesh to on 65 mesh. Although the use of abrasives in cleaning compositions is well known, the prior art teaches away from the présent invention in requiring very fine abrasives to prevent scratching of surfaces. Such very fine abrasives are shown to be inoperative as scouring agents when used in minor amounts in dishwashing compositions.

SUMMARY OF THE INVENTION
. . . __ . . __ .
The instant invention provides a granular detergent composition containing from about 20% to about 35% of a surface-ac-tive agent by weight of the composition,the surface-active agent being selected from the group consisting ;~
of anionic, nonionic, ampholytic, zwitterionic surface-active agents and mixtures thereof, and from about 5% to about 20 by weight of the composition of a water-insoluble abrasive :~:
material having a particle diameter in the range from about 850 microns to about 300 microns.

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DETAILED DESCRIPrI~N OF ~IE INVENTION
The granular detergent compositions of the instant invention can be any the compositions intended for washing clothing and~or dishes wieh the addition of a minor proportion of abrasive. Thus the compositions of the invention comprise a high proportion of surfactant.
Optionally the compositions can contain inorganic and organic builder salts, processing aids, corrosion inhibitors, fillers, buffer salts, suds boosters, suds inhibitors, dyes and perfumes~

SURFACTANT
The instant dishwashing compositions contain from about 20% to about 35% of a surfactant selected from the group consisting of anionic, nonionic, ampholytic, zwitterionic surface active agents and mixtures thereof.
Usually they should be solids but liquid materials find use where they can be absorbed on a component of the -~
composition by procedures known to the art. Preferred compositions cGntain from about 25% to about 30Gb of surfac-~ant, by weight of the composition. Especially preferred are anionic surfactants.
Many anionic detergents can be broadly described ; as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their ;
molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the !~ group consisting of sulfonic acid and sulfuric acid ester radicals. (Included innthe terrn alkyl is the alkyl portion of higher acyl radicals.~ Important examples of the anionic synthetic detergents which can form the surfactant component of the compositions of the present invention are the sodium or , `' .: , - , . , . : . .", ~ - ', " ':: , , .

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potassium alkyl sulfates, especially those obtained b~ ;
sul~ating the higher alcohols (C8 -C18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl ben~ene or toluene sulfonates, ::
in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); sodium alkyl glyceryl ether sulfonates, especially ~hose ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction ~:
product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols~ and about 1 to 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to 10 units of ethylene oxide per molecule and in which the alkyl radicals.contain from 8 to about 12 carbon atoms; the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids~ for example, are derived from coconut oil and sodi~m or potassium ~-acetoxy- or ~-acetamido-aklanesulfonates where the alkane has from 8 to 22 carbon atoms.
Nonionic surface active agents operable in the i.nstant compositions can be any of three basic types --the alkylene oxide condensates, the amides and the semi-polar nonionics.
The alkylene oxide condensates are broadly defined -as compounds produced by the condensation o~ alkylene oxide ..
3Q groups (.hydrophilic in nature) with.an organic hydrophobic . ~ .-. ~ .. . . . . . .
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~4~336;5 compound, whlch can be aliph~tic or alkyl aromatic in na-ture.
The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Examples of such alkylene oxide condensates include:
(1) The condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation pro~
duct of about 6 moles of ethylene oxide with 1 mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the con-densation product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the above-described coconut alcohol. Examples of commercially available nonionic surfactants of this type include Softanol 30 marketed by the Japan Catalytic Chemical Company, Neodol 23-6.5 marketed by the Shell Chemical Company and Kyr ~ ~ ;
EOB marketed by the Procter & Gamble Company.
(2~ The polyethylene oxide condensates of alkyl ~-phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or , . , ~ , :, ' ~ ~ , ,, `, , branched chain confiyuration, with ethylene oxide, the said e~hylene oxi~e being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene, octene, or nonene. Examples o~ compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol, dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol, dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol, di-isooctylphenyl condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially av~lable nonionic surfactants of this type include Igepal~ CO-610 marketed by the GAF
`Corporation; and Trito ~ X-45, X-114, X-100 and X-102, all marketed by the Rohm and Haas Company.
(3) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion o~ these compounds has a molecular weight of from about 1500 to 1800 and of course exhibits water insol- ~-ubility. The addition of polyoxyethylene moieties to this hydrophobic por~ion tends to increase the water-solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxy-e~hylene content is about 50% of the total weight of the condensation product. Examples of compounds of this type include certain of the commercially available Pluronic sur~
factants marketed by the Wyandotte Chemicals Corporation.
(4) The condensation products of ethylene oxide with the product resulting from the reaction of propylene -6- `

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, . . , -33~5 oxide and ethylene diamine. The hydrophobic base o~ these products consists of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of from about 2500 to about 3000. This base is condensed with ethylene oxide to the extent that the conden-sation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about S,000 to about 11,000. Examples of this type of nonionic surfa ~ant include certain of the commercially available Tetronic compounds marketed by the Wyandotbe Chemicals Corporation.
Examples of the amide type of nonionic surface active agent include the ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms. These acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be ~-derived synthetically, e.g., by the oxidation of pet~oleum, ;~
or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
Examples of the semi-polar type of nonionic surface active agents are the amine oxides, phosphine oxides and ;~
sulfoxides. These materials are described more fully in Berry, U.S. Patent 3,819,528, issuèd June 25, 1974 Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic amines which contain a long chain o~ about 8 to 18 carbon atoms and an anionic ~:
water-solubilizing group, e.g. carboxy, sulfo or sulfato. ~-Examples of compounds falling within this de~inition are sodium 3-dodecylamino-propionate, sodium -3-dodecylamino propane sulfonate, and dodecyl dimethylammonium hexanoate.

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Zwitterionic surface active agents operable in the instant composition are broadly described as internally-neutralized derivatives of aliphatlc quaternary ammonium and phosphinoim and tertiary sulfonium compounds, in which the aliphatic radical can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono.
Specific examples of alkyl sulfate salts which can be employed in the instant detergent compositions include sodium lauryl alkyl sulfate, sodium stearyl alkyl sulfate sodium palmityl alkyl sulfate, sodium decyl sulfate, sodium myristyl alkyl sulfate, potassium lauryl alkyl sulfate, potassium stearyl alkyl sulfate, potassium decyl sulfate, ~
; potassium palmityl alkyl sulfate, potassium myristyl alkyl ~ ~ ;
sulfate, sodium dodecyl sulfate, potassium dodecyl sulfate, potasslum tallow alkyl sulfate, sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, potassium coconut alkyl sulfate ; ,-and mixtures of these surfactants. Highly preferred alkyl sulfates are sodium coconut alkyl sulfate, potassium coconut ;;~
alkyl sulfate, potassium lauryl alkyl sulfate and sodium lauryl alkyl sulfate.
Suitabl~e alkyl ether sulfates include the alkali metal ~lithium, sodium and potassium) and alkanolamine ;
salts of ethoxylated, sulfated fatty alcohols. Fatty alcohol precursors of these surfactants include the ; same materials enumerated above in discussion of the - preferred alkyl sulfate surfactants for use in liquid systems. Hiyhly preferred alkyl ether sulfates are the sodium and potassium alkyl ether sulfates which contain '~

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~48365 from about 12 to 18 carbon atoms in the alkyl group (i.e., tallow alcohol derivatives~ and which contain an average of from about 2.0 to 3.5 moles of ethylene oxide per mole of surfactant.
Suitable alkylbenzene or alkyltoluene sulfonates ;nclude the alkali metal (lithium, sodium, potassium) and alkanolamine salts oE straight-or branched-chain alkyl-benzene or alkyltoluene sulfonic acids. Alkylbenzene sulfonic acids useful as precursors for these surfactants include decyl benzene sulfonic acid, undècyl benzene sulfonic acid, dodecyl benzene sulfonic acid, tridecyl benzene sulfonic acid, tetradecyl benzene sulfonic acid and tetrapropylene benzene sulfonic acid. Preferred sulfonic acids as precursors of alkyl-benzene sulfonates useful for granular compositions herein are those in which the alkyl chain is linear and averages about 12 carbon atoms in length. Examples of ~

commercially available alkyl benzene sulfonic ~ids ~ , (R) -useful in the present invention include Conoco~SA 515, SA 597, and Sa 697 all marketed by the Continental~Oil Company and Calsof LAS 99 marketed by the Pilot Chemical Company.
Nonionic surface-active agents, in amounts from 4 to 6~ by weight of the composition; can conveniently be added to anionic surface-active containing compositions of this invention by spraying said agents onto the granular composi-tion.
ABRASI~E
The abrasive agent can be any of the water-insoluble abrasive materials well ~nown in the art.
Included are materials such as agate, garnet, quartz, carborundum, kieselguhr, silica, marble, tripoli, _~_ .. .. .
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flin~, feldspar, emery, pumice, alumina, perlite, expanded perlite, volcanic ash, diatomaceous earth, bentonite, talc, etc. an~ mixtures thereof As employed in this invention the sieve fraction usable is that particle size which passes through a 20 mesh screen (sieve ~-opening - approximately 850 microns) and is retained on a 65 mesh screen (approximately 200 micron opening) using U.~. Tyler Standard sieves. The preferred particle size is the through 20-on ~8 sieve fraction (approximately sieve opening range - 850 to 300 microns) and especially preferred is the through 35-on 4~ sieve fraction (approximate sieve opening range is 425 to 300 microns). The specific gravity of the abrasive material is not critical. For example expanded perlite having a specific gravity of 0.2 and baddeleyite having a specific gravity of about 6.0 are both sùitable in t~is invention. ;
The amount of abrasive included in the compositions `~
is in the range of from about 5% to about 20% of the total composition by weight. Preferred compositions contain from ~ ~
about 10~ to about 15~ by ~eight of abrasive. Abrasive ~ -contents of higher than 20~ are operable but are not req~ired.
It has been discovered that in making formulations containing minor amounts of abrasive the particle size;~is very important. Very fine particles - thru 100 mesh and ~iner - which are taught by the prior art as desirable ~or scouring purposes, are inoperative when used in the instant detergent compositions. While not wishing to be bound by any theory it appears that the high surfactant acts to mask any scouring effect oE very fine particles. Another possible explanation is that in the presence of greasy soils the minor amount of ..... . . ..... . . .

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~6341~365 very fine abrasive may hecome coated with grease and not be able to provide any scouring properties. In any event, it has been discovered that particle sizes heretofore considered too coarse for safe use are operable in minor amounts with no discernible scratching oE hard surfaces. Apparently, those factors ~hich adversely affect the scouring properties of very fine particles also are present when larger particles of abrasive are used to moderate any scratching tendency inherent in the larger particles by themselves. Nevertheless it is recognized that abrasive particles of relatively large diameter could cause scratches on some surfaces and the especially preferred particle diameter range of from about 425 to about 300 microns was chosen to minimize the possibility of scratching surfaces under some conditions of use.
It should be noted that while the average particle diameter of the abrasive material will fall within the ranges specified above for the s2eve fractions considered, due to the inherent non-uniform nature of the particles and the adhering of some fine particles to coarser particles, minor amounts of abrasive material outside the quoted range will be present. Such particle amounts are expected to be less than about 5% fines and less than about 5% of particles having a diameter greater than the desired range.

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-OTHER INGREDIENTS
In addition to the surfactant and the abrasive mat-erial, the compositions of this invention in their simplest form need only contain a suitable material such as sodium sulfate. Minor amounts of water may also be present. Thus the simplest compositions of this invention will contain from 45% to about 75~ of sodium sulfate by weight. If other adjuvants are added to the composition then the amount of ;
fillex material will be correspondingly reduced by the weight of adjuvants added. Thus, the amount of filler, such as sodium sulfate, can be present at levels of from about 30% to about 75%, with a preferred range of from about 30%
to about 40%.
The compositions of this invention can contain ~rom about 4~ to about 16~ by weight of soluble silicate solids. ;~
Soluble silicates are useful in preventing aluminum cor rosion, providing an alkaline pH in the range of about 9 to about 10 for solutions of the instant compositions and in contributing to making a crisp free flowing spray-dried granule. Potassium or preferably sodium sllicates having a weight ratio of SiO2/M20 of from about 1.0 to about 3.2 and preferably from 1.6 to about 2.6 can be used. M in this ~; ~
ratio refers to sodium or potassium. -The compositions of this invention can contain from 5~ to about 30~ by weight of water-soluble alkaline detergency builder salts either of the organic or inorganic types.
~xamples of water-soluble inorganic builder salts which can be used, alone or in admixture with themselves (and organic alkaline sequestrant builder salts) are alkali metal car- ;~
bonates, phosphates, polyphosphates, and silicates. Specific examples of such salts are sodium tripolyphosphate, sodium ca~xnate, potassium carbonate, sodium pyrnphosphate, potassium pyro-phosphate, p~ssium ~l~~

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tripolyphosphate, and sodium hexameta~hosphate. Examplesof organic alkaline sequestrant builder;salts which can ~e used alone or in admixt~re with each other or with the preceding inorganic alkaline bullder salts, are alkali metal amino polycarboxylates (e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates (NTA) and sodium and potassium N-(2-hydroxyethyl)-nitrilo diacetates). Other organic builder salts include the alkali metal salts of 10phytic acid, e.g.; sodium phytate (see U.S. Patent 2,739,942).
Water-soluble salts of ethano-l-hydroxy-l,l-diphosphonate (EHDP), e.g., the trisodium and tripotassium salts, are suitable. Mixtures of any of the preceding organic or inorganic builder salts can be used, especially the EHDP-containing mixtures described in U.S. Patent 3,392,121 issued to surton H. Gedge III, on July Y, lY68.
The composition of this invention can contain ~ ~
builder salts selected from certain zeolites or alumino- ~ ;
silicates. One such aluminosilicate which is useful in the compositions of the invention is an amorphous water-insoluble hydrated compound of the formula Nax(xAl02-ySiO2), wherein x is a-number from 1 to 1.2 and y is 1, said amorphous compound being further characterized y a Mg exchange capacity o~ from about 50 mg. eq. CaCO3/g. to about 150 mg. eq.
CaCO3/g. This ion exchange builder is more fully described in Gedge et al's French patent 2,237,839 published February 14, lY75, ~- A second water-insoluble synthetic aluminosilicate ion exchange material useful herein has the formula Na [AlOz)z. (SiO2)y] xH2O, wherein z and y are integers of at :. .

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le~st 6; the molar ratio o~ z to y is i~ the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264;
said aluminosilicate ion exchange material ha~ing a particle size diameter from about 0.1 micron to about 100 microns; a calcium ion exchange capacity of at least about 200 mg. eq./g; ~ -and a calcium ion exchange rate of at least about 2 grains/
~allon/minute/gram. This ion exchange builder is more fully described in Belgian patent 814,874 issued on November 12, 1974 to Corkill et al.
Preferably, the builder salts are tripolyphosphates, pyrophosphates, NTA or EHDP and mixtures thereof, preferably --~ , - .
the sodium salts.
The compositions of this invention can contain from about 0.5% to about 5~ of an organic suds builder select~d from the group consisting of C10-Cl6 fatty alcohols and normal amides, monoethanol amid0s, diethanol amides, isopropanol amides and butanol amides of C10_ fatty acids. The mono- and diethanol am.ides and normal amides of such acids are preferred. .
The detergent compositions of this invention can contain, if desired any o~ the usual adjuvants, diluents and additives, for example moisture, perfumes, dyes, other organic detergent sur~actants, antitarnishing agents, anti-redeposition agents, bacteriostatic agents, fluorescers, suds depressors and the like, without i detracting from the advantageous properties of the compositions.
The granular compositions of this invention can conveniently be prepared by admixture of the components ~ i ~ and in a slurry and spray drying the mixture to obtain the granular composition. This method is especially ' :.. ~ : ' : . . . . . . .

convenient when the amount of abrasive mate~ial present in the final composition is about 5~ to about 10%.
An alternative procedure for making the composition of this invention is to admix the abrasive material with a spray dried granular detergent composition which contains all the ingredients of the final composition except for the abrasive. This approach has the advantage of requiring less drying capacity and in avoiding the possible wear on pumps etc. used in spray drying. 'ro avoid segregation of the physical mix because of possible differences in specific gravity the abrasive material can be sprayed with a melted non~interfering adhering substance just prior to mixing the abrasive material with the granular component.
A suitable normally solid adhering material for this ;~
purpose is a polymer of ethylene glycol (widely known as PEG) having a molecular weight in the range of 2000 to about 8000. ;
The following examples are glven to illustrate --the invention. All amounts and percentages in the specification and claims are by weight unless otherwise indicated.
Example I
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~ spray dried granular detergent composition having the following composition was prepared~
Control Composition A 70:30 mixture of C12aV branched chain al ..
alkylbenzene ~-70%~ and C12av alkyltoluene (-30%) sulfonate, Na salt 28.0%
Na toluene sulfonate 2.8 Silicate solids (SiO2:Na2O ~ 2:1)15.0 NaCl 3,0 Na2S4 44.4 ~;
H2O & misc. 6.8 ~;

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Compositions containing ar~ abrasive were prepared -by simply mixing the appropriate amount of the above com-position with the amount of abrasive desired in the finished composition.
The abrasive used in this test was pumice which as received had the following sieve analysis~
U.S. Tyler sieves on 20 mesh 6.Y5 on 48 mesh 18.35 on 65 mesh 10.~8 on 100 mesh 8.59 ~ -thru 100 mesh 55.11 ~;
The pumice was incorporated into the desired compositions on an `'as received" basis and by sieve fractions. Thus the thru 20-on 48, thru 48-on 65, thru 65-on 100 and through 100 represent sieve fractions of the pumice.
The compositions ~o be tested were prepared by dissolving 32 grams of the composition in 800 cc of water at ambient temperature (65-70F.l.
The compositions were tested in a blind paired ~ ;
comparison manner by a technician washing 12 naturally ~`
soiled ceramic plates and 2 pots~pans with each solution.
A sponge was used by the technician in the washing process.
At the complet~on OI the s,lashing comparison the technician was asked to judge whlch solution cleaned faster and easier.
The results of the tests are summarized in TABLE I.

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TABLE I
DISHWP~SHING TEST

Composition judged to be faster/easier Test No. Compositions Compared in dishwashing ~ vs B
1 C vs C-~5% P A

2 C vs C+10%~P B

3 C vs C+10% P s

4 C vs C+15% P B
C+5% P vs C+15% P B :~
6 C+10% P vs C+15~ P B
7 C+15% P vs C+10% P s 8 C vs C~5% P B
9 C+5% P vs C+10% P A ~
~ C vs C+10~ P "on 48" B ~ :
11 C vs C+10% P "on 65" B
12 C+10% P "on 48"vs C+10% P "on 65" A
13 C+10~ P "on 65"vs C+10~ P "on 100" A
14 C vs C+10% P "on 48" B
P = Pumice ~ :
C - "Control" composition -~
C+X%P = compositions arrived at by mixing the appropriate amount of C with - the level of P desired in the composition :~
to give 32 grams of product~
The results clearly show that faster and easier : . .
cleaning of soiled dishes was obtained when pumice was : -added to the composition. The level of 5% pumice appears to be at the threshold of getting an observable advantage as shown by comparing tests 1 and 8. When sieve fractions of the pumice are compared, the thru 20-on 48 fraction ; ~:
was best, the thru 48-on 65 fraction was next best and ~.

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the thru 65-on 100 fraction was third. ;
Substantiall~ similar results were obtained when `
the Control composition is adjusted by the addition of Na2SO4 to equalize the surfactant levels in solution for the compositions being compared.
Example II
Formulations were tested in the washing of chinaware stained with a cooking sauce ~chili sauce) and chinaware stained with uncooked scrambled egg. The cooking sauce contains a variety of materials including chocolate, hot peppers, tomato paste, onions and other ingredients and is popularity known in Mexico as "Mole" sauce. Three dishes were completely and evenly coated for each product to be , tested and then allowed to dry before being washed. The , results obtained l,product preferred) were subjected to statistical analysis. The results of the test are su~marized in TABLE 2. The solution preparation and the washing technique was as in Example Io STAINED DISH TEST

Ease of Removal Test No. Compositions Compared Rating -,, A B Mole Sauce C vs C+5% P ~ NSD NSD

16 C vs C~5% P NSD NSD

17 C vs C+10% P B B

18 C+10% P vs C~15% P NSD NSD

19 C vs C~5% P NSD B ~

C vs C~10% P B B ~ ;

21 C+5% P ~s C+10% P NSD NSD ~ ;

P-Pumice NSD-no significant differences at the 95% confidence level.
.

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The results again show that the addition of abrasive to the composition aided in getting faster and easier cleaning. That the advanta~e was not statis- :
tically significant in all the test ~uns is not surprising in view of the small size of each test but it will be noted that in no test was the composition without abrasive .:
better than the compositi.ons with abrasive.
Example 3 The Control formulation with 10% pumice - the thru 20-on 48 sieve fractions - was tested for safety to kitchenware by daily washing for a period of one month the items listed below which had been stained with Mole sauae. The washing procedure used was as in Example 1 with the addition that each item is washed for 30 seconds.
TAsLE 3 .
No. stained :;
Item and washed daily .
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Glass plates 1 ~: :

~lastic plates 4 Chinaware 2 ;~

Glasses ~ 2 Pans (Teflon ) 2 ~;

Pottery 2 An equal number of the above items were washed .

~: with a solution of the control composition without abrasive.
~. .
After one month careful examination of the items showed no difference between washing treatments except for the plastic plates on which minute scratches were observed for ~;
those plates washed with the composition containing abrasive.
These scratches are not noticeable to the casual observer and are considered of no importance.

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Exam~ 4 The "Control" composition in Example 1 is further compared in dishwashing against the control ~ -composition diluted with 20~ pumice (particle diameter in the range of about 425 to about 3no microns). The advantage of including the abrasive to make the washing of dishes faster and easier is agàin observed.
Examp_e 5 In Example 4 the pumice is respectively replaced by quartz, feldspar, perlite, expanded perlite and silica having comparable particle size diameters. Substantially similar advantageous results for the abrasive containing compositions are obtained.
Example 6 In Example 1 the control composition is replaced by compositions differing only in additionally containing up to 30g inorganic builder salts selected from the group ~-consisting of sodium tripolyphosphate, sodium pyrophos-phate, sodium carbonate and mixtures thereof. Substan-tially similar advantageous resuIts are obtained for the composition containing the abrasive material.
Example_7 The surface-active agent in the control composi-tion of Example 1 is respectively replaced by a surface-active agent selected from the group consisting of the ;
sodium salt of coconut alkyl sulfate, the sodium salt of C13 alkylbenzene sulfonate, the sodium salt of coconut alkyl ether sulfate wherein one mole of alcohol is reacted with 3 moles of ethylene oxide before sulfation and mixtures thereof. Substantially similar advantageous results for the inclusion of the abrasive materialare obtained.

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Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A granular detergent composition containing from about 20% to about 35% of a surface-active agent by weight of the composition, the surface-active agent being selected from the group consisting of anionic, nonionic, ampholytic, zwitterionic surface-active agents and mixtures thereof, and from about 5% to about 20% by weight of the composition of a water-insoluble abrasive material having a particle diameter in the range from about 850 microns to about 300 microns.

2. A composition according to Claim 1 wherein the particle diameter of the abrasive material is from about 425 to about 300 microns.

3. A composition according to Claim 1 wherein the abrasive material is present at from about 10% to 15% by weight of the composition.

4. A composition according to Claim 1 wherein the surface-active agent is an anionic surface-active agent selected from the group consisting of the alkali metal salts of alkyl sulfates having from 8 to 18 carbon atoms in the alkyl chain, the alkali metal salts of alkylbenzene having 9 to 15 carbon atoms in the alkyl chain, the alkali metal salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol and about 1 to 10 moles of ethylene oxide and mixtures thereof.

5. A composition according to Claim 1 wherein the abrasive material is selected from the group consisting of silica, perlite, expanded perlite, diatomaceous earth, feldspar, bentonite, emery, pumice and mixtures thereof.

6. A composition according to Claim 4 wherein the abrasive material is selected from the group consisting of silica, perlite, expanded perlite and pumice.

7. A composition according to Claim 5 wherein the abrasive material is pumice.

8. A composition according to Claim 1 which ad-ditionally contains from about 4% to about 16% of sodium or potassium silicate having an SiO2:M2O ratio of from about 1.0 to about 3.2.

9. A composition according to claim 1 which ad-ditionally contains from about 5% to about 30% of a builder salt.

10. A composition according to Claim 8 wherein the builder salt is selected from the group consisting of alkali metal tripolyphosphates, alkali metal pyrophosphates, alkali metal carbonates, alkali metal nitrilotriacetates and mixtures thereof.

11. A granular detergent composition consisting essentially of (a) from about 20% to about 35% of a surface-active agent selected from the group consisting of the sodium salt of C11-12 alkylbenzene sulfonate, the sodium salt of C11-12 alkyltoluene sulfonate and mixtures thereof;
(b) from about 5% to about 20% of an abrasive material selected from the group consisting of pumice, perlite, expanded perlite, silica and mixtures thereof and having a particle diameter in the range of from about 425 to about 300 microns;
(c) from about 4% to about 16% of sodium silicate having an SiO2/Na2O ratio of from 1.6 to about 2.6;
(d) from about 30% to about 75% sodium sulfate; and (e) from about 6 to about 15% of moisture.

12. The composition of Claim 10 which additionally contains from about 5% to about 30% of a builder salt selected from the group consisting of sodium tripolyphosphate, sodium pyrophosphate, sodium carbonate, trisodium nitrilo-triacetate and mixtures thereof.

13. A granular detergent composition consisting essentially of (a) from about 25% to about 30% of the sodium salt of a 60:40 to 70:30 mixture of C11-12 alkyl-benzene and C11-12 alkyltoluene sulfonate;
(b) from about 2% to about 3.5% of sodium toluene sulfonate;
(c) from about 10% to about 15% of pumice having a particle diameter in the range of from 425 to about 300 microns;
(d) from about 14% to about 16% of sodium silicate having an SiO2/Na2O ratio of from 1.8 to about 2.2;
(e) from about 30% to about 40% of sodium sulfate; and (f) from about 2.5% to about 3.5% sodium chloride; and (g) from about 6 to 9% of moisture.