3,577,347 United States Patent Office Patented May 4, 1971 2 problem, they resulted in a composition which was un 3,577,347 stable if it contained a bleach. WATER-SOLUBLE SCOURING COMPOSITION Therefore, it is an object of this invention to provide John Alexander Monick, 102 Jasper Ave., a stable, non-gritty, bleach containing scouring composi Teaneck, N.J. 07666 tion. No Drawing. Filed Apr. 3, 1968, Ser. No. 718,325 5 Int, C. Cld 7/56 Another object of the instant invention is to provide U.S. C. 252-99 4 Claims a stable chlorine bleach containing composition compris ing a chlorine bleach, detergent, and a water soluble salt. ABSTRACT OF THE DISCLOSURE Another object of the instant invention is to provide 10 a stable chlorine containing cleanser comprising a chlorine A stable nongritty cleanser composition comprising a - containing compound, a hydrated water soluble salt, and detergent, bleach, and a water soluble salt, said salt hav a detergent. ing less than 6 molecules of water of hydration. Yet another object of the instant invention is to pro associal vide a stable cleanser composition containing a water soluble salt having less than 6 molecules of water of This invention is directed to a stable non-gritty chlorine hydration. bleach containing cleanser composition. Still another object of the instant invention is to provide It is well known in the art to use a bleach in composi a stable chlorine bleach containing cleanser composition tions which are intended for use as cleansers. In general 20 comprising a water soluble salt having less than 6 mole the compounds employed as bleaches are chlorine con cules of water of hydration, a detergent and a bleaching taining salts which, when contacted with Water, release compound containing chlorine. their chlorine which acts to remove stains. As an aid in Yet a further object of this invention is to provide a the removal of stains, it is also customary to include an scouring composition comprising more than fifty percent insoluble compound as an abrasive to loosen any surface of a water soluble abrasive compound having less than dirt which the scouring composition may be used to re 6 molecules of water of hydration, an anionic or non move. In the past the insoluble salts have included ground ionic surface active agent, and a bleach. quartz, marble, limestone, dolomite, pumice stone or The instant invention is directed to a composition com ground rock. Furthermore, it has been customary to in prising a detergent compound, a bleaching compound and clude in compositions of this type anionic and nonionic 30 a water soluble salt containing less than 6 molecules of detergents which impart surface active properties to the water of hydration. composition. The previously used anionic detergents have The useful detergents which may be used in conjunc included sodium dodecylbenzenesulfonate, potassium do tion with the instant scouring composition include anionic decylbenzenesulfonate, sodium laurylbenzenesulfonate, detergents such as alkylbenzene-sulfonic acid and its salts, sodium cetylbenzenesulfonate; the alkali metal salts of and compounds of the formula alkyl-phenyl-SO3-M, the higher alkylsulfonic acids and the alkali metal dialkyl wherein alkyl may be straight or branched and M is hydro sulfosuccinates, e.g., sodium dioctylsulfosuccinate, and gen or an alkali metal, which compounds comprise a well sodium dihexylsulfosuccinate, sodium sulfoethylphthalate, known class of anionic detergents and include sodium sodium oleyl-p-anisidinesulfonate; sodium tetradecanesul dodecylbenzene sulfonate, potassium dodecylbenzenesul fonate; sodium diisopropylnaphthalenesulfonate; sodium 40 fonate, sodium laurylbenzenesulfonate, sodium cetylben octylphenoxyethoxyethylsulfate, etc. and the alkali metal Zenesulfonate; the alkali metal salts of the higher alkyl alkyl sulfates, e.g. sodium lauryl sulfate. In addition, the Sulfonic acids and the alkali metal dialky sulfosuccinates, specific nonionic surface active agents have included e.g., sodium dioctylsulfoSuccinate, and sodium dihexylsul alkaryl polyglycol detergents such as alkyl-phenolethylene fosuccinate, sodium sulfoethylphthalate, sodium oley-p- oxide condensates (2-200 moles ethylene oxide), e.g., anisidinesulfonate; sodium tetradecanesulfonate; sodium p-isooctyl phenol-polyethylene oxide (10 ethylene oxide diisopropylnaphthalenesulfonate; sodium octylphenoxy units), long chain alcohol-ethylene oxide condensation ethoxyethylsulfonate, etc.; and the alkali metal alkyl sul products (2-200 moles ethylene oxide), e.g., dodecyl al fates, e.g., sodium lauryl Sulfate. cohol-polyethylene oxides having 4 to 16 ethylene oxide Among the above-noted alkylbenzene-sulfonic acid and units per molecule, polyglycerol monolaurate, glycol di 50 Salts thereof, there are included those which are biode oleate, sorbitan monolaurate, Sorbitan sesquioleate, the gradable and which are particularly characterized by a condensation products of ethylene oxide with sorbitan linear alkyl Substituent of from Co to C2 and preferably esters of long chain fatty acids (Tweens), alkylolamides, from C12 to C15. It is, of course, understood that the amine oxides, phosphine oxides, sulfoxides, etc. carbon chain length represents, in general, an average While compositions of this type have been effective, 55 chain length since the method for producing such products there have been certain problems associated with their usually employs alkylating reagents of mixed chain length. use, that is to say, that the insoluble compounds used It is clear, however, that substantially pure olefins as well as abrasives result in an unpleasant gritty residue which as alkylating compounds used in other techniques can and is left on the surface on which the composition has been do give alkylated benzene sulfonates wherein the alkyl employed. This necessitates expending considerable addi 60 moiety is substantially (i.e. at least 99%) of one chain tion effort to remove this undesirable gritty film. length, i.e., C12, C13, C14, or C15. The linear alkyl benzene In an effort to eliminate this problem, it has been con Sulfonates are further characterized by the position of ventional to substitute a soluble salt for all or part of the the benzene ring in the linear alkyl chain, with any of insoluble compound. By substituting a soluble salt for the position isomers (i.e. alpha to omega) being operable an insoluble one, one obtains a composition which rinses 65 and contemplated. away and leaves no residue, as all the components of the The linear alkyl benzene sulfonates are generally and composition are then soluble and are rinsed away in the conveniently prepared by sulfonating the corresponding normal cleaning process. The salts conventionally used in alkyl benzene hydrocarbons which in turn may be pre a composition of this type include hydrated salts such as pared by alkylating benzene with a linear alkyl halide, a carbonates, bicarbonates, phosphates, borates, and halo O 1-alkene or a linear primary or secondary alcohol. Pure gen salts of alkali and alkaline earth metals. While these isomers (of the 1-phenyl isomer) are prepared by reduc salts eliminated the gritty residue which was formerly a tion of the acylated benzene (alkyl phenyl ketone) using 3,577,347 3 4. a modification of the Wolff-Keshner reaction. The 2 It has unexpectedly been found that when one com phenyl isomer is obtained from n-undecyl phenyl ketone bines the above ingredients with more than fifty percent and methyl magnesium bromide to form the tertiary alco of a water soluble salt containing less than 6 molecules of hol which is dehydrated to the alkene and then hydro water of crystallization, one obtains a stable, nongritty genated. The 5-phenyl isomer is obtained similarly from scouring composition. While the use of compounds simi n-heptyl phenyl ketone and n-butyl magnesium bromide. lar to those generally described is old, the salts previously The other isomers are obtained in a similar manner from employed have included a lesser amount of salts such as: the appropriate n-alkyl phenylketone and n-alkyl magne sium bromide. sodium borate decahydrate In addition to the benzene sulfonates one may also em sodium sulfate decahydrate ploy the lower alkyl (C. to C4) analogs of benzene such O sodium carbonate decahydrate as toluene, xylene, the trimethyl benzenes, ethylbenzene, Sodium hypophosphate decahydrate isopropyl benzene and the like. The sulfonates are gen Sodium phosphate dodecal hydrate erally employed in the water soluble salt form which calcium chloride hexahydrate include as the cation, the alkali metals, ammonium, and 5 all of which result in a composition which is unstable due lower amine and alkanolamine. to deterioration of the chlorine containing components. It Examples of suitable linear alkylbenzene sulfonates: has now been found, however, that this can be overcome Sodium in-decyl benzene sulfonate by limiting the molecules of water of hydration that the Sodium n-dodecyl benzene sulfonate water soluble salt employed in the composition contains sodium n-tetradecyl benzene sulfonate 20 and by using more than fifty percent thereof. Useful Sodium n-pentadecyl benzene sulfonate water soluble salts may be exemplified by, but are not Sodium n-hexadecyl benzene sulfonate limited to: lithium phosphate hemihydrate and the corresponding lower alkyl substituted homologues lithium potassium tartrate monohydrate of benzene as well as the salts of the cations previously 25 lithium tartrate monohydrate referred to. Mixtures of these sulfonates may, of course, lithium borate pentahydrate also be used which mixtures which may include com lithium bromide monohydrate pounds wherein the linear alkyl chain is smaller or larger anhydrous lithium carbonate than indicated herein provided that the average chain lithium chloride length in the mixture conforms to the specific require 30 lithium citrate tetrahydrate ments of Clio to C22. lithium fluoride The linear paraffin sulfonates are also a well-known lithium iodide trihydrate group of compounds and include water soluble salts (al anhydrous lithium nitrate kali metal, amine, alkanolamine, and ammonium) of: magnesium biphosphate trihydrate 1-decane sulfonic acid dibasic magnesium citrate pentahydrate 1-dodecane sulfonic acid dibasic magnesium phosphate trihydrate 1-tridecane sulfonic acid tribasic magnesium phosphate pentahydrate 1-tetradecane sulfonic acid sodium ammonium phosphate tetrahydrate 1-pentadecane sulfonic acid Sodium ammonium sulfate tetrahydrate 40 anhydrous sodium bicarbonate 1-hexadecane sulfonic acid sodium bisulfate monohydrate as well as the other position isomers of the sulfonic acid anhydrous sodium bisulfite group. sodium bitartrate monohydrate In addition to the paraffin sulfonates illustrated above, anhydrous sodium bromate others with the general range of Co to C2a alkyls may be 45 anhydrous sodium bromide used, with the most preferable range being from C to Sodium carbonate monohydrate C20. anhydrous sodium carbonate The linear alkyl sulfates which are contemplated in this sodium chloride invention comprise the range of Co to Cao. Specific sodium citrate dihydrate examples include Sodium n-decyl sulfate; sodium n-dodec 50 Sodium hypophosphate monohydrate yl Sulfate; sodium n-hexadecyl sulfate; sodium n-hepta anhydrous sodium nitrate decyl sulfate; sodium n-octadecyl sulfate; and the ethoxyl anhydrous sodium nitrite ated (1 to 100 moles ethylene oxide) derivatives; and, of Sodium borate pentahydrate course, the other water-soluble salt-forming cations men sodium perborate tetrahydrate tioned above. 55 monobasic sodium phosphate monohydrate Also useful in conjunction with the instant invention dibasic sodium phosphate pentahydrate are nonionic detergents such as alkaryl poylglycol deter sodium sulfide gents such as alkyl-phenol-ethylene oxide condensates (2- anhydrous calcium bromide 200 moles ethylene oxide), e.g., p-isooctyl phenol-poly anhydrous calcium carbonate ethylene oxide (10 ethylene oxide units), long chain alco 60 calcium chloride dihydrate hol-ethylene oxide condensation products (2-200 moles calcium nitrate monohydrate ethylene oxide), e.g., dodecyl alcohol-polyethylene oxides calcium nitrite monohydrate having 4 to 16 ethylene oxide units per molecule, poly dibasic calcium phosphate monohydrate glycerol monolaurate, glycol dioleate, sorbitan mono-lau monobasic calcium phosphate dihydrate 65 calcium Sulfate dihydrate rate, Sorbitan monostearate, sorbitan monopalmitate, sor anhydrous calcium sulfate bitan monooleate, Sorbitan sesquioleate, the condensation calcium Sufite dihydrate products of ethylene oxide with sorbitan esters of long potassium bicarbonate chain fatty acids (Tweens), alkylolamides, amine oxides, anhydrous potassium bisulfate phosphine oxides, sulfoxides, etc. 70 potassium borate pentahydrate The bleaching compositions useful in the instant inven anhydrous potassium bromide tion include solid chlorine yielding compounds such as anhydrous potassium carbonate trichlorocyanuric acid and its salts, dichlorocyanuric acid potassium carbonate 1.1/2 water and its Salts, chlorinated trisodium phosphate, calcium potassium chloride hypochlorite, and compounds of a similar type. 75 potassium citrate monohydrate 3,577,847 5 6 potassium fluoride EXAMPLE IV monobasic potassium phosphite A composition comprising: anhydrous potassium iodate potassium iodide Sodium chloride ------87.840 anyhdrous potassium nitrate Perfume ------250 anhydrous potassium nitrite Phthalocyanine Blue ------125 potassium percarbonate monohydrate Sodium bromide ------700 monobasic potassium phosphate Sprayed LAS' detergent ------6. (S35 potassium pyrophosphate trihydrate Trisodium phosphate, anhydrous ------3.950 anhydrous potassium Sulfate O Trichlorocyanuric acid, Sodium Salt ------500 potassium sulfite dihydrate Linear tridecylbenzene sulfonate. potassium tartrate hemihydrate was formulated in a ball mill. This composition was tested The composition of the instant invention, in addition to by the method of Example I. As a result of these tests the the water soluble salt with less than six molecules of water composition of this example was unexpectedly determined of hydration, bleach, and detergent, may contain builders, 5 to be stable as the chlorine containing compound had not brighteners, germicides, soil suspending agents, anti-redep deteriorated and the weight loss of the composition was osition agents, anti-oxidants, coloring materials (dyes negligible. and pigments), perfumes, water-soluble alcohols, non EXAMPLE V detergent alkali metal benzene sulfonates, etc. The following examples are provided as being exem 20 A composition comprising: plary of the composition of the instant invention which is Sodium chloride ------40,000 not to be deemed as being limited thereto. In addition, Fine silex ------47.840 these examples teach the criticality of the degree of hydra Perfume ------0.250 tion of the Water soluble salt employed in the instant com Phthalocyanine Blue ------0.125 position and the concentration thereof in relation to the 25 Sodium bromide ------0.700 stability of the total composition. Sprayed LAS detergent ------6.63.5 Trisodium phosphate, anhydrous ------3.950 EXAMPLE I Trichlorocyanuric acid, sodium salt ------0.500 A composition comprising: 30 Linear tridecylbenzene sulfonate. Was formulated in a ball mill. This composition was tested Borax (decahydrate) ------90.4 by the method of Example I. As a result of these tests, the Linear tridecyl Sodium salt ------9.0 bleaching compound contained in the formulation, i.e. Sodium salt of trichlorocyanuric acid ------0.5 Sodium trichlorocyanuric acid, deteriorated and the com Perfume ------0.1 position was therefore deemed unstable. Was formulated in a ball mill and packaged to test the stability thereof over a controlled time period in com EXAMPLE VI parison with the composition of Example II. The com A composition comprising: positions were stored at 120 F., 90 F., and at room tem Calcim sulfate ------90.4 perature for a period of three, six and twelve weeks. The 40 Sodium dodecyl benzene sulfonate ------9.0. composition of this example lost considerable weight at Trichlorocyanuric acid ------0.5 each of the indicated temperatures during each of the in Perfume ------0.1 tervals. was also formulated. The above composition was tested EXAMPLE II as in Example II and found to be stable and was also A composition comprising: 45 found to leave no gritty residue on a cleaned porcelain Borax Pentahydrate ------90.4 surface. Linear tridecyl Sodium Salt ------9.0 EXAMPLE VII Sodium salt of trichloro-cyanuric acid ------0.5 A composition comprising: Perfume ------0.1 50 Potassium bisulfate ------90.4 was formulated in a ball mill and packaged to test the Sodium lauryl benzene Sulfonate ------9.0 stability thereof over a controlled time period. In addition, Dichlorocyanuric acid ------0.5 this composition was tested to determine if a residue was Perfume ------0. left after the cleaning of a porcelain surface. This com was also formulated. The above composition was tested position lost less weight and did not cake during the time 55 as in Example II and found to be stable and was also intervals and at the temperatures of Example I, while the found to leave no gritty residue on a cleaned porcelain composition of Example I caked at each of the indicated surface. temperatures. EXAMPLE VIII EXAMPLE III 60 A composition comprising: A composition comprising: Potassium borate pentahydrate ------90.4 Fine silex ------87.840 Potassium dodecyl benzene sulfonate ------9.1 Perfume ------0.250 Sodium salt of trichlorocyanuric acid ------0.5 Perfume ------0.1 Phthalocyanine Blue ------0.125 65 Sodium bromide ------0.700 Was also formulated. The above composition was tested Sprayed LAS detergent ------6.635 as in Example II and found to be stable and was also Trisodium phosphate, anhydrous ------3.950 found to leave no gritty residue on a cleaned porcelain Trichlorocyanuric acid, sodium Salt ------0.500 surface. 1 Linear tridecylbenzene sulfonate. O EXAMPLE X was formulated in a ball mill. This composition was tested A composition comprising: by the method of Example I. As a result of these tests, the Potassium carbonate ------90.4 bleaching compound contained in the formulation, i.e. Sodium dioctyl SulfoSuccinate ------9.1 sodium trichlorocyanuric acid, deteriorated and the com Sodium salt of dichlorocyanuric acid ------0.5 position was therefore deemed unstable. 75 Perfume ------0.1 3,577,847 7 8 was also formulated. The above composition was tested EXAMPLE XVI as in Example II and found to be stable and was also found to leave no gritty residue on a cleaned porcelain A composition comprising: Surface. Sodium carbonate ------90.4 EXAMPLE X Sodium lauryl Sulfonate ------9.0 Calcium hypochlorite ------0.5 A composition comprising: Perfume ------as a -- a-- run an - -n - - as an as 0.1 Calcium nitrite monohydrate ------90.4 was also formulated. The above composition was tested Sodium hexadecyl benzene sulfonate ------9.0 as in Example II and found to be stable and was also Calcium hypochlorite ------0.5 O found to leave no gritty residue on a cleaned porcelain Perfume ------0.1 surface. was also formulated. The above composition was tested EXAMPLE XVII as in Example II and found to be stable and was also A composition comprising: found to leave no gritty residue on a cleaned porcelain 15 Sodium bicarbonate ------90.4 surface. Sodium cetyl benzene Sulfonate ------9.0 EXAMPLE X Chlorinated trisodium phosphate ------0.5 A composition comprising: Perfume ------0.1 Calcium nitrate monohydrate ------90.4 20 was also formulated. The above composition was tested Sodium n-heptadecyl sulfate ------9.0 as in Example II and found to be stable and was also Chlorinated trisodium phosphate ------0.5 found to leave no gritty residue on a cleaned porcelain Perfume ------0.1 Surface. EXAMPLE XVIII was also formulated. The above composition was tested as in Example II and found to be stable and was also 25 A composition comprising: found to leave no gritty residue on a cleaned porcelain Ammonium chloride ------90.4 surface. Sodium hexyl Sulfosuccinate ------9.0 EXAMPLE XII Trichlorocyanuric acid ------0.5 A composition comprising: 30 Perfume ------0.1 was also formulated. The above composition was tested Calcium chloride dihydrate ------90.4 as in Example II and found to be stable and was also Sorbitan monolaurate ------9.0 found to leave no gritty residue on a cleaned porcelain Trichlorocyanuric acid ------0.5 surface. Perfume ------0.1 35 Each of the ingredients of the instant invention are was also formulated. The above composition was tested employed in ranges in which they are conventionally used. as in Example II and found to be stable and was also The amount of detergent may range from 1-30% and found to leave no gritty residue on a cleaned porcelain one may use from 0.01-15% bleach. In all cases, how surface. ever, the amount of water soluble salt having less than 40 six molecules of water of hydration is more than fifty EXAMPLE XIII percent. A composition comprising: EXAMPLE XIX

Lithium carbonate ------wn as a me a who at a r reaw 90.4 Example III was repeated, employing in separate formu Sorbitan monostearate ------9.0 lations the composition of Example III and two addi 45 tional formulations, wherein the fine silex was replaced Dichlorocyanuric acid ------0.5 from the composition of Example III by an equal amount Perfume ------an as n m r n m an as a sa -- a-- rom or r------0.1 of borax pentahydrate in one formulation and an equal was also formulated. The above composition was tested amount of borax decahydrate in another formulation. as in Example II and found to be stable and was also These three compositions were studied for their stability found to leave no gritty residue on a cleaned porcelain 50 under ambient conditions. This study was run concur Surface. rently, and after five weeks storage in conventional con EXAMPLE XIV tainers these two compositions, along with the composi tion of Example III, were analyzed for percent chlorine A composition comprising: loss. The results are as follows: Lithium chloride ------90.4 55 Chlorine loss (percent) Sodium n-pentadecyl Sulfonate ------9.0 Composition of Example III ------28 Sodium salt of trichlorocyanuric acid ------0.5 Composition of Example III having silex replaced Perfume ------0.1 With borax pentahydrate ------11 Composition of Example III having silex replaced was also formulated. The above composition was tested 60 as in Example II and found to be stable and was also With borax decahydrate ------48 found to leave no gritty residue on a cleaned porcelain While various preferred embodiments of the present surface. invention have been illustrated by way of specific ex EXAMPLE XV ample, it is to be understood that the present invention is in no way to be deemed as limited thereto, but should A composition comprising: 65 be construed as broadly as any or all equivalents thereof. I claim: Sodium pyrophosphate ------90.4 1. In a method for cleaning surfaces by scouring foll Sodium n-octadecyl sulfonate ------9.0 lowed by rinsing with water, the improvement which com Sodium salt of dichlorocyanuric acid ------0.5 prises employing as a scouring composition a stable, Perfume ------0.1 70 compatible, non-gritty composition consisting essentially was also formulated. The above composition was tested of, as in Example II and found to be stable and was also (a) 1 to 30% by weight of a detergent selected from found to leave no gritty residue on a cleaned porcelain the group consisting of anionic and nonionic de Surface. 75 tergents, 3,577,347 9 10 (b) from 0.01 to 15% by weight of a chlorine bleach sodium borate, sodium sulfate, sodium carbonate, and ing compound, and Sodium prosphate. (c) at least more than 50% by weight of a water References Cited soluble abrasive salt having less than six molecules UNITED STATES PATENTS of water of hydration, and selected from the group consisting of alkali and alkaline earth metal salts, 2,534,781 12/1950 MacMahon ------252-99 said components a, b and c constituting substantially 2,590,794 3/1952 Robson ------252-187 the entire composition. 2,634,238 4/1953 Soule ------252-99 2. The process of claim 1 wherein the bleaching com 2,980,622 4/1961 Symes ------252-99 pound is selected from the group consisting of trichloro 3,108,079 10/1963 Wixon ------252-99 cyanuric acid, the sodium salt of trichlorocyanuric acid, O 3,120,378 2/1964 Lee et al. ------252-95 dichlorocyanuric acid, the sodium salt of dichlorocyanuric 3,256,199 6/1966 Symes ------252-99 acid, calcium hypochlorite, and chlorinated trisodium 3,336,228 8/1967 Fuchs et al. ------252-99 phosphate. 3,361,675 1/1968 Fuchs et al. ------252-99 3. The process of claim 1 wherein the detergent is 5 selected from the class consisting of linear alkyl benzene MAYER WEINBLATT, Primary Examiner sulfonates. U.S. C. X.R. 4. The process of claim 1 wherein the water soluble salt having less than six molecules of water of hydration 252-95, 187; 8-111 is selected from the group consisting of sodium chloride, 20