Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents
  • C11D3/3955—Organic bleaching agents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents
  • C11D3/3953—Inorganic bleaching agents

Definitions

• a dry, granular, bleaching and disinfecting composition having improved effectiveness against food (e.g., ferric tannate and tea) stains, consisting essentially of from to about 95% water-insoluble abrasive; a stable compound which is a source of available chlorine in an amount to give from about 0.05% to about available chlorine; 0 to about water-soluble organic detergent; from 0 to about 60% by Weight alkaline detergency builder; and sulfamic acid or water-soluble sulfamate to provide a ratio of available chlorine to sulfamic acid or sulfamate based on sulfamic acid content of from about 500:1 to about 1:1 the composition having a pH under use conditions of at least 10.5.
• food e.g., ferric tannate and tea
• the present invention relates to cleanser compositions containing a stable compound which is a source of available chlorine characterized in that the composition also contains sulfamic acid, or water-soluble sulfamate, which under the conditions of use, improves the speed of bleaching and cleaning of the composition when the composition is used on food stains, while the composition is stable in storage.
• the prior art has disclosed that the combination of a hypochlorite bleach and sulfamic acid is a slower, less rigorous bleaching agent than the hypochlorite alone when used in the bleaching of paper pulp, it has been surprisingly discovered that under the conditions which occur in the use of an alkaline cleanser, such as described herein, the sulfamic acid improves the speed of bleaching of the cleanser when it is used on, e.g., tea stains and ferric tannate stains which are representative of stains from foods containing tannic acid. High alkalinity and hypochlorite bleaches will normally remove most stains readily. However, some stains such as ferric tannate and tea stains are difficult to remove quickly.
• compositions of this invention remove tannate and tea stains from dishes, sinks, etc. is enhanced by the presence of the sulfamic acid or sulfamate.
• Another stain which is removed at a faster rate when the sulfamic acid is present is FD & C #4 Red food coloring.
• Suitable compounds which provide a source of available chlorine include chlorinated trisodium orthophosphate, trichlorocyanuric acid, potassium and sodium dichlorocyanurates, 5,5 dimethyl 1,3 dichlorohydantoin, sodium and potassium benzenesulfonchloramines, sodium and potassium para-toluenesulfonchloramines, sodium and potassium chloro bromo cyanurates, lchloro-3-bromo-5, S-dimethyl hydantoin, N-chloro succinimide, trichloroand hexachloro-melamines, and mixtures thereof.
• the preferred chloro compound is chlorinated trisodium orthophosphate since it is relatively inexpensive.
• the composition can also contain inorganic bromides, organic bromides or compounds which provide available bromine.
• Suitable inorganic bromides are those which are water-soluble especially the alkali metal bromides such as sodium and potassium bromides.
• Suitable organic bromides include tetramethyl ammonium bromide, tetraethyl ammonium bromide, dimethyl coconut alkyl benzyl ammonium bromide, trimethyl dodecyl ammonium bromide and trimethyl benzyl ammonium bromides.
• Suitable compounds which provide available bromine include the chloro bromo cyanurates, succinimides, and hydantoins mentioned above and the corresponding dibromo cyanurates, bromo succinimide, and dibromo hydantoin.
• Other sources of available bromine include the bromo melamines and brominated trisodium orthophosphate. These bromides and sources of available bromine also increase the speed of bleaching of the compositions containing available chlorine.
• the bromide ion can be from about 1% to about 150% by weight of the amount of available chlorine present, preferably from about 25% to about 135%, and the bromine can range from about 0.5% to about 50% by weight of the amount of available chlorine present, preferably from about 17% to about 35%.
• the utility of bromides in combination with hypochlorite bleaches is described in more detail in US. Pat. 2,815,311. The disclosure of this patent is incorporated herein by reference.
• the sulfamic acid, or water-soluble sulfamate is present in an amount sufficient to provide a ratio of available chlorine to sulfamic acid (molar equivalents of sulfamate can be substituted for the sulfamic acid) of from about 500:1 to about 1:1; preferably from about :1 to about 1.5 :1; more preferably from about 10:1 to about 15:1, and most preferably from about 6:1 to about 3:1.
• a ratio of available chlorine to sulfamic acid preferably from about :1 to about 1.5 :1; more preferably from about 10:1 to about 15:1, and most preferably from about 6:1 to about 3:1.
• Excess sulfamic acid tends to hurt performance by slowing the speed of bleaching and adds to the cost of the product.
• a small drop in detergency will result from using excess sulfamic acid since it undesirably lowers the pH of the composition.
• Sulfamic acid as used herein also includes water-soluble sulfamates which give the sulfamic ion in solution.
• Especially preferred sulfamates include sodium and potassium sulfamates.
• Other water-soluble sulfamates include magnesium, calcium, lithium, and aluminum sulfamates.
• Sulfamic acid itself is preferred since it is not very hygroscopic.
• Sodium and potassium sulfamates are also preferred.
• the sulfamates are dissolved in water and sprayed on the abrasive described hereinafter, and dried to provide a composition which is unexpectedly relatively unaffected by the hygroscopicity of the sulfamates.
• the sulfamic acid and sulfamates are unique in that they provide improved bleaching performance without adversely affecting the physical characteristics and other performance characteristics of the compositions. For example, bromides can increase the speed of bleaching, but they can affect the odor of the composition during use.
• compositions of this invention contain from about 0.01% to about 1% perfume, preferably from about 0.1% to about 0.3%.
• the sulfamate stabilizes the perfume in the presence of the available chlorine, especially when the perfume contains aldehydes, alcohols,
• esters, and/or ketones Protection for the aldehydes appears to last for a shorter time than for the alcohols, ketones, or esters, but in all cases there is an improvement in perfume stability. This is very surprising when considered against the background that the sulfamic acid and/or sulfamates improve the speed of bleaching.
• a water-insoluble abrasive comprises a major portion of the cleanser to provide a scouring cleanser.
• the scouring cleansers of this invention contain at least 60% by weight abrasive, preferably from about 60% to about 95%. Almost any water-insoluble particulate abrasive can be used in the compositions of this invention.
• water-insoluble abrasives suitable for use in the cleanser compositions of the present invention include finely divided particulate siliceous abrasives such as quartz, silica, feldspar, pumice, pumicite, zirconium silicate, volcanic ash, diatomaceous earth, china clay, whiting, bentonite, talc and the like, calcium carbonate and aluminum oxide.
• a suitable particle size for this abrasive material is from about 0.5 mm. diameter to about 0.001 mm. diameter. Finer particles can also be used.
• the amount of abrasive used is determined by the end use. If the cleanser is to be used for dishwashing in an automatic dishwashing machine, then there should not be any abrasive in the composition.
• the water-soluble organic detergents which can be used in the scouring cleanser composition of this invention are anionic, nonionic, zwitterionic and cationic organic detergents.
• the preferred class of organic detergents is the anionic non-soap class.
• the preferred anionic detergents are alkali metal alkyl benzene sulfonates wherein the alkyl group contains from about to about 18 carbon atoms and alkyl sulfates which contain from about 10 to about 18 carbon atoms and wherein said alkyl groups are preferably straight chain alkyl groups.
• Suitable detergents for use in scouring cleanser compositions of this invention include those detergents described in US. Pat. 3,318,817 at column 4, line 37, through column 6, line 30, and column 9, line 6 through line 57. This list is merely illustrative. The disclosure of this patent is incorporated herein by reference.
• Suitable cationic detergents are those having the formula RN(R X wherein R is an alkyl chain containing from about 8 to about 20 carbon atoms, each R is selected from the group consisting of alkyl and alkanol groups containing from 1 to 4 carbon atoms and benzyl groups there being normally no more than one benzyl group and two R groups can be joined by either a carboncarbon, ether, or imino linkage to form a ring structure, and X represents a halogen atom, sulfate group, nitrate group or other pseudohalogen group.
• Specific examples are coconut alkyl trimethyl amine chloride, dodecyl dimethyl benzyl bromide, and dodecyl methyl morpholino chloride.
• the above organic detergents are used in amounts not to exceed 10% by weight of the composition and preferably in amounts of about 1% to about 6% by weight of the composition.
• the purpose of the organic detergent is to provide the primary detergency effect in cooperation with the alkaline detergency builders described hereinafter.
• the lower limit is set by the detergency requirement and the upper limit is set based on such considerations as streaking, rinsing, sudsing, etc.
• the alkaline detergency builders provide the proper pH for the composition and enhance the detergency effect of the organic detergent.
• the alkaline detergency builder should be used in amounts less than about 60% by weight of the composition preferably in amounts from about 3.5% to about 15% by Weight of the composition.
• Suitable examples of alkaline detergency builders include those described in US. Pat. 3,309,319 at column 4, line 44 through column 5, line 9. The disclosure of this patent is incorporated herein by reference.
• compositions can also contain up to about 5% by weight of the composition of borax (sodium tetraborate decahydrate) in accordance with the disclosure of the copending application of Franklin Dale Moore, Ser. No. 649,021, filed June 26, 1967. The disclosure of this application is incorporated herein by reference.
• borax is preferably used with chlorinated trisodium phosphate which it stabilizes during storage. The stabilization of the chlorinated trisodium phosphate also improves the odor of the compositions.
• Suitable inert inorganic salts can also be included in the compositions in amounts less than about 20% by weight of the composition.
• inert inorganic salts include sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, etc.
• Other minor ingredients which can be included are soil suspending agents such as sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose, optical brighteners, dyes pigments, antibacterial agents, tarnish inhibitors such as benzotriazole, etc.
• Formica panels were cleaned with silica abrasive and oxalic acid. The panels were then covered with a concentrated tea solution, then with 0.1 M FeSO -7H O, then with 0.1 M Na CO and finally with the concentrated tea solution again. The panels were then dried, rinsed, and wiped. This procedure was repeated until a uniform stain was obtained.
• the powdered detergent was a spray dried granule having the formula Sodium alkyl (Cu) benzene sulionate 17.3%; sodium toluene sulionate, 2.0%; sodium tripolyphosphate, 49.5%; sodium silicate (1.6 ratio), 6.1%; sodium sulfate, 13.9%; minor ingredients including unsulfonated materials, pigment, etc., 1.2%; and water, balance.
• Cu Sodium alkyl
• EXAMPLE II In this example, varying amounts of sulfamic acid were added to composition 3 of Example I, replacing abrasive.
• composition 1 2 3 4 5 6 7 Percent snllarnic acid Available chlorine/sulfamic acid 12 6 4 3 2 1.5 Whiteness (fast bleaching test) 6.7 7.3 9.5 9.5
• EXAMPLE III In this example, varying amounts of phosphoric acid (to adjust pH) were added to compositions corresponding to Composition 4 of Example I. Compositions 2, 4, 6 and 8 also contained sulfamic acid.
• composition 1 2 3 4 5 6 7 8 Percent sulfamic acid 0.0 0. 12 0. 0 0. 12 0.0 0.12 0. 0 0. 12 pH 9. 0 9. 0 10.0 10. 0 11. 0 11.0 11. 5 11.5 Whiteness (fast bleaching test) 3. 8 2. 5 5. 0 4 2 5. 5 6. 5 7. 4 8. 7
• Ratio of available Percent chlorine to Average time sulfamic sulfamic to bleach Run acid acid (seconds) In the following runs (7-12), varying amounts of sulfamic acid were added to the basic formula of 13.3% of the detergent of Example I, 21.8% chlorinated TSP (.71% of available chlorine), 0.15% perfume, 3.0% borax, and the balance the silica sand abrasive of Example I.
• Ratio of available Percent chlorine to Average time sulfamic sulfamic to bleach acid acid (seconds) The sulfamic acid increased the speed of bleaching of the chlorinated trisodium orthophosphate in the above composition.
• composition I Percent by weight of the Perfume component: Perfume composition Phenyl ethyl alcohol 25 Citronellol 15 Geraniol 15 Linalool 10 Terpineol 25 Cinnamic alcohol Borneol 5 Eucalyptol 1 Eu genol l Rhodinol 1 Nerol 1 Why alcohol 1
• Composition II Percent by weight of the Perfume component: perfume composition Benzaldehyde 5 Citral 5 Cinnamic aldehyde 5 Cuminic aldehyde 5 Decyl aldehyde Undecyl aldehyde 10 Nonyl aldehyde 10 Vanillin 10 Heliotropin 10 Paratertiary butyl alpha methyl hydro cinnamic aldehyde 10 Hydroxy citronellal 10 Phenyl acetaldehyde 10 Composition III Percent by weight of the Perfume component: perfume composition Hexyl salicylate 8 Benzyl acetate 8 Terpinyl
• Composition 1 is stabilized to a lesser extent and Composition IV is stabilized the least amount by the sodium sulfamate.
• Sulfarnic acid and other water-soluble sulfamates, e.g., potassium sulfamate when substituted on a molar basis for the sodium sulfamate will also stabilize the perfume compositions of this example.
• the following builders are substituted, either wholly or in part, e.g., a 1:1 ratio, for the sodium tripolyphosphate, substantially equivalent results are obtained in that the sulfamic acid and/or sulfamates improve the speed of bleaching of the compositions so long as the pH of the composition under usage conditions is maintained above about 10.5: carbonates, tripolyphosphates, pyrophosphates, hexametaphosphates, ethylenediaminetetraacetates, N (2 hydroxyethyl)- ethylene diamine triacetates, nitrilotriacetates, N-(2-hydroxyethyl)-nitrilodiacetates, phytates, ethane-l-hydroxyl,l diphosphonates, methylene diphosphonates, ethylidenediphosphonates, isopropylidene diphosphonates, benzylmethylidene, diphosphonates, chloromethylidene diphosphonates, benzy
• abrasives When in the above examples the following abrasives are substituted, either wholly or in part, (e.g., a 1:1 ratio by weight), for the silica abrasive, substantially equivalent results are obtained in that the sulfamic acid and/or water soluble sulfamates improve the speed of bleaching of the compositions: feldspar, pumic, pumicite, zirconium silicate, volcanic ash, diatomaceous earth, China clay, whiting, bentonite, talc, calcium carbonate and aluminum oxide where the above abrasives have the same particle size as the silica in the above examples.
• Alkyl sulfonates prepared by sulfonating alpha olefins containing an average of about 12 carbon atoms;
• alkyl phenol ethylene oxides wherein the alkyl group contains about 12 carbon atoms and there are approximately 10 moles of ethylene oxide per mole of alkyl phenol the condensation product of alcohols derived from coconut oil and about 10 moles of ethylene oxide per mole of coconut alcohol;
• mixtures thereof e.g. 1:1 mixtures of coconut soap and alkyl sulfonates; alkyl sulfates and alkyl benzene sulfonates; coconut oil fatty acid monoglyceride sulfates and fatty acyl isethionates; and alkyl phenol ethylene oxide and dodecyl dimethyl amine oxide.
• the following sources of available chlorine are substituted either wholly or in part (e.g., a 1:1 ratio by weight) for the chlorinated trisodium orthophosphate substantially equivalent results are obtained in that the sulfamic acid and/or sulfamates improve the speed of bleaching of the compositions: trichlorocyanuric acid, potassium and sodium dichlorocyanurates, 5,5-dimethyl-1,3-dichlorohydantoin, sodium and potassium benzenesulfonchloramines, sodium and potassium para-toluene sulfonchloramines, sodium and potassium chloro bromo cyanurates, 1-chloro-3-bromo-5, S-dimethyl hydantoin, N-chloro succinimide, trichloro and hexachloro melamines, and mixtures thereof.
• the following compounds are substituted either wholly or in part (e.g. a 1:1 ratio by weight) for the sulfamic acid and/ or sodium sulfamate, substantially equivalent results are obtained in that the speed of bleaching of the compositions is improved: Potassium sulfamate, lithium sulfamate, magnesium sulfamate, calcium sulfamate, and aluminum sulfamate.
• the sulfamic acid/or water-soluble sulfamates improve the speed of bleaching of the compositions: sodium bromide, potassium bromide, tetramethyl ammonium bromide, tetraethylammonium bromide, dimethyl coconut-alkyl benzyl ammonium bromide, trimethyl dodecyl ammonium bromide, trimethyl benzyl ammonium bromide, sodium and potassium dibromocyanurates, bromo succinimide, dibromo hydantoin, tetrabromomelamine, and brominated trisodium orthophosphate.
• compositions can be used to bleach tea stains by forming aqueous slurries or solutions containing from about 1% to about 50% of the compositions so as to prepare an aqueous bleaching composition containing from about 0.006% to about .3% available chlorine and then applying said aqueous bleaching composition to said tea stains.
• the sulfamic acid and/or water soluble sulfamate will improve the speed of bleaching of the compositions of this invention without adversely alfecting the stability of the composition. It is also surprising that it is only in alkaline media, buffered against pHs below about 10.5, that the sulfamic acid and/or water-soluble sulfamate improve the speed of bleaching of the compositions of this invention. It is also surprising that the compositions of this invention can be used so effectively against tea stains when similar bleaching compositions, without the sulfamic acid or sulfamate present, are less eflfective.
• compositions of this invention do not contain ammonium or substituted ammonium salts since ammonium and substituted ammonium cations react with the available chlorine, thereby decreasing the bleaching capacity of the compositions.
• a bleaching cleanser composition having a superior ability to bleach food stains consisting essentially of:
• sufiicient sulfamic acid or water-soluble sulfamate to provide a ratio of available chlorine to sulfamic acid of from about 500:1 to about 1: 1, the composition having a pH under use conditions of at least 2.
• the composition of claim 1 wherein there is from about 60% to about 95 abrasive.
• composition of claim 1 wherein the source of available chlorine is selected from the group consisting of: chlorinated trisodium orthophosphate, trichlorocyanuric acid, potassium and sodium dichlorocyanurates, 5,5- dimethyl 1,3 dichlorohydantoin, sodium and potassium benzenesulfonchloramines, sodium and potassium paratoluenesulfonchloramine, sodium and potassium chloro bromo cyanurates, l-chloro-3bromo-5,5-dimethyl hydantoin, N-chloro succinimide, trichloro and hexachloromelamines, and mixtures thereof.
• the source of available chlorine is selected from the group consisting of: chlorinated trisodium orthophosphate, trichlorocyanuric acid, potassium and sodium dichlorocyanurates, 5,5- dimethyl 1,3 dichlorohydantoin, sodium and potassium benzenesulfonchloramines, sodium and potassium paratolu
• composition of claim 1 wherein the source of available chlorine is chlorinated trisodium orthophosphate.
• composition of claim 1 wherein the water-soluble organic detergent is from about 1% to about 6% by weight of the composition.
• composition of claim 1 wherein the alkaline detergency builder is from about 3.5% to about 15% by weight of the composition.
• composition of claim 5 wherein the water-solu ble organic detergent is selected from the group consisting of alkali metal alkyl benzene sulfonates wherein the alkyl group contains from about 10 to about 18 carbon atoms and alkali metal alkyl sulfates which contain from about 10 to about 18 carbon atoms.
• composition of claim 1 wherein the ratio of available chlorine to sulfamic acid is from about 3:1 to about 6: 1.
• composition of claim 1 containing as an additional ingredient a compound selected from the group consisting of inorganic bromides, organic bromides and compounds which provide available bromine in amounts to provide from about 1% to about of bromide ion by weight of the amount of available chlorine present when the bromides are present and to provide from about 0.5% to about 50% of bromine by weight of the amount of available chlorine present when the compounds which provide available bromine are present.
• composition of claim 1 wherein the ratio of available chlorine to sulfamic acid is from about 10:1 to about 1.5:1.
• composition of claim 13 wherein the ratio of available chlorine to sulfamic acid is from about 100:1 to about 1.5 :1.
• composition of claim 1 containing as an additional ingredient from about 0.01% to about 1% of a perfume composition consisting essentially of perfume components selected from the group consisting of alcohols, esters, aldehydes, ketones and mixtures thereof.
• composition of claim 14 wherein there is from about 0.1% to about 0.3% of said perfume composition.

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (2)

Publications (1)

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Country Status (6)

Cited By (14)

• 0
  • DK DK133825D patent/DK133825A/da unknown
• 1968
  • 1968-09-16 US US760053A patent/US3583922A/en not_active Expired - Lifetime
  • 1968-10-01 DK DK472568AA patent/DK133825B/da unknown
  • 1968-10-01 NO NO3883/68A patent/NO125592B/no unknown
  • 1968-10-01 SE SE6813241A patent/SE371839B/xx unknown
  • 1968-10-02 FI FI682783A patent/FI49060C/fi active
  • 1968-10-02 GB GB46719/68A patent/GB1197689A/en not_active Expired

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