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Publication numberUS3458446 A
Publication typeGrant
Publication dateJul 29, 1969
Filing dateMay 18, 1966
Priority dateMay 18, 1966
Also published asCA813300A, DE1669103A1
Publication numberUS 3458446 A, US 3458446A, US-A-3458446, US3458446 A, US3458446A
InventorsRamon Bruno Diaz
Original AssigneeColgate Palmolive Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Abrasive scouring cleanser
US 3458446 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,458,446 ABRASIVE SCOURING CLEANSER Ramon Bruno Diaz, Douglaston, N.Y., assignor to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Filed May 18, 1966, Ser. No. 550,967 lint. Cl. Clld 7/18 US. Cl. 252-99 8 Claims ABSTRACT OF THE DISCLOSURE An abrasive scouring cleanser comprising as essential ingredients a water-insoluble, inorganic, siliceous abrasive material, a water-soluble, organic detergent compound, an alkali metal monopersulfate salt and a water-soluble alkali metal or alkaline earth metal bromide salt.

This invention relates to abrasive scouring cleansers. More particularly, it relates to abrasive scouring cleansers of the type which contain monopersulfates as bleaching and oxidizing constituents.

It has now been discovered that the stain removal efficacy of abrasive scouring cleansers which contain monopersulfate oxidizing agents is substantially benefited by the inclusion in such compositions of a small amount of a water-soluble bromide salt. Thus, the abrasive scouring cleansers of the instant invention are characterized by highly rapid and complete stain and soil removal, oxidizing and disinfecting action. This action appears to be substantially greater than is achieved by comparable chloride salts. In addition, by virtue of the absence of the hypochlorites or chlorine liberating constituents (such an water-soluble chloride salts) previously proposed for use in abrasive scouring cleansers, the instant compositions are characterized (when unperfumed) by a pleasant odor which is relatively non-irritating, both on use with water and with respect to residual odor effects on the hands of users. The elimination of hypochlorites from the instant cleansers also facilitates perfuming thereof by conventional essential oils and perfumery constituents. In addition, these improved compositions are highly stable on storage and eificacious in polishing tarnished metal surfaces and in removal of smears or deposits of soft materials such as aluminum on porcelain surfaces.

In accordance with the present invention, an abrasive scouring cleanser comprises at least about 60% by weight of a Water-insoluble inorganic siliceous abrasive material having a particle size (diameter) of less than about 0.5 mm., about 0.1 to 20% by weight of an alkali metal monopersulfate salt, about 0.5 to 15% by weight of a water-soluble organic detergent compound substantially stable in the presence of said monopersulfate salt, and about 0.1 to 10% by weight of a water-soluble bromide salt.

The abrasive agents of the scouring cleansers of the present invention include siliceous materials such as silica, feldspar, pumice, vulcanic ash, diatomaceous earth, bentonite and talc, and mixtures thereof. For general use, it is preferred to use either silica or feldspar of various degrees of fineness for they are relatively hard and result in a whiter product. The abrasives may vary in hardness, particle size and shape, and the choice for a particular composition is generally dependent upon the contemplated field of application. The particle size of the abrasive is less than 0.5 mm. and in general, the maximum particle size of substantially all of the abrasive is about 0.15 mm. Normally the abrasive employed will have a particle size such that at least about 85% and preferably 99% by Weight thereof passes through a sieve having 0.074

' mm. openings. On the other hand, in the interest of effecice tive cleansing action, it is appropriate for at least about 8% by weight of the abrasive particles to have a diameter of about 0.037 mm. or larger. The abrasive is present in a proportion of at least about 60%, and preferably at least about to by weight of the cleanser.

The alkali metal monopersulfate salts of the instant compositions preferably are the potassium or sodium salts, which are commercially available. The potassium salt is most preferred and may, if desired, be employed in the form of a triple salt with potassium bisulfate and potassium sulfate, e.g., KHSO KHSO -K SO in the mole ratio of about 221:1.

The third essential ingredient of the present novel abrasive cleansers is a water-soluble organic detergent which is stable in the presence of the contemplated hypochlorite-liberating component. These organic detergents may be anionic, cationic, amphoteric or non-ionic in character, provided that they are compatible with the compositions as a whole in the proportions employed. Where they are liquids under normal conditions, such as the non-ionic agents generally, they may be prepared in particular solid form after absorption upon diatomaceous earth or other similar agents in procedures Well known in the art.

As examples of suitable anionic detersive compounds contemplated within the ambit of the invention are the soaps and the sulfated and sulfonated synthetic detergents, especially those anionic detergents having about 8 to about 26 and perferably about 12 to about 22 carbon atoms to the molecule. The soaps are generally the watersoluble salts of saturated higher fatty acids and mixtures thereof.

The sulfated and sulfonated detersive compounds are also well-known in the art and may be prepared from suitable organic materials which are applicable to sulfonation (true sulfonation and/or sulfation). Of the vast variety of sulfates and sulfonates suitable, it is preferred to use the aliphatic sulfates and sulfonates of about 8 to 22 carbon atoms and the alkyl aromatic sulfonates.

The alkyl aromatic sulfonate detergents referred to may be mononuclear or polynuclear in structure. More particularly, the aromatic nucleus may be derived from benzene, toluene, xylene, phenol, cresols, phenol ethers, naphthalene, derivatives of phenanthrene nuclei, etc. It has also been found that the alkyl group may vary similarly. Thus, for example, the alkyl groups may be straight or branch chained and may consist of such radicals as dodecyl, pentadecyl, octyl, nonyl, decyl, keryl, mixed alkyls derived from fatty materials, cracked paraffin wax olefins and polymers of lower mono olefins, etc. While the number of sulfonic acid groups present on the nucleus may vary, it is usual to have only one such group present in order to preserve as much as possible a balance between hydrophilic and hydrophobic portions of the molecule.

More specific examples of suitable alkyl aromatic sulfonate detergents are the propylated naphthalene sulfonates, the mixed butyl naphthalene sulfonates, tetrahydronaphthalene sulfonates, the various butylated diphenyl sulfonates and phenyl-phenol sulfonates. It is preferred, however, to use the higher alkyl aromatic sulfonates rather than the lower alkyl substituted detergents. Typical examples of this preferred class are the sulfonated and alkylated benzene type compounds wherein the alkyl group is at least 8 and preferably about 10 to about 16 carbon atoms. The benzene ring may possess other substituents including alkyl and hydroxy groups.

Other suitable agents are the surface-active sulfated or sulfonated aliphatic compounds, preferably having 8-22 carbon atoms. Within the scope of such definition are the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e.g., coconut oil monoglyceride monosulfate, tallow diglyceride monosulfate; the long chain pure or mixed alkyl sulfates, e.g., lauryl sulfate, cetyl sulfate; the hydroxy sulfonated higher fatty acid esters, e.g., higher fatty acid esters of low molecular weight alkylol sulfonic acids, e.g., fatty acid esters of isethionic acid; the fatty acid ethanolamide sulfates; the fatty acid amides of amino alkyl sulfonic acids, e.g., lauric amide of taurine, and the like. More particularly, it is preferred to use the sulfated aliphatic compounds containing at least about 8 carbon atoms, especially those having 12 to about 22 carbon atoms to the molecule.

Although the anionic detergents are preferred, cationic, non-ionic and amphoteric detergents may be also employed in whole or as part of the detergent component, provided they are compatible with the other elements of the composition under conditions of storage and use thereof. As cationic detergents there may be noted the long chain alkyl quaternary ammonium compounds, e.g., cetyl quaternary ammonium salts. Within this group are included cetyl tri-methyl ammonium sulfate and cetyl pyridinium sulfate. Another equivalent cationic agent is the diethylene amino ethyl oleyl amide product.

The nonionic agents are also well-known in the art including the polyoxyethylene ethers of alkyl aromatic hydroxy bodies (e.g., the alkylated polyoxyethylene phenols), the polyoxyethylene ethers of long chain aliphatic alcohols, the polyoxyethylene ethers of hydrophobic propylene oxide polymers, and higher alkyl amine oxides such as lauryl dimethyl amine oxide. Amphoteric detergents which also are contemplated, examples thereof including the salts of higher alkyl beta amino propionic acids, e.g., sodium N-lauryl beta alanine; the higher alkyl substituted betaines such as lauryl dimethylammonium acetic acid; and the imidazoline type exemplified by the disodium salt of 1-(2 hydroxyethyl)-1-(carboxymethyl)- 2-(hendecyl)-4,5 dihydroimidazolinium hydroxide.

The anionic and cationic surface active agents are commonly used in the form of their water-soluble salts. For the synthetic anionic compounds, the alkali metal (e.g. sodium, potassium) salts are preferred, though other salts such as ammonium amine, alkylolamine, and alkaline earth metals (e.g. calcium, magnesium) salts may be used if desired. For the cationic agents the chloride, sulfate, acetate and like salts may be employed satisfactorily.

The amount of organic detergent to be used in the present compositions is from about 0.5% up to about 15% by weight, and preferably from about 1% to about 5%. Commercial detergent compositions in which these organic detergents are the active ingredients and are compounded with other materials including sodium sulfate, the various phosphates, etc. may be employed with satisfactory results.

The bromide salt of the instant compositions is a solid, water-soluble bromide which preferably is of substantially neutral or slightly alkaline nature, providing a ready source of bromide ions on dissolution in water. It is preferred to employ alkali metal bromides such as sodium bromide, sodium bromide dihydrate, lithium bromide and potassium bromide, although alkaline earth metal bromides such as strontium bromide and magnesium bromide may also be employed in those instances in which these water hardness-producing cations are not objectionable. The preferred bromides are anhydrous. Preferably the bromide is employed in a proportion of about 0.1% to by weight of the product.

Suitable various adjuvant materials may also be used in the instant abrasive detersive compositions. These additives may be inorganic or organic in structure and may be included in compositions of the present invention. Inorganic water-soluble alkaline builders such as the alkali metal silicates, nitrates, carbonates, bicarbonates, phosphates and borates may be added in any suitable amounts, usually up to about 25% and preferably up to about Examples of such builders include sodium carbonate, sodium bicarbonate, sodium metasilicate, trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate and the corresponding potassium salts. Similarly, there may be employed minor amounts of sequestering agents such as nitrilotriacetic acid, ethylene diamine tetracetic acid, diethylene triamine pentaacetic acid and their salts (e.g. sodium salts), wood pulp, sawdust, magnesite, whiting, sodium carboxymethylcellulose, anti-caking agents, optical brighteners, and the like. These constituents as well as all of the other constituents of the instant cleansers, desirably are of the same fine particle size as the abrasive constituent and suitably may be ground in an attrition mill, if necessary, in order to insure the preparation of a uniform product of smooth appearance.

The following examples are illustrative of the present invention and it will be understood that the invention is not limited thereto. (All of the solid constituents employed in the compositions of these examples have a maximum particle diameter of less than 0.5 mm. and at least 8% by weight of the abrasive, e.g., silica and feldspar, particles have a diameter in the range of 0.0370.l5 mm.) In these examples, and elsewhere throughout the specification and claims, all proportions and ratios are by weight unless otherwise specified.

EXAMPLE I An excellent scouring cleanser preparation is prepared by intimately commingling:

Parts by weight Silica (at least 88% by weight passes through a wire sieve in which the opening between the wires are 0.074 mm.) 86.1

Silica (at least 99% by weight passes through wire sieve in which the openings between the wires are 0.074 mm.) 80.0

Commercial potassium monopersulfate 2.5 Sodium dodecylbenzene sulfonate' 4.0 Sodium sulfate 2.3 Sodium silicate 0.7 Trisodium phosphate 3.0 Potassium bromide 7.5

1 Consists of a mixture of potassium monopersulfate, potas sium bisulfate, and potassium sulfate in a 2/1/1 mole ratio. While there has been disclosed and described what is at present considered to be the preferred embodiment of the invention, it will be understood, of course, that many changes, modifications and substitutions may be made therein without departing from the true scope of the invention as defined in the appended claims.

What is claimed is:

1. An abrasive scouring cleanser consisting essentially of at least 60% by weight of a water-insoluble, inorganic, siliceous abrasive material having a particle size of less than about 0.5 him, about 0.1 to 20% by weight of an alkali metal monopersulfate salt, about 0.5 to 15% by weight of a water-soluble organic detergent compound substantially stable in the presence of said monopersulfate salt, and about 0.1 to 10% by weight of a water-soluble salt selected from the group consisting of alkali metal and alkaline earth metal bromide salts.

2. An abrasive scouring cleanser as set forth in claim 1 which contains at least by weight of silica as the inorganic siliceous abrasive material.

3. An abrasive scouring cleanser as set forth in claim 1 which is free of water-soluble chloride salts which react with alkali metal monopersulfatcs to form hypochlorites.

4. An abrasive scouring cleanser as set forth in claim 1 in which the water-soluble bromide salt is an alkali metal bromide.

5. An abrasive scouring cleanser as set forth in claim 4 in which the alkali metal bromide is sodium bromide.

6. An abrasive scouring cleanser as set forth in claim 1 in which the alkali metal monopersulfate salt is potassium monopersulfate.

7. An abrasive scouring cleanser which consists essentially of at least about 60% by weight of a water-insoluble inorganic siliceous abrasive material having a particle size of less than about 0.15 mm. and such that at least 85% by weight thereof passes through a sieve having 0.074 mm. openings, about 0.2 to 15% by weight of potassium monopersulfate, about 1 to 5% by weight of a watersoluble anionic organic detergent compound substantially stable in the presence of said potassium monopersulfate, and 0.1 to 10% by weight of sodium bromide.

8. An abrasive scouring cleanser which consists essentially of about 86.1% by Weight of silica having a particle size of less than about 0.15 mm. and such that at least 85% by weight thereof passes through a sieve having 0.074 mm. openings, about 1.0% of a mixture of po- References Cited UNITED STATES PATENTS 8/ 1967 Puetzer et al 25299 FOREIGN PATENTS 4/1960 Great Britain.

OTHER REFERENCES Oxone Mono Persulfate Compound, Du Pont, Wilmington, Del. January 1961, p. 8.

MAYER WEINBLATT, Primary Examiner U.S. C1. X.R.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3337466 *May 27, 1965Aug 22, 1967RevlonEffervescent dental cleaner compositions
GB832105A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3715314 *May 25, 1972Feb 6, 1973Procter & GambleScouring cleanser composition
US4028263 *Aug 24, 1973Jun 7, 1977Colgate-Palmolive CompanyBleaching and brightening detergent composition
US4051056 *Sep 4, 1975Sep 27, 1977The Procter & Gamble CompanyAbrasive scouring compositions
US4116878 *Oct 26, 1976Sep 26, 1978Lever Brothers CompanyDetergent composition
US4123376 *Jul 6, 1976Oct 31, 1978Colgate-Palmolive CompanyPeroxymonosulfate-base bleaching and bleaching detergent compositions
US4300897 *Oct 30, 1978Nov 17, 1981Colgate-Palmolive CompanyMethod for bleaching with peroxymonosulfate-based compositions
US4362639 *Aug 31, 1981Dec 7, 1982Warner-Lambert CompanyCleanser with improved afterodor and tarnish resistance
US4405486 *May 20, 1982Sep 20, 1983Warner-Lambert CompanyMethod for preparing granulated perborate salts containing a polymeric fluorocarbon
US4409118 *May 20, 1982Oct 11, 1983Warner-Lambert CompanyTablet forming cleanser composition and method of preparation
US4613332 *Jul 11, 1984Sep 23, 1986The Clorox CompanyControlled generation hypochlorite compositions and method
US4618444 *Sep 17, 1984Oct 21, 1986Purex CorporationHousehold laundry detergent with dual strength bleach
US4895669 *Oct 26, 1988Jan 23, 1990The Clorox CompanyAqueous based acidic hard surface cleaner
EP0265709A2 *Oct 2, 1987May 4, 1988Laporte Industries LimitedA method and composition for the treatment of bathtubs
EP0265709A3 *Oct 2, 1987Jul 11, 1990Laporte Industries LimitedA method and composition for the treatment of bathtubs
EP0271189A2 *Oct 7, 1987Jun 15, 1988The Clorox CompanyAqueous acidic hard surface cleaner
EP0271189A3 *Oct 7, 1987May 24, 1989The Clorox CompanyAqueous acidic hard surface cleaner
Classifications
U.S. Classification510/368, 510/512, 8/108.1, 252/186.43, 510/108
International ClassificationC11D3/14, C11D3/395, C09K3/14, C11D17/00, C11D3/39, C11D3/12, C11D3/02
Cooperative ClassificationC11D17/00, C11D3/3958, C11D3/3955, C11D3/046, C11D3/3953, C11D3/124, C11D3/3942, C11D3/12
European ClassificationC11D3/04S, C11D3/39D, C11D3/12G