US3042622A - Abrasive cleaning composition - Google Patents

Abrasive cleaning composition Download PDF

Info

Publication number
US3042622A
US3042622A US693803A US69380357A US3042622A US 3042622 A US3042622 A US 3042622A US 693803 A US693803 A US 693803A US 69380357 A US69380357 A US 69380357A US 3042622 A US3042622 A US 3042622A
Authority
US
United States
Prior art keywords
water
alkaline
solution
acidic
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US693803A
Inventor
Kirschenbauer Hans George
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US693803A priority Critical patent/US3042622A/en
Application granted granted Critical
Publication of US3042622A publication Critical patent/US3042622A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/08Acids

Definitions

  • the present invention relates to an abrasive cleaning composition exhibiting alkaline and acidic pH conditions in a predetermined order of succession in water, and to a process for preparing the same.
  • Scouring powders and similar abrasive compositions are well-known in the art. Such cleansers may contain alkaline inorganic salts for certain cleansing effects, particularly for grease removal. Cleaning compositions containing abrasive material and an acidic ingredient to obtain more effective removal of stains from metal surfaces have been proposed also.
  • abrasive preparations containing both acidic and alkaline ingredients have not been made as articles of commerce. It would appear that the presence of both acidic and alkaline ingredients in one composition would result in a tendency of these materials to neutralize one another upon admixture with water such that separate and distinct alkaline and acidic cleansing properties would not be obtained thereby.
  • an abrasive cleansing composition comprising essentially a mixture of a waterinsoluble abrasive material, and an alkaline ingredient and an acidic ingredient, said composition exerting both alkaline and acidic cleansing properties in water in any desired order.
  • the present invention relates to an abrasive cleaning composition which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition to the resulting cleaning solution in a predetermined order of succession which comprises essentially a mixture of a Water-insoluble abrasive material, a water-soluble alkaline ingredient which upon contact with water renders the solution alkaline, a water-soluble acidic ingredient which upon contact with water renders the solution acidic, one of the two latter ingredients dissolving sufliciently upon admixture of said composition with water so that the resulting cleansing solution initially has either an alkaline or acidic condition and the other ingredient being adapted to dissolve in an amount sufiicient to subsequently convert said cleansing solution to the opposite pI-I condition.
  • a preferred embodiment relates to a scouring cleanser containing a major proportion of a water-insoluble siliceous abrasive, and minor proportions of a water-soluble alkaline builder salt and a normally solid water-soluble acid, said acid having a coating of a water-dispersible material to retard the rate of solubility of said acid.
  • the ingredient which produces the abrasivecharacteristics primarily is a water-insoluble abrasive'material in particulate form.
  • abrasive agents suitable for use in scouring powders and the like are well-known in the art and are generally siliceous materials.
  • Y Suitable examples are silex, tripoli, pumice, volcanic ash, pumicite, bentonite, diatom-aceous earth, feldspar, etc. and'mixtures thereof.
  • the abrasive may vary in hardness and particle size as desired with the mesh size of the particles varying from about 40 to about 400 generally, and preferably being not larger than 100 mesh, as determined on a US. standard sieve.
  • the amount of the abrasive is variable but is usually a major proportion of the total solids (e.g. at least about and preferably about 60 to about 98% by weight.
  • Any water-soluble ingredient which yields an alkaline pH of above 7, preferably a pH of 8 to 12, to the aqueous solution or slurry may be employed in admixture with the abrasive.
  • Such materials are known and abrasive compositions containing the same are disclosed in US. Patent No. 2,625,514, issued January 13, 1953.
  • the alkaline materials are the water-soluble inorganic alkaline builder salts preferably, such as the alkali metal carbonates (e.g. sodium carbonate), the alkali metal phosphates (e.g.
  • any suitable base such as sodium and potassium hydroxide, and tetramethylammonium hydroxide may be employed also. It is preferred to use the normally solid alkaline salts and bases but, if desired, a normally liquid alkaline material may be employed by suitable combination with a solid carrier such as by adsorption upon diatomaceous earth, bentonite or the like.
  • the alkaline ingredient may be used in any desired amount depending upon the specific ingredient, but there is used usually about /2 to about 25% and preferably about 1 to 15% by weight. These alkaline ingredients are used generally in the form of particles of any suitable size. The particle size of the alkaline ingredient is not critical and may correspond to the approximate particle size of the abrasive.
  • Any water-soluble acidic ingredient which will dissolve in the cleansing solution to yield an acidic pH of below 7, preferably a pH from 2 to 7, to the slurry may be employed in the product.
  • a normally solid acid or acid salt in particulate form.
  • a normally liquid material may be employed by suitable combination with a solid carrier in particulate form, such as diatomaceous earth or bentonite.
  • the particle size of the acidic material is not critical and it may be employed in any suitable size as illustrated for the abrasive. Examples of suitable materials are the organic acids such as tartaric acid, maleic acid, boric acid, glutamic acid, citric acid, acetic acid, oxalic acid, gluconic acid and its lactone, and the like.
  • Suitable inorganic acids and acid salts such as sulfamic and phosphoric acids and sodium bisulfate may be employed also. These materials enhance the removal of tarnish and oxidant stains, particularly from metallic surfaces such as copper, aluminum, steel and the like during use of the product.
  • the acidic ingredient should be used in any amount sufi'icient to convert the alkaline solution to an acidic solution, preferably to a solution having a pH from about 2 to 5, when the quantity of acid has been dissolved or otherwise released in the cleansing solution.
  • the amount of acid be from about /2 to 25 and preferably from about 1 to 15% by weight. If a mixture containing the alkaline and acidic ingredients in powdered form are added to water, the two materials tend to neutralize one another such that the cleansing solution will have either an alkaline or an acidic pH condition depending upon the proportion and strength of the different ingredients. In order to obtain successive action of a separate and distinct nature it has been found that.
  • the rate of soluticn of the acidic constituent is to be sufiicien-tly depressed to permit the alkaline builder on use to dissolve first.
  • the acidic constituent must then be present in stoichiometric excess over the alkaline ingredient so that when it is dissolved or released after a predetermined time the pH of the cleansing solution is reduced to the desired acidic level.
  • the rate of solubility of the acidic constituent may be reduced in any suitable manner. It is preferred to coat the normally solid acid particles with a solution inhibitor such as a Water-dispersible coating agent. The presence of such a film or coating upon the particles of the acid will inhibit and retard the solubility of the acid when the composition is admixed with water.
  • the amount of the coating is not critical and may vary from a monomolecular film to a coating of any particular size depending upon the specific coating agent, its water-dispersibility and the particular time interval which is desired before the change in the pH condition of the aqueous cleaning solution.
  • the predetermined time interval may be controlled so as to be a few seconds up to any point desired in the use of the product such as up to about 30 minutes. It is preferred that the change in pH occur from about 15 seconds to 15 minutes after the product is slurried in Water.
  • any suitable material may be used as the coating agent such as the higher fatty alcohols, preferably having 12 to 18 carbon atoms (e.g. lauryl alcohol, coconut fatty alcohol, cetyl alcohol, stearyl alcohol), mineral oil, the higher fatty acid amide compounds, preferably having 12 to 18 carbon atoms in the acyl radical (lauric acid and coconut acid and myristic acid primary amides and the corresponding monoethanolamides, isopropanolamides and diethanolamides) and their ethylene oxide reaction products having up to about 5 moles of ethylene oxide; the higher fatty acids, preferably having 12 to 18 carbons also such as stearic acid, palmitic acid, tallow fatty acids and the like.
  • the higher fatty acids preferably having 12 to 18 carbons also such as stearic acid, palmitic acid, tallow fatty acids and the like.
  • coating materials are the waxlike polymers of ethylene glycol such as Carbowax 1500, 2025 and 4000, the soluble starches and dextrins and the like. These materials may have highly limited solubility in water to extreme water solubility but are effective to delay the solubility or release of the acid in the cleansing solution.
  • water-dispersible coating agent or equivalent refers to agents of varying water solubility or dispersibility but which have been found to be dispersed or dissolved under conditions of use of the product.
  • organic materials such as lauryl alcohol and lauric acid amides and alkylolamides have limited water solubility but in the presence of organic detergent material tend to dissolve in the cleansing solution.
  • the coating agent may be applied to the particles of the acid in any suitable manner. It is preferred that the coating agent be dissolved, suspended or dispersed in an appropriate solvent or heated to molten form and then sprayed or atomized on the individual acid particles to form the desired coating.
  • Any suitable solvent may be employed, such as a normally gaseous propellant in a pressure container. Examples are the normally gaseous low-molecular weight hydrocarbon and halogenated hydrocarbon propellants, such as propane, butane, halogenated ethanes and methanes.
  • the propellants known as the Freons and Genetrons are suitable, examples being dichlorodifluoromethane and monochlorodifluoroethane.
  • solvents or dispersing mediums such as ethanol, isopropanol and aqueous alcoholic mixtures may be suitably employed also.
  • the coating agent is normally solid, it will dry to a film, and where it is normally liquid it will be adsorbed or absorbed upon the surfaces of the particles.
  • the coating material may be applied also in solid form to the surfaces of the acid particles by mixing the coating agent in powdered form with the acid particles by suitable means for 22 carbon atoms.
  • the final composition is slurried in water to form an aqueous slurry or solution
  • the Water-soluble alkaline ingredient dissolves to form an alkaline solution.
  • the acid particles are coated with lauryl alcohol or any other suitable coating as indicated, its rate of solution is sufliciently depressed to permit the alkaline builder to dissolve first.
  • the coating material disperses in the aqueous medium whereupon the acid is released and dissolves so that the pH is reduced to the desired acidic condition.
  • the alkaline ingredient may be coated in the manner described above so that uncoated acid particles are permitted to ionize or dissolve initially forming an acidic condition followed by release of the alkaline ingredient after the coating has been removed sufficiently.
  • an organic surface-active detersive agent be present in the composition.
  • Such organic detersive agents may be either anionic, cationic or non-ionic agents as described in US. Patent No. 2,625,514.
  • suitable anionic detergents are the water-soluble soaps and sulfated and sulfonated synthetic detergents. More particularly, it is preferred to employ an alkyl benzene sulfonate detergent wherein the alkyl group has about 8 to 16 carbon atoms.
  • Suitable examples are sodium decyl benzene sulfonate, sodium dodecyl and pentadecyl sulfonates wherein the dodecyl and pentadecyl groups are derived from a propylene polymer, and sodium keryl benzene sulfonate.
  • Other suitable agents are the surface-active sulfated or sulfonated aliphatic compounds, preferably having 8 to Examples thereof are sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids (e.g. coconut oil monoglyceride monosulfate), the long-chain pure or mixed higher alkyl sulfates (e.g.
  • lauryl sulfate coconut fatty alcohol sulfate
  • higher fatty acid ethanolamide sulfates the higher fatty acid amides of amino alkyl sulfonic acids (e.g. lauric acid amide of taurine), the higher fatty acid esters of isethionic acid and the like.
  • Suitable cationic detergents which may be employed are the long-chain alkyl quaternary ammonium compounds (e.g. cetyl quaternary ammonium salts). Suitable examples are cetyl trimethyl ammonium chloride, cetyl pyridinium chloride, and the like.
  • non-ionic agents such as the non-ionic polyalkylene oxide condensates with an aliphatic or aromatic hydrophobic group.
  • Such agents have about 5 to 50 alkylene oxide groups usually.
  • examples are the polyethylene oxide condensate with alkyl phenols having 8 to 20 carbons in the alkyl group such as Igepal CA and CO, the polyethylene oxide esters with higher fatty acids such as tall oil or lauric acid condensed with about 16 or 20 ethylene oxide groups, the polyethylene oxide condensates with higher aliphatic alcohols such as lauryl, myristyl, oleyl or stearyl alcohol with 6 to 30 moles ethylene oxide, and the like.
  • anionic and cationic surface-active agents are used commonly in the form of Water-soluble salts.
  • the anionic compounds the alkali metal and ammonium salts are preferred whereas for the cationic agents the chloride, sulfate and acetate and the like acid salts are employed commonly.
  • any amount of the detersive compound may be employed which does not substantially adversely affect the desired characteristics of the product.
  • the detergent be present in amounts from about /2 to about 15% by weight and preferably from 1 to 10% by weight.
  • the anionic and non-ionic surface-active agents in a form where these materials have been premixed with the alkaline builder salts.
  • the mixture containing the detergent and alkaline salts in the form of anaqueous slurry may be subjected to the usual drying procedures in order to obtain a relatively dry homogeneous product such as by drum drying or spray drying of the mixture in known manner.
  • the abrasive material, alkaline and acidic ingredients containing a coating upon one of the latter two materials are mixed in particulate form to produce a dry, cleansing powder.
  • the ingredients are admixed mechanically by tumbling, fluidizing or the like in conventional soap powder mixers known in the art or by any other suitable means for mechanical admixture.
  • the product may contain a bleaching agent which results in effective bleaching action during use of the product.
  • the bleaching agent may be incorporated into the product in any suitable manner, such as during or after the mixing of the essential ingredients. In general, bleaching agents are more etfective in one pH condition than another. Since the product during use will form both acid and alkaline solutions, there will be obtained at some stage optimum conditions for a particular bleaching agent.
  • the bleaching agent may be coated with any suitable material such as the coating agents previously described so that the bleaching agent is released in the same manner.
  • bleaching agents are the known oxygen and chlorine-releasing substances, such as sodium perborate, sodium, calcium and lithium hypochlorites, dichlorocyanuric acid, trichlorocyanuric acid, Chloramine T, dichlorodimethyl hydantoin and the like.
  • the amount of bleaching agent is not critical but will be usually from about 0.01 to 25% of the product.
  • a suitable color indicator which would demonstrate to the consumer when the change from one pH condition to the other pH condition occurs or when a particular pH level is obtained during use.
  • the quantity of indicator is not critical'except that it should be capable of producing a detectable coloration to the cleansing solution. In general, the amount of color indicator will vary with thetype of indicator but is usually from about 5 parts per million to 3% of the product. If methyl orange is employed, the color of the slurry initially is yellow when the acid is coated, but when the acid dissolves subsequently the cleansing solution turns red.
  • Another suitable color indicator is bromo thymol blue which changes color from blue to yellow on conversion of the cleansing solution from an alkaline to an acid nature.
  • the color indicator may be incorporated in any suitable manner such as by spraying it directly upon the particles at any suitable stage in the mixing operation. If the indicator is solid it may be dissolved or'dispersedin a suitable aqueous or alcoholic solution in order to form a liquid solution for ease of application to the particles. When the indicator solution driesupon-the particles the particles will then have a coating of dye which dissolves or disperses upon the initial admixture of the product with water. able dyes are phenol red, t-hymol blue, metacresol purple, etc.
  • Suitable examples are minor amounts of anti-caking agents such as hydrated magnesium trisilicate, sodium carboxymethyl-cellulose, perfume, antiseptics, germicides, skin emollient materials and thelike. 1
  • Example I A powdered sulfamic acid is pretreated to apply a coating to the particles as follows: 200 parts of the powdered sulfamic acid are tumbled in a Mason jar. Through an opening in the cover of the jar, a spray of a lauryl alcohol solution is introduced until 1 part of the lauryl alcohol has been deposited on the surface of the sulfamic acid powder.
  • the spraying composition conther suittains 30% lauryl alcohol dissolved in 70% of a 1:1 mixture of Freon-11 and 12 in a pressure resistant container.
  • An abrasive alkaline scouring cleanser is prepared by tumbling about 89 parts of silex particles, about 0.5 parts of sodium per-borate powder and about 10.5 parts of an alkaline detergent material.
  • This alkaline detergent material is a spray-dried product containing about 30% sodium dodecyl benzene sulfonate detergent, about 40% sodium tripolyphosphate, with the balance being primarily sodium sulfate.
  • about 5 drops of methyl orange indicator are added slowly to obtain good distribution.
  • About 6 parts of the coated sulfamic acid particles are added and the agitation is continued until the product is a uniform, homogeneous mixture.
  • composition shows effective cleansing and bleaching properties during use.
  • Example II The procedure of Example I is repeated except that the lauric acid amide is applied similarly to the alkaline detergent particles and not to the sulfamic acid. The ingredients are mixed thereafter in the same manner and the resulting product exhibits initially an acidic reaction in Water followed by an alkaline reaction.
  • Example 111 The procedure of Example I is repeated using 240 parts of powdered sodium bisulfate in place of the 200 parts of sulfamic acid with similar results.
  • An abrasive cleaning composition Whichfupon admixture with Water is adapted to yield an alkaline pH condition and an acidic pHcondition to the resulting cleaning solution in a predetermined order of succession which comprises a mixture of a major proportion of a water-insolublesiliceous abrasive material, about /2 to 25% by weight of a water-soluble alkaline inorganic builder salt which upon contact with water renders the solution alkaline, about /2 to 25% by weight of a watersoluble normally solid acid which upon contact with water renders the solution acidic, one of the two latter ingredients dissolving sufficiently upon admixture of said composition with water so that the resulting cleansing solution initially has one of said pH conditions and the i 7 material resulting in a retarded rate of solubility so that it is not sufficiently soluble in said solution initially but subsequently dissolves in said solution to convert it to the other of said pH conditions.
  • An abrasive cleaning composition which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition to the resulting cleaning solution in a predetermined order of succession which comprises a mixture a major proportion of a water-insoluble siliceous abrasive material, a minor proportion from about /2 to 25% by Weight of a watersoluble alkaline ingredient which upon contact with water renders the solution alkaline, and a minor proportion from about /2 to 25% by weight of a Water-soluble acidic ingredient which upon contact with water renders the solution acidic, one of the two latter ingredients dissolving sufliciently upon admixture of said composition with water so that the resulting cleaning solution initially has one of said pH conditions and the other ingredient having a coating of a water-dispersible material to retard its initial solubility but being present in a stoichiometric excess so that it subsequently converts said cleaning solution to the other of said pH conditions.
  • An abrasive cleaning composition in accordance with claim 2 which contains about /2 to 15% by weight of a water-soluble organic detergent.
  • An abrasive cleaning composition in accordance with claim 2 which contains about /2 to 25% by Weight of a bleaching agent.
  • An abrasive cleaning composition in accordance with claim 2 which contains a color indicator whereby said composition upon admixture with water results in diiTerently colored solutions in said alkaline and acidic pH conditions.
  • An abrasive cleaning composition which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition successively to the resulting cleaning solution which comprises a mixture of a major proportion of a water-insoluble siliceous abrasive material, about /2 to 25% by weight of a water-soluble inorganic phosphate salt which upon contact with water renders it alkaline, about /2 to 25% by weight of a watersoluble normally solid acid which upon contact with water renders it acidic, said acid having a coating of a water-dispersible material and said composition upon admixture with water yielding an alkaline pH condition in water which is subsequently converted to an acidic pH condition.
  • An abrasive cleaning composition in accordance with claim 8 which contains particles of sulfamic acid coated with said material.
  • An abrasive cleaning composition in accordance with claim 8 which contains about A: to 25 by weight of sodium perborate.
  • An abrasive cleaning composition in accordance with claim 8 which contains a color indicator to indicate by color change when the cleaning solution is converted from said alkaline to said acidic pH condition.
  • An abrasive cleaning composition which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition successively to the resulting cleaning solution which comprises a mixture of a major proportion of a water-insoluble siliceous abrasive material, about /2 to 25 of a water-soluble inorganic alkaline builder salt which upon contact with the water renders the solution alkaline, about /i to 25% by weight of water-soluble normally solid acid which upon contact with the water renders it acidic, said acid having a coating of a water-dispersible material to retard its rate of solubility, but being present in stoichiometric excess so that said composition upon admixture with water yields an alkaline pH condition initially which is subsequently converted to an acidic pH condition.
  • a method of preparing an abrasive cleaning composition characterized by a mixture of a major proportion of a water-insoluble siliceous abrasive material, a minor proportion from about /2 to 25% by weight of a water-soluble alkaline compound and a minor proportion from about /2 to 25% by Weight of a water-soluble acidic compound which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition to the resulting cleaning solution in a predetermined order of succession which comprises coating with a water-dispersible compound one of the latter two ingredients to retard its rate of solubility in water, and admixing the resulting coated compound in an amount in stoichiometric excess with the other ingredient and with said abrasive to form a uniform mixture.
  • a method of preparing an abrasive cleaning composition characterized by a mixture of a major proportion of water-insoluble siliceous abrasive material, and minor proportions of about /2 to 25% by weight each of a water-soluble alkaline ingredient and a water-soluble acidic ingredient adapted to yield an alkaline pH condition and an acidic pH condition successively upon admixture
  • water which comprises treating said acidic ingredient to apply a coating of a Water-dispersible material, and admixing the coated acidic material with said abrasive and alkaline material to 'form a homogeneous mixture.
  • a method in accordance with claim 14 which comprises admixing a color indicator with said mixture to indicate by color change when the resulting cleaning solution is converted from said alkaline to said acidic pH condition.

Description

United States Patent Oil 3,942,622 Patented July 3, 1962 3,042,622 ABRASIVE CLEANING COMPOSITION Hans George Kirschenbauer, Allendale, N..l., assignor to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Nov. 1, 1957, Ser. No. 693,803 16 Claims. (Cl. 25299) The present invention relates to an abrasive cleaning composition exhibiting alkaline and acidic pH conditions in a predetermined order of succession in water, and to a process for preparing the same.
Scouring powders and similar abrasive compositions are well-known in the art. Such cleansers may contain alkaline inorganic salts for certain cleansing effects, particularly for grease removal. Cleaning compositions containing abrasive material and an acidic ingredient to obtain more effective removal of stains from metal surfaces have been proposed also. Heretofore, abrasive preparations containing both acidic and alkaline ingredients have not been made as articles of commerce. It would appear that the presence of both acidic and alkaline ingredients in one composition would result in a tendency of these materials to neutralize one another upon admixture with water such that separate and distinct alkaline and acidic cleansing properties would not be obtained thereby.
In accordance with the present invention, it has been discovered that there can be prepared an abrasive cleansing composition comprising essentially a mixture of a waterinsoluble abrasive material, and an alkaline ingredient and an acidic ingredient, said composition exerting both alkaline and acidic cleansing properties in water in any desired order. More particularly, the present invention relates to an abrasive cleaning composition which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition to the resulting cleaning solution in a predetermined order of succession which comprises essentially a mixture of a Water-insoluble abrasive material, a water-soluble alkaline ingredient which upon contact with water renders the solution alkaline, a water-soluble acidic ingredient which upon contact with water renders the solution acidic, one of the two latter ingredients dissolving sufliciently upon admixture of said composition with water so that the resulting cleansing solution initially has either an alkaline or acidic condition and the other ingredient being adapted to dissolve in an amount sufiicient to subsequently convert said cleansing solution to the opposite pI-I condition. A preferred embodiment relates to a scouring cleanser containing a major proportion of a water-insoluble siliceous abrasive, and minor proportions of a water-soluble alkaline builder salt and a normally solid water-soluble acid, said acid having a coating of a water-dispersible material to retard the rate of solubility of said acid. Various other preferred embodiments will be apparent in the following description.
For convenience of illustration, the invention will be described particularly with respect to the composition yielding successive alkaline and acidic pH conditions though it is to be understood that compositions exhibiting the inverse order are within the scope of the invention. Where reference is made to either an alkaline or acidic pH condition in the specification and claims, it is intended that such condition be illustrated by a 20% slurry of the composition in water.
The ingredient which produces the abrasivecharacteristics primarily is a water-insoluble abrasive'material in particulate form. These abrasive agents suitable for use in scouring powders and the like are well-known in the art and are generally siliceous materials. Y Suitable examples are silex, tripoli, pumice, volcanic ash, pumicite, bentonite, diatom-aceous earth, feldspar, etc. and'mixtures thereof. The abrasive may vary in hardness and particle size as desired with the mesh size of the particles varying from about 40 to about 400 generally, and preferably being not larger than 100 mesh, as determined on a US. standard sieve. The amount of the abrasive is variable but is usually a major proportion of the total solids (e.g. at least about and preferably about 60 to about 98% by weight. Any water-soluble ingredient which yields an alkaline pH of above 7, preferably a pH of 8 to 12, to the aqueous solution or slurry may be employed in admixture with the abrasive. Such materials are known and abrasive compositions containing the same are disclosed in US. Patent No. 2,625,514, issued January 13, 1953. The alkaline materials are the water-soluble inorganic alkaline builder salts preferably, such as the alkali metal carbonates (e.g. sodium carbonate), the alkali metal phosphates (e.g. trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate), the alkali metal silicates (e.g. sodium metasilicate) and the alkali metal borates (e.g. sodium borate) Any suitable base such as sodium and potassium hydroxide, and tetramethylammonium hydroxide may be employed also. It is preferred to use the normally solid alkaline salts and bases but, if desired, a normally liquid alkaline material may be employed by suitable combination with a solid carrier such as by adsorption upon diatomaceous earth, bentonite or the like. The alkaline ingredient may be used in any desired amount depending upon the specific ingredient, but there is used usually about /2 to about 25% and preferably about 1 to 15% by weight. These alkaline ingredients are used generally in the form of particles of any suitable size. The particle size of the alkaline ingredient is not critical and may correspond to the approximate particle size of the abrasive.
Any water-soluble acidic ingredient which will dissolve in the cleansing solution to yield an acidic pH of below 7, preferably a pH from 2 to 7, to the slurry may be employed in the product. In general, it is preferred to employ a normally solid acid or acid salt in particulate form. If desired, a normally liquid material may be employed by suitable combination with a solid carrier in particulate form, such as diatomaceous earth or bentonite. The particle size of the acidic material is not critical and it may be employed in any suitable size as illustrated for the abrasive. Examples of suitable materials are the organic acids such as tartaric acid, maleic acid, boric acid, glutamic acid, citric acid, acetic acid, oxalic acid, gluconic acid and its lactone, and the like. Suitable inorganic acids and acid salts such as sulfamic and phosphoric acids and sodium bisulfate may be employed also. These materials enhance the removal of tarnish and oxidant stains, particularly from metallic surfaces such as copper, aluminum, steel and the like during use of the product.
The acidic ingredient should be used in any amount sufi'icient to convert the alkaline solution to an acidic solution, preferably to a solution having a pH from about 2 to 5, when the quantity of acid has been dissolved or otherwise released in the cleansing solution. In general, it is preferred that the amount of acid be from about /2 to 25 and preferably from about 1 to 15% by weight. If a mixture containing the alkaline and acidic ingredients in powdered form are added to water, the two materials tend to neutralize one another such that the cleansing solution will have either an alkaline or an acidic pH condition depending upon the proportion and strength of the different ingredients. In order to obtain successive action of a separate and distinct nature it has been found that.
it is necessary to defer or retard the rate of solubility of one of these essential ingredients, preferably of-the solid acid constituent. For example, this deferred acidification permits the user to utilizeinitially the alkaline properties of the product followed by' use of the'acidic properties of the product. Accordingly, the rate of soluticn of the acidic constituent is to be sufiicien-tly depressed to permit the alkaline builder on use to dissolve first. The acidic constituent must then be present in stoichiometric excess over the alkaline ingredient so that when it is dissolved or released after a predetermined time the pH of the cleansing solution is reduced to the desired acidic level.
The rate of solubility of the acidic constituent may be reduced in any suitable manner. It is preferred to coat the normally solid acid particles with a solution inhibitor such as a Water-dispersible coating agent. The presence of such a film or coating upon the particles of the acid will inhibit and retard the solubility of the acid when the composition is admixed with water. The amount of the coating is not critical and may vary from a monomolecular film to a coating of any particular size depending upon the specific coating agent, its water-dispersibility and the particular time interval which is desired before the change in the pH condition of the aqueous cleaning solution. Thus, the predetermined time interval may be controlled so as to be a few seconds up to any point desired in the use of the product such as up to about 30 minutes. It is preferred that the change in pH occur from about 15 seconds to 15 minutes after the product is slurried in Water.
Any suitable material may be used as the coating agent such as the higher fatty alcohols, preferably having 12 to 18 carbon atoms (e.g. lauryl alcohol, coconut fatty alcohol, cetyl alcohol, stearyl alcohol), mineral oil, the higher fatty acid amide compounds, preferably having 12 to 18 carbon atoms in the acyl radical (lauric acid and coconut acid and myristic acid primary amides and the corresponding monoethanolamides, isopropanolamides and diethanolamides) and their ethylene oxide reaction products having up to about 5 moles of ethylene oxide; the higher fatty acids, preferably having 12 to 18 carbons also such as stearic acid, palmitic acid, tallow fatty acids and the like. Other coating materials are the waxlike polymers of ethylene glycol such as Carbowax 1500, 2025 and 4000, the soluble starches and dextrins and the like. These materials may have highly limited solubility in water to extreme water solubility but are effective to delay the solubility or release of the acid in the cleansing solution. The term water-dispersible coating agent or equivalent as used herein refers to agents of varying water solubility or dispersibility but which have been found to be dispersed or dissolved under conditions of use of the product. For example, organic materials such as lauryl alcohol and lauric acid amides and alkylolamides have limited water solubility but in the presence of organic detergent material tend to dissolve in the cleansing solution.
The coating agent may be applied to the particles of the acid in any suitable manner. It is preferred that the coating agent be dissolved, suspended or dispersed in an appropriate solvent or heated to molten form and then sprayed or atomized on the individual acid particles to form the desired coating. Any suitable solvent may be employed, such as a normally gaseous propellant in a pressure container. Examples are the normally gaseous low-molecular weight hydrocarbon and halogenated hydrocarbon propellants, such as propane, butane, halogenated ethanes and methanes. The propellants known as the Freons and Genetrons are suitable, examples being dichlorodifluoromethane and monochlorodifluoroethane. Other solvents or dispersing mediums such as ethanol, isopropanol and aqueous alcoholic mixtures may be suitably employed also. In this manner there may be obtained complete or incomplete coating or film on the surface of the acid particles as desired. Where the coating agent is normally solid, it will dry to a film, and where it is normally liquid it will be adsorbed or absorbed upon the surfaces of the particles. The coating material may be applied also in solid form to the surfaces of the acid particles by mixing the coating agent in powdered form with the acid particles by suitable means for 22 carbon atoms.
mechanical admixture including tumbling in a rotary drum. When the final composition is slurried in water to form an aqueous slurry or solution, the Water-soluble alkaline ingredient dissolves to form an alkaline solution. Since the acid particles are coated with lauryl alcohol or any other suitable coating as indicated, its rate of solution is sufliciently depressed to permit the alkaline builder to dissolve first. After a predetermined time, which may be controlled as desired by selection of the particular coating agent, the coating material disperses in the aqueous medium whereupon the acid is released and dissolves so that the pH is reduced to the desired acidic condition.
As indicated, the alkaline ingredient may be coated in the manner described above so that uncoated acid particles are permitted to ionize or dissolve initially forming an acidic condition followed by release of the alkaline ingredient after the coating has been removed sufficiently.
A more specific feature of this invention is that an organic surface-active detersive agent be present in the composition. Such organic detersive agents may be either anionic, cationic or non-ionic agents as described in US. Patent No. 2,625,514. Examples of suitable anionic detergents are the water-soluble soaps and sulfated and sulfonated synthetic detergents. More particularly, it is preferred to employ an alkyl benzene sulfonate detergent wherein the alkyl group has about 8 to 16 carbon atoms. Suitable examples are sodium decyl benzene sulfonate, sodium dodecyl and pentadecyl sulfonates wherein the dodecyl and pentadecyl groups are derived from a propylene polymer, and sodium keryl benzene sulfonate. Other suitable agents are the surface-active sulfated or sulfonated aliphatic compounds, preferably having 8 to Examples thereof are sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids (e.g. coconut oil monoglyceride monosulfate), the long-chain pure or mixed higher alkyl sulfates (e.g. lauryl sulfate, coconut fatty alcohol sulfate), the higher fatty acid ethanolamide sulfates; the higher fatty acid amides of amino alkyl sulfonic acids (e.g. lauric acid amide of taurine), the higher fatty acid esters of isethionic acid and the like.
Suitable cationic detergents which may be employed are the long-chain alkyl quaternary ammonium compounds (e.g. cetyl quaternary ammonium salts). Suitable examples are cetyl trimethyl ammonium chloride, cetyl pyridinium chloride, and the like.
Various non-ionic agents may be employed also, such as the non-ionic polyalkylene oxide condensates with an aliphatic or aromatic hydrophobic group. Such agents have about 5 to 50 alkylene oxide groups usually. Examples are the polyethylene oxide condensate with alkyl phenols having 8 to 20 carbons in the alkyl group such as Igepal CA and CO, the polyethylene oxide esters with higher fatty acids such as tall oil or lauric acid condensed with about 16 or 20 ethylene oxide groups, the polyethylene oxide condensates with higher aliphatic alcohols such as lauryl, myristyl, oleyl or stearyl alcohol with 6 to 30 moles ethylene oxide, and the like.
The anionic and cationic surface-active agents are used commonly in the form of Water-soluble salts. For the anionic compounds the alkali metal and ammonium salts are preferred whereas for the cationic agents the chloride, sulfate and acetate and the like acid salts are employed commonly.
Any amount of the detersive compound may be employed which does not substantially adversely affect the desired characteristics of the product. In general, it is preferred that the detergent be present in amounts from about /2 to about 15% by weight and preferably from 1 to 10% by weight. It is'preferred to employ the anionic and non-ionic surface-active agents in a form where these materials have been premixed with the alkaline builder salts. The mixture containing the detergent and alkaline salts in the form of anaqueous slurry may be subjected to the usual drying procedures in order to obtain a relatively dry homogeneous product such as by drum drying or spray drying of the mixture in known manner.
The abrasive material, alkaline and acidic ingredients containing a coating upon one of the latter two materials are mixed in particulate form to produce a dry, cleansing powder. The ingredients are admixed mechanically by tumbling, fluidizing or the like in conventional soap powder mixers known in the art or by any other suitable means for mechanical admixture.
It is a further feature of the present invention that the product may contain a bleaching agent which results in effective bleaching action during use of the product. The bleaching agent may be incorporated into the product in any suitable manner, such as during or after the mixing of the essential ingredients. In general, bleaching agents are more etfective in one pH condition than another. Since the product during use will form both acid and alkaline solutions, there will be obtained at some stage optimum conditions for a particular bleaching agent. If desired, the bleaching agent may be coated with any suitable material such as the coating agents previously described so that the bleaching agent is released in the same manner. Examples of suitable bleaching agents are the known oxygen and chlorine-releasing substances, such as sodium perborate, sodium, calcium and lithium hypochlorites, dichlorocyanuric acid, trichlorocyanuric acid, Chloramine T, dichlorodimethyl hydantoin and the like. The amount of bleaching agent is not critical but will be usually from about 0.01 to 25% of the product.
There may be incorporated in the product a suitable color indicator which would demonstrate to the consumer when the change from one pH condition to the other pH condition occurs or when a particular pH level is obtained during use. The quantity of indicator is not critical'except that it should be capable of producing a detectable coloration to the cleansing solution. In general, the amount of color indicator will vary with thetype of indicator but is usually from about 5 parts per million to 3% of the product. If methyl orange is employed, the color of the slurry initially is yellow when the acid is coated, but when the acid dissolves subsequently the cleansing solution turns red. Another suitable color indicator is bromo thymol blue which changes color from blue to yellow on conversion of the cleansing solution from an alkaline to an acid nature. The color indicator may be incorporated in any suitable manner such as by spraying it directly upon the particles at any suitable stage in the mixing operation. If the indicator is solid it may be dissolved or'dispersedin a suitable aqueous or alcoholic solution in order to form a liquid solution for ease of application to the particles. When the indicator solution driesupon-the particles the particles will then have a coating of dye which dissolves or disperses upon the initial admixture of the product with water. able dyes are phenol red, t-hymol blue, metacresol purple, etc. a a a 7 Various known materialsmay be incorporated in the product also as desired.- Suitable examples are minor amounts of anti-caking agents such as hydrated magnesium trisilicate, sodium carboxymethyl-cellulose, perfume, antiseptics, germicides, skin emollient materials and thelike. 1
The following'examples are illustrative of the present invention and it will be understood that the invention is not limited thereto. All proportions indicated are by weight unless otherwise specified.
Example I --A powdered sulfamic acid is pretreated to apply a coating to the particles as follows: 200 parts of the powdered sulfamic acid are tumbled in a Mason jar. Through an opening in the cover of the jar, a spray of a lauryl alcohol solution is introduced until 1 part of the lauryl alcohol has been deposited on the surface of the sulfamic acid powder. The spraying composition conther suittains 30% lauryl alcohol dissolved in 70% of a 1:1 mixture of Freon-11 and 12 in a pressure resistant container.
An abrasive alkaline scouring cleanser is prepared by tumbling about 89 parts of silex particles, about 0.5 parts of sodium per-borate powder and about 10.5 parts of an alkaline detergent material. This alkaline detergent material is a spray-dried product containing about 30% sodium dodecyl benzene sulfonate detergent, about 40% sodium tripolyphosphate, with the balance being primarily sodium sulfate. During this mixing operation, about 5 drops of methyl orange indicator are added slowly to obtain good distribution. About 6 parts of the coated sulfamic acid particles are added and the agitation is continued until the product is a uniform, homogeneous mixture.
When one volume of this composition is added to two volumes of water with mild agitation the resulting slurry turns a yellow color indicating that the product gives an alkaline reaction initially. After 2 minutes and 25 seconds the cleansing solution and the slurried produce change to a red color indicating an acidic reaction. The
composition shows effective cleansing and bleaching properties during use.
In comparison a'product prepared in similar manner except that uncoate'd powdered sulfamate acid particles are admixed withthe alkaline scouring cleanser does not yield equivalent results. When the product is added to water with mild agitation, the color turns red immediately indicating that the product did not give an alkaline reaction at any time.
' Example II The procedure of Example I is repeated except that the lauric acid amide is applied similarly to the alkaline detergent particles and not to the sulfamic acid. The ingredients are mixed thereafter in the same manner and the resulting product exhibits initially an acidic reaction in Water followed by an alkaline reaction.
7 Example 111 The procedure of Example I is repeated using 240 parts of powdered sodium bisulfate in place of the 200 parts of sulfamic acid with similar results.
Example 1V Following the procedure of all of the above examples,
the 'followingcoating materials are employed in place of the lauryl alcohol in Example I and the lauric acid amide in Example II with equivalent results: coconut fatty acid diethanolamide, lauric and stearic monoethanolamide, cetyl alcohol, tearyl alcohol, Carbowax 1500 and 4000 and commercial stearic acid. Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefor without departing from the principles and true spirit of the invention. I
What is claimed is:
1. An abrasive cleaning composition Whichfupon admixture with Water is adapted to yield an alkaline pH condition and an acidic pHcondition to the resulting cleaning solution in a predetermined order of succession which comprises a mixture of a major proportion of a water-insolublesiliceous abrasive material, about /2 to 25% by weight of a water-soluble alkaline inorganic builder salt which upon contact with water renders the solution alkaline, about /2 to 25% by weight of a watersoluble normally solid acid which upon contact with water renders the solution acidic, one of the two latter ingredients dissolving sufficiently upon admixture of said composition with water so that the resulting cleansing solution initially has one of said pH conditions and the i 7 material resulting in a retarded rate of solubility so that it is not sufficiently soluble in said solution initially but subsequently dissolves in said solution to convert it to the other of said pH conditions.
2. An abrasive cleaning composition which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition to the resulting cleaning solution in a predetermined order of succession which comprises a mixture a major proportion of a water-insoluble siliceous abrasive material, a minor proportion from about /2 to 25% by Weight of a watersoluble alkaline ingredient which upon contact with water renders the solution alkaline, and a minor proportion from about /2 to 25% by weight of a Water-soluble acidic ingredient which upon contact with water renders the solution acidic, one of the two latter ingredients dissolving sufliciently upon admixture of said composition with water so that the resulting cleaning solution initially has one of said pH conditions and the other ingredient having a coating of a water-dispersible material to retard its initial solubility but being present in a stoichiometric excess so that it subsequently converts said cleaning solution to the other of said pH conditions.
3. An abrasive cleaning composition in accordance with claim 2 wherein said acid is sulfamic acid.
4. An abrasive cleaning composition in accordance with claim 2 wherein said coating is a higher fatty alcohol.
5. An abrasive cleaning composition in accordance with claim 2 which contains about /2 to 15% by weight of a water-soluble organic detergent.
6. An abrasive cleaning composition in accordance with claim 2 which contains about /2 to 25% by Weight of a bleaching agent.
7. An abrasive cleaning composition in accordance with claim 2 which contains a color indicator whereby said composition upon admixture with water results in diiTerently colored solutions in said alkaline and acidic pH conditions.
8. An abrasive cleaning composition which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition successively to the resulting cleaning solution which comprises a mixture of a major proportion of a water-insoluble siliceous abrasive material, about /2 to 25% by weight of a water-soluble inorganic phosphate salt which upon contact with water renders it alkaline, about /2 to 25% by weight of a watersoluble normally solid acid which upon contact with water renders it acidic, said acid having a coating of a water-dispersible material and said composition upon admixture with water yielding an alkaline pH condition in water which is subsequently converted to an acidic pH condition.
9. An abrasive cleaning composition in accordance with claim 8 which contains particles of sulfamic acid coated with said material.
10. An abrasive cleaning composition in accordance with claim 8 which contains about A: to 25 by weight of sodium perborate.
11. An abrasive cleaning composition in accordance with claim 8 which contains a color indicator to indicate by color change when the cleaning solution is converted from said alkaline to said acidic pH condition.
12. An abrasive cleaning composition which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition successively to the resulting cleaning solution which comprises a mixture of a major proportion of a water-insoluble siliceous abrasive material, about /2 to 25 of a water-soluble inorganic alkaline builder salt which upon contact with the water renders the solution alkaline, about /i to 25% by weight of water-soluble normally solid acid which upon contact with the water renders it acidic, said acid having a coating of a water-dispersible material to retard its rate of solubility, but being present in stoichiometric excess so that said composition upon admixture with water yields an alkaline pH condition initially which is subsequently converted to an acidic pH condition.
13. A method of preparing an abrasive cleaning composition characterized by a mixture of a major proportion of a water-insoluble siliceous abrasive material, a minor proportion from about /2 to 25% by weight of a water-soluble alkaline compound and a minor proportion from about /2 to 25% by Weight of a water-soluble acidic compound which upon admixture with water is adapted to yield an alkaline pH condition and an acidic pH condition to the resulting cleaning solution in a predetermined order of succession which comprises coating with a water-dispersible compound one of the latter two ingredients to retard its rate of solubility in water, and admixing the resulting coated compound in an amount in stoichiometric excess with the other ingredient and with said abrasive to form a uniform mixture.
14. A method of preparing an abrasive cleaning composition characterized by a mixture of a major proportion of water-insoluble siliceous abrasive material, and minor proportions of about /2 to 25% by weight each of a water-soluble alkaline ingredient and a water-soluble acidic ingredient adapted to yield an alkaline pH condition and an acidic pH condition successively upon admixture With water which comprises treating said acidic ingredient to apply a coating of a Water-dispersible material, and admixing the coated acidic material with said abrasive and alkaline material to 'form a homogeneous mixture.
15. A method in accordance with claim 14 wherein said acidic ingredient is a normally solid water-soluble acid.
16. A method in accordance with claim 14 which comprises admixing a color indicator with said mixture to indicate by color change when the resulting cleaning solution is converted from said alkaline to said acidic pH condition.
References Cited in the file of this patent UNITED STATES PATENTS 284,494 Michaelis Sept. 4, 1883 856,672 Best et al. June 11, 1907 871,612 Nesfield Nov. 19, 1907 980,936 Federer Jan. 10, 1911 1,075,663 Meerbott Oct. 14, 1913 1,854,235 Stoddard Apr. 19, 1932 1,966,203 Gravell July 10, 1934 1,989,765 Moss et a1. Feb. 5, 1935 2,034,361 Sutton Mar. 17, 1936 2,196,901 Ham et a1. Apr. 9, 1940 2,228,483 Raeke Jan. 14, 1941 2,308,992 Mertens Jan. 19, 1943 2,430,233 Magill Nov. 4, 1947 2,497,057 Pape et a1 Feb. 7, 1950 2,498,344 Rider et a1. Feb. 21, 1950 2,540,253 Gakenheimer Feb. 6, 1951 2,578,270 Strain Dec. 11, 1951 2,589,108 Mark Mar. 11, 1952 2,625,514 Kirschenbauer Ian. 13, 1953 2,763,618 Hendrix Sept. 18, 1956 FOREIGN PATENTS 749,857 Great Britain June 6, 1956

Claims (1)

1. AN ABRASIVE CLEANING COMPOSITION WHICH UPON ADMIXTURE WITH WATER IS ADAPTED TO YEILD AN ALKALINE PH CONDITION AND AN ACIDIC PH CONDITION TO THE RESULTING CLEANING SOLUTION IN A PREDETERMINED ORDER OF SUCCESSION WHICH COMPRISES A MIXTURE OF A MAJOR PROPORTION OF A WATER-INSOLUBLE SILICEOUS ABRASIVE MATERIAL, ABOUT 1/2 TO 25% BY WEIGHT OF A WATER-SOLUBLE ALKALINE INORGANIC BUILDER SALT WHICH UPON CONTACT WITH WATER RENDERS THE SOLUTION ALKALINE, ABOUT 1/2 TO 25% BY WEIGHT OF A WATERSOLUBLE NORMALLY SOLID ACID WHICH UPON CONTACT WITH WATER RENDERS THE SOLUTION ACIDIC, ONE OF THE TWO LATTER INGREDIENTS DISSOLVING SUFFICIENTLY UPON ADMIXTURE OF SAID COMPOSITION WITH WATER SO THAT THE RESULTING CLEANSING SOLUTION INTIALLY HAS ONE OF SAID PH CONDITIONS AND THE OTHER INGERDIENT HAVING A COATING OF WATER-DISPERSIBLE MATERIAL RESULTING IN A RETARDED RATE OF SOLUBILITY SO THAT IT IS NOT SUFFICIENTLY SOLUBLE IN SAID SOLUTION INITIALLY BUT SUBSEQUENTLY DISSOLVES IN SAID SOLUTION TO CONVERT IT TO BE OTHER OF SAID PH CONDITIONS.
US693803A 1957-11-01 1957-11-01 Abrasive cleaning composition Expired - Lifetime US3042622A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US693803A US3042622A (en) 1957-11-01 1957-11-01 Abrasive cleaning composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US693803A US3042622A (en) 1957-11-01 1957-11-01 Abrasive cleaning composition

Publications (1)

Publication Number Publication Date
US3042622A true US3042622A (en) 1962-07-03

Family

ID=24786179

Family Applications (1)

Application Number Title Priority Date Filing Date
US693803A Expired - Lifetime US3042622A (en) 1957-11-01 1957-11-01 Abrasive cleaning composition

Country Status (1)

Country Link
US (1) US3042622A (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297578A (en) * 1963-07-26 1967-01-10 Monsanto Co Bleaching, sterilizing, disinfecting, and deterging compositions
US3325411A (en) * 1964-06-02 1967-06-13 Jr Frank N Stepanek Compositions containing chlorinated isocyanurates and methods for stabilizing and tabletting the same
US3345302A (en) * 1965-07-19 1967-10-03 Philadelphia Quartz Co Stable mixtures
US3353902A (en) * 1964-05-08 1967-11-21 Fmc Corp Method of using quaternary ammonium peroxysulfates
US3650831A (en) * 1969-03-10 1972-03-21 Armour Dial Inc Method of cleaning surfaces
US3985668A (en) * 1974-04-17 1976-10-12 The Procter & Gamble Company Scouring compositions
US4005027A (en) * 1973-07-10 1977-01-25 The Procter & Gamble Company Scouring compositions
US4051056A (en) * 1974-09-09 1977-09-27 The Procter & Gamble Company Abrasive scouring compositions
FR2396076A1 (en) * 1977-06-27 1979-01-26 Akzo Nv DETERGENT COMPOSITION CONTAINING AN ALKALINE CARBONATE
US4234442A (en) * 1978-07-14 1980-11-18 Akzo N.V. Feed unit of a detergent composition based on alkali carbonate
US4417993A (en) * 1979-10-30 1983-11-29 Gerhard Gergely Cleansing tablets for tooth prostheses
US4599186A (en) * 1984-04-20 1986-07-08 The Clorox Company Thickened aqueous abrasive scouring cleanser
US4664836A (en) * 1985-09-18 1987-05-12 Amway Corporation Drain cleaner
WO1987006757A1 (en) * 1986-05-02 1987-11-05 Mandel Frederick S Novel compositions and method for neutralization and solidification of hazardous alkali spills
US4788005A (en) * 1987-05-15 1988-11-29 The Clorox Company Thickened aqueous abrasive cleanser exhibiting no syneresis
US5190742A (en) * 1989-06-28 1993-03-02 Sorin Biomedica S.P.A. Device and method for carrying out a plurality of sequential transformations of a substrate
US20060110464A1 (en) * 2003-02-11 2006-05-25 Walls John E Material encapsulation system
US20070111913A1 (en) * 2005-11-17 2007-05-17 Albright Robert L Color changing paint and varnish remover
EP2105277A1 (en) * 2008-03-25 2009-09-30 Granula Polymer GmbH Cleaning agent for devices meant for processing or production of plastic, usage of same, method for production and method for cleaning

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US284494A (en) * 1883-09-04 Machine
US856672A (en) * 1905-06-14 1907-06-11 Otto Best Baking-powder and process of making the same.
US871612A (en) * 1904-01-02 1907-11-19 Vincent Blumhardt Nesfield Sterilizing-tablet.
US980936A (en) * 1909-12-16 1911-01-10 Chem Fab Vorm Goldenberg Geromont & Cie Manufacture and production of baking-powder.
US1075663A (en) * 1912-10-21 1913-10-14 John T Stanley Composition of matter.
US1854235A (en) * 1930-01-18 1932-04-19 Conover Company Detergent composition
US1966203A (en) * 1932-03-26 1934-07-10 American Chem Paint Co Method of and material for removing soldering fluxes
US1989765A (en) * 1930-06-25 1935-02-05 Swann Res Inc Sodium meta silicate detergent
US2034361A (en) * 1929-03-23 1936-03-17 Roy C Sutton Alkaline detergent powder and method of making the same
US2196901A (en) * 1939-11-06 1940-04-09 American Cyanamid Co Photographic developer
US2228483A (en) * 1938-05-18 1941-01-14 Henkel & Cie Gmbh Process for the preparation of products delivering carbonic acid gas
US2308992A (en) * 1937-10-03 1943-01-19 Procter & Gamble Method for producing washing, cleansing, bleaching, and rinsing agents containing percompounds
US2430233A (en) * 1944-06-05 1947-11-04 Du Pont Halogen-yielding compositions
US2497057A (en) * 1950-02-07 Toilet bowl -gleanee
US2498344A (en) * 1944-12-23 1950-02-21 Lever Brothers Ltd Denture cleansers
US2540253A (en) * 1949-02-08 1951-02-06 Merck & Co Inc Granulation process
US2578270A (en) * 1949-09-23 1951-12-11 Pittsburgh Plate Glass Co Stable chlorinated melamine composition
US2589108A (en) * 1943-08-02 1952-03-11 Us Sec War Chlorinated lime composition
US2625514A (en) * 1949-12-24 1953-01-13 Colgate Palmolive Peet Co Noncaking abrasive detergent compositions
GB749857A (en) * 1952-10-23 1956-06-06 Unilever Ltd Improvements in or relating to soap powders
US2763618A (en) * 1955-09-07 1956-09-18 Pro Nyl Chemicals Inc Whitening and brightening wash and rinse powder composition

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2497057A (en) * 1950-02-07 Toilet bowl -gleanee
US284494A (en) * 1883-09-04 Machine
US871612A (en) * 1904-01-02 1907-11-19 Vincent Blumhardt Nesfield Sterilizing-tablet.
US856672A (en) * 1905-06-14 1907-06-11 Otto Best Baking-powder and process of making the same.
US980936A (en) * 1909-12-16 1911-01-10 Chem Fab Vorm Goldenberg Geromont & Cie Manufacture and production of baking-powder.
US1075663A (en) * 1912-10-21 1913-10-14 John T Stanley Composition of matter.
US2034361A (en) * 1929-03-23 1936-03-17 Roy C Sutton Alkaline detergent powder and method of making the same
US1854235A (en) * 1930-01-18 1932-04-19 Conover Company Detergent composition
US1989765A (en) * 1930-06-25 1935-02-05 Swann Res Inc Sodium meta silicate detergent
US1966203A (en) * 1932-03-26 1934-07-10 American Chem Paint Co Method of and material for removing soldering fluxes
US2308992A (en) * 1937-10-03 1943-01-19 Procter & Gamble Method for producing washing, cleansing, bleaching, and rinsing agents containing percompounds
US2228483A (en) * 1938-05-18 1941-01-14 Henkel & Cie Gmbh Process for the preparation of products delivering carbonic acid gas
US2196901A (en) * 1939-11-06 1940-04-09 American Cyanamid Co Photographic developer
US2589108A (en) * 1943-08-02 1952-03-11 Us Sec War Chlorinated lime composition
US2430233A (en) * 1944-06-05 1947-11-04 Du Pont Halogen-yielding compositions
US2498344A (en) * 1944-12-23 1950-02-21 Lever Brothers Ltd Denture cleansers
US2540253A (en) * 1949-02-08 1951-02-06 Merck & Co Inc Granulation process
US2578270A (en) * 1949-09-23 1951-12-11 Pittsburgh Plate Glass Co Stable chlorinated melamine composition
US2625514A (en) * 1949-12-24 1953-01-13 Colgate Palmolive Peet Co Noncaking abrasive detergent compositions
GB749857A (en) * 1952-10-23 1956-06-06 Unilever Ltd Improvements in or relating to soap powders
US2763618A (en) * 1955-09-07 1956-09-18 Pro Nyl Chemicals Inc Whitening and brightening wash and rinse powder composition

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297578A (en) * 1963-07-26 1967-01-10 Monsanto Co Bleaching, sterilizing, disinfecting, and deterging compositions
US3353902A (en) * 1964-05-08 1967-11-21 Fmc Corp Method of using quaternary ammonium peroxysulfates
US3325411A (en) * 1964-06-02 1967-06-13 Jr Frank N Stepanek Compositions containing chlorinated isocyanurates and methods for stabilizing and tabletting the same
US3345302A (en) * 1965-07-19 1967-10-03 Philadelphia Quartz Co Stable mixtures
US3650831A (en) * 1969-03-10 1972-03-21 Armour Dial Inc Method of cleaning surfaces
US4005027A (en) * 1973-07-10 1977-01-25 The Procter & Gamble Company Scouring compositions
US3985668A (en) * 1974-04-17 1976-10-12 The Procter & Gamble Company Scouring compositions
US4051056A (en) * 1974-09-09 1977-09-27 The Procter & Gamble Company Abrasive scouring compositions
FR2396076A1 (en) * 1977-06-27 1979-01-26 Akzo Nv DETERGENT COMPOSITION CONTAINING AN ALKALINE CARBONATE
US4234442A (en) * 1978-07-14 1980-11-18 Akzo N.V. Feed unit of a detergent composition based on alkali carbonate
US4417993A (en) * 1979-10-30 1983-11-29 Gerhard Gergely Cleansing tablets for tooth prostheses
US4599186A (en) * 1984-04-20 1986-07-08 The Clorox Company Thickened aqueous abrasive scouring cleanser
US4664836A (en) * 1985-09-18 1987-05-12 Amway Corporation Drain cleaner
WO1987006757A1 (en) * 1986-05-02 1987-11-05 Mandel Frederick S Novel compositions and method for neutralization and solidification of hazardous alkali spills
GB2199840A (en) * 1986-05-02 1988-07-20 Frederick S Mandel Novel compositions and method for neutralization and solidification of hazardous alkali spills
US4913835A (en) * 1986-05-02 1990-04-03 Wormald U.S. Inc. Novel compositions and method for neutralization and solidification of hazardous alkali spills
GB2199840B (en) * 1986-05-02 1991-01-02 Frederick S Mandel Compositions for neutralization and solidification of hazardous alkali spills
US4788005A (en) * 1987-05-15 1988-11-29 The Clorox Company Thickened aqueous abrasive cleanser exhibiting no syneresis
US5190742A (en) * 1989-06-28 1993-03-02 Sorin Biomedica S.P.A. Device and method for carrying out a plurality of sequential transformations of a substrate
US20060110464A1 (en) * 2003-02-11 2006-05-25 Walls John E Material encapsulation system
US8834934B2 (en) * 2003-02-11 2014-09-16 Haviland Products Company Material encapsulation system
US20070111913A1 (en) * 2005-11-17 2007-05-17 Albright Robert L Color changing paint and varnish remover
US7304021B2 (en) * 2005-11-17 2007-12-04 Dynacraft Industries, Inc Color changing paint and varnish remover
EP2105277A1 (en) * 2008-03-25 2009-09-30 Granula Polymer GmbH Cleaning agent for devices meant for processing or production of plastic, usage of same, method for production and method for cleaning

Similar Documents

Publication Publication Date Title
US3042621A (en) Detergent composition
US3042622A (en) Abrasive cleaning composition
US4145184A (en) Detergent composition containing encapsulated perfume
US4203851A (en) Fabric softening compositions and methods for manufacture thereof
US4539135A (en) Perfume-containing carrier for laundry compositions
US3669891A (en) Chemical compositions
US3503884A (en) Scouring cleanser composition
US4447349A (en) Suds suppressing granules for use in detergent compositions
CA1054016A (en) Liquid detergent
CA1096740A (en) Concentrated heavy duty particulate laundry detergent
US3715314A (en) Scouring cleanser composition
US4655780A (en) Encapsulated bleach particles coated with a mixture of C16 -C18 and C12 -C14 fatty acid soaps
CA1232413A (en) Fabric softener agglomerates
JPH0333196A (en) Pereume particle used for cleaning and conditioning compounds
US4411809A (en) Concentrated heavy duty particulate laundry detergent
KR950002354B1 (en) Detergent composition and process for its production
GB1591518A (en) Detergent compositions
JPH0258319B2 (en)
US4416809A (en) Granular detergent composition
US4615814A (en) Porous substrate with absorbed antistat or softener, used with detergent
GB1259027A (en)
US3819526A (en) Coated detergent compositions
GB1579261A (en) Detergent compositions and components thereof
US3265624A (en) Detergent composition
US4276326A (en) Free flowing builder beads and detergents