US2587637A - Detergent composition - Google Patents

Detergent composition Download PDF

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US2587637A
US2587637A US792617A US79261747A US2587637A US 2587637 A US2587637 A US 2587637A US 792617 A US792617 A US 792617A US 79261747 A US79261747 A US 79261747A US 2587637 A US2587637 A US 2587637A
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soap
ethyl cellulose
water
detergent
sodium
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Mcdonald Louis
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    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • C11D9/262—Organic compounds, e.g. vitamins containing oxygen containing carbohydrates
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen

Definitions

  • the present invention relates to detergent compositions and it particularly relates to detergent which will not too quickly dissolve or melt away when utilized with hot or cold soft waters and which will be efiective over longperiods of time with undiminished detergent efliciency; 1
  • Another object of the present invention is to provide novel detergent compositions which may be incorporated with paper fibers or toweling, steel wool, various abrasives such as emery and sand and which will not tend to dissolve away too quickly from the material with which they are incorporated or by which they are carried before theyhave had the opportunity of being efiectively used for their detergent properties.
  • Another object of the present invention is to provide novel detergent materials which may be readily' employed either in the home or indus trially and which will retain their effectiveness over long periods of time and which will have high detergent properties even with salt water orwith waters having widely varying degrees of temporary or permanent hardness or having varying temperatures.
  • fatty soap may be sodium, am
  • cellulose ethers particularly ethyl cellulose, being preferred.
  • Propyl, butyl and amyl celluloses may also be employed as may also benzyl cellulose in lieu of part or all of the ethyl cellulose.
  • an inorganic crystalloid detergent salt such as sodium carbonate, sodium phosphate or sodium hexametaphosphate.
  • water thickening agents or protective colloids such as various gums, like gum acacia, gum tragacanth, gum arabic, agar agar, pectin, deXtrin, British gum, gum Shiraz or water soluble cellulose derivatives, such as meth- Methyl celluloses in contrast to ethyl cellulose are usually water soluble.
  • the preferred methyl cellulose has a solubility of 64 grams per 100 ml. at 25 C. with 2.6 methoxy groups per 12 carbon cellulose unit.
  • compositions may be mixedwith fillers and/or abrasives, such as powdered sand, infusorial earth, kieselguhr, whiting, or it may be impregnated upon cloth, paper or other fibrous materials, or upon aluminum, steel or other metal wools or upon glass rock, or mineral wool or upon fibrous mattings, such as those made from hemp or artificial fibers.
  • abrasives such as powdered sand, infusorial earth, kieselguhr, whiting, or it may be impregnated upon cloth, paper or other fibrous materials, or upon aluminum, steel or other metal wools or upon glass rock, or mineral wool or upon fibrous mattings, such as those made from hemp or artificial fibers.
  • the detergent base have self-emulsifying ethyl cellulose binders which retard the dissolution or emulsification of thedetergent material from the filler or carrier material with which it has been incorporated or onto which it has been impregnated, and where desired, the final composition may be caused to incorporate substantial quantities of air which will cause it to be a floating soap which when floated upon Water will not readily emulsify or dissolve.
  • ethyl cellulose is normally Water insoluble and can only be dispersed in .water by way of an emulsion.
  • Such dispersion may be made in the following manner: The ethyl cellulose, for example 50 parts by Weight of ethyl cellulose having 2.5 ethoxy groups per glucose residue, is first dissolved in toluene ethanol mixture (40 parts tolueneparts ethanol by weight) These are mixed in a high speed mixer or colloid mill and then after initial emulsification they are homogenized. The final product is a heavy creamy emulsion containing about ethyl cellulose.
  • methyl cellulose containing 2.5 methoxy groups per glucose residue is water soluble and is used as an emulsion stabilizer, as a sizing gum and if mixed with soap or a detergent would not act in any respect as ethyl cellulose. It
  • methyl cellulose if used in the same quantities as the ethyl cellulose would have no such effect.
  • Ethyl cellulose slows rate of solution of soap by 50% to 300% depending upon proportionment. Methyl cellulose does not have this effect. Methyl cellulose may be mixed with soap up to 40% directly without substantially decreasing insolubility of the soap. Butethyl cellulose can only be incorporated up to about 2% above which it would render soap virtually insoluble.
  • the composition in lieu of all or part of the polyethylene glycol esters, small amounts' from 1 to- 50% by weight ofhighly effective surface active agents, such as, for example, normal polymerized alkyl sulphonates, such as of the nature of dibutyl naphthalene sodium sulphonates, or of alkyl esters of di-basic carboxylic acids, such as the dioctyl ester of sulfonsuccinic acid, or sodium fatty alcohol sulfates such as sodium lauryl sulfates.
  • highly effective surface active agents such as, for example, normal polymerized alkyl sulphonates, such as of the nature of dibutyl naphthalene sodium sulphonates, or of alkyl esters of di-basic carboxylic acids, such as the dioctyl ester of sulfonsuccinic acid, or sodium fatty alcohol sulfates such as sodium lauryl sulfates.
  • Cationic agents are less preferable for most applications but may be advantageously used for low pH types of soils.
  • Triton 770 Triton NE
  • Arctic Syntex M Triton NE
  • Igepal CA Igepon T or other collamids
  • Tween 20 and Tween 60 Triton 770, Triton NE, Arctic Syntex M, Igepal CA, Igepon T or other collamids, Tween 20 and Tween 60.
  • R-CONH-CI-IzCHzSOsNa AIY1(SO3H) 1/0 (CnHZnO) z-CnHZnSOIlH Arctic Syntex M has the general formula:
  • Triton and Igepal CA are the same products and consist of polyethylene oxide condensates having (-CCOC-C)nOI-I groupings with molecular weights of 750 to 1000.
  • Triton NE has the following formula:
  • Igepal CA is identified by the formula:
  • the commercial material contains about 6 ethyle'ne oxide groups.
  • Tween 60 is sorbitan monostearate
  • fJI EXAMPLE I A metal cleaning detergent composition which may be impregnated on cloth, paper or other wool, rock wool, or fibrous mattings made of hemp, or artificial fibers, may be made up in the following manner:
  • composition is prepared with gentle mixing at a temperature of about 40 C.:
  • Preferred Range Oleic acid .l 20 5-30 Monoethanolamine 7 2-10 Ammonium gluconate 5 0-10 Sodium hexametaphosphate. 10 0-20 Diethanolamine 10 2-15 Whiting (finest bolted). 50-150 Infusorial earth (#200). 50 25-100 Methyl cellulose ether 4 0-50 Isopropyl alcohol 25 0-50 Dibutyl naphthalene sodium sulfonate 35 0-50 Water 300 -600 After each of batch A and batch B hasbeeni thoroughly mixed they are separately warmed to 70 C. and then batch A is poured into batch B with rapid agitation, emulsification taking place immediately.
  • the mass is agitated until it cools to 50" C. and it is transferred to a colloidal mill and homogenized.
  • the resultant emulsion may be impregnated upon paper or cloth or other fibrous materials, and the impregnated product may be dried under a vacuum or by gentle heating.
  • the finished product may be used for cleaning metals by dampening the impregnated material with warm water and rubbing on the tarnished metal object until all tarnish is removed.
  • composition set forth above other oils may be utilized in lieu of castor oil and other alkalies or alkaline materials may be used in lieu of the ethanolamines specified.
  • Dibutyl phthalate is merely a plasticizer'and may be replaced by other plasticizers and in lieu of oleic acid, it is possible to use other fatty acids to combine with the alkali present.
  • the ingredients of batch B are first mixed in the water at about 30, while the chemicals of batch A are mixed at about C. and poured into batch B with rapid agitation, which agitation is continued until the emulsion cools to 20 C.
  • the emulsion is then transferred to a colloid mill and homogenized and then used asa detergent as such with or without the addition of filler, or it may be impregnated upon paper, cloth, or
  • the ethyl cellulose acts as a binder.
  • the sodium hexametaphosphate will act as a I cleansing agent.
  • EXAMPLE III L To obtain a floating soap composition, /10 gram of benzyl cellulose having 25 benzyloxy groups per glucose residue may be emulsified with grams of diglyool oleate and then to the emulsion there may be added grams of hard soap and 'l /grgrams of sodium laurylsulfonate.
  • Theentire mass is heated to about C.
  • finished cake is a floating detergent which will not rapidly dissolve while floating on water.
  • the detergent functions satisfactorily in hard water'and the formation of calcium and magnesium soap curd is repressed by the diglycol oleate d'jthe sodium lauryl sulfonate or sulfate.
  • This d i 'i' ent cake is not sensitive to the changes in atmospheric conditions. It does not lose weight in warm, dry weather, nor does it absorb moisture and become soggy in humid weather.
  • EXAMPLE IV One gram of polyvinyllalcohol is emulsified-j with 5 grams of mannidemonooleate. To this mixture is added 90 grams of kettle soap and the entire mass is transferred to a paste mill. The temperature is brought up to 100 C. and the mass is kneaded. V
  • Kettle soap is 65% soap and the balance water and glycerin. After a mass of .even consistency is attained, 2 grams of tetrasodium pyrophosphate dissolved in 8 cc. of hot water are added and mixingis continned.” The. mass is then transferred to a vac uum .oven and dried and molded into cake form or to soap frames and cooled or molded into cake form. The finished cake is .smooth and has the appearance of conventional soap.
  • This detergent may be used in hard waterwith complete satisfaction.
  • This composition enables incorporation of a crystalline electrolyte water softening agent which was not previously possible with soap compositions.
  • a crystalline electrolyte water softening agent which was not previously possible with soap compositions.
  • polyvinyl alcohol dimethylol urea having more than 4 mole units'per-molecules, diomeric or triomeric methacrylates, and diomeric or triomeric vinylidene chlorides or acetates may be used. These areall water insoluble and organic solvent soluble resins.
  • EXAMPLE V steel or metal wool and then dried in a vacuum or two grams of mannitan monooleatetank and is impregnated onto paper toweling in the conventional manner.
  • the product is dried in a vacuum drier or by gentle heating.
  • the impregnated paper is stable under various climatic conditions and may be rolled or packaged in out form.
  • the product may be cast or rolled into a film without fibrous backing.
  • the paper towelling made with this composition may be dispensed'with ordinary dispensing machines in public wash rooms and may be used to eliminate the inconvenience of liquid, powdered and cake soaps in public wash rooms.
  • the detergent will re-emulsify and cleanse the object with the above composition.
  • This detergent product also functions eifejci 1.
  • compositions described above may be impregnated onto paper or other fibrous material in the process. of. manufacture of such. material.
  • the detergent chemicals can. be mixed in the beateralong. with. the. pulp and binding; materials; andwill not be removed with. the wash. water,
  • Atissue paper which may be used for cleaning.
  • silver and other fine metals may be made as fol, lows:
  • Abeater mass is made up with. twentypounds of sulfite. pulp dispersed with 400 lbs. of. water. While the pulp is agitating in the beater, 1.0 pounds of detergent emulsion is made up in Example I or II.
  • the drip liquid from the screen can be re-- covered and used again. in the. beater.
  • compositions for :cleaning metals such as aluminum, gold, silver, tin, brass, copper, nickel, etcwhich are impregnated on metal wools or abrasives or paper or cloth carriers and rubbed on. the. utensil or other metal object that is being. cleaned
  • the composition may desirably include. a polyhydroxy organic. acid, lactone or polyhydroxy organic salt suspended in. an emulsified binder with a polishing; agent. and wetting agent.
  • polyhydroxy organic. acids and. lactones such as gluconic acid and gluconodeltalactorie: are preferred. 7 1
  • the mixture may be impregnated into a. car rier such as canton flannel or similar textile material, crepe paper toweling or. tissue paper, or a suitable metal wool such as aluminum wool or a fibrous or wool. siliceous.- mass. such. as. mineral wool and rock wool.
  • a. car rier such as canton flannel or similar textile material, crepe paper toweling or. tissue paper, or a suitable metal wool such as aluminum wool or a fibrous or wool. siliceous.- mass. such. as. mineral wool and rock wool.
  • the cleaner composition. and the fibrous wool. carrier or abrasive maylbe modified for the cleansing and polishing of. ditferent metals, and all the agents used. should benon-toxic and non-irritating to'thee skin. 3;
  • a composition suitable. for cleaning silver, gold or platinum impregnated into canton flannel or Similar textile material is made up in. two batches of the following ingredients:
  • batch B is poured into batch rapid: stirring.
  • Emulsification takes place immediately and; the mass is stirred rapidly until the temperature. drops to 50 C. The mixture is then run through a homogenizer to complete emulsification.
  • the temperature is then adjusted to 35 to 40 C. and the emulsion is transferred to a tank.
  • a ribbon of canton flannel or similar textile is run. through the emulsion and the fibres of the textile become impregnated. The excess emulsion is scraped off the bottom of the cloth and the wet impregnated mass is run through a vacuum dryer or is dried by gentle heating.
  • the finished. impregnated cloth. may be used. for cleaning silver by moistening, the cloth with. a small. amount of warm. water and then rubbing on the tarnished silver.
  • the impregnated. chemicals re-emulsify and are liberated from the cloth to. act on the soil. and. tarnish. After. the tarnish is removed the. silver isrinsed with. warm water and is ready for use.
  • EXAMPLE IX A similar cleansing, composition may be. made by impregnating crepe of tissue or other soft.
  • the dried impregnated paper may be cut into rolled strips and. dispensed in. much the same manner as rolled paper towels.
  • the impregnated. cleaning. paper is torn off from the roll. and used as. needed.
  • the paper is moistened. with warm and rubbed on a tarnished silver article until it is cleaned. Then the soiled paper may be discarded.
  • the cyclonol or cyclo hexanone glycerol acetal and the diethylene glycol-monobutyl ether acetate act as high boiling solvents which keep the emulsion at impregnating consistency and also act to plasticize the binder.
  • the cyclonol- also acts as a grease solvent.
  • Cyclonol also acts as a true non-emulsifying plasticizer for the ethyl cellulose.
  • the isothymol acts as a preservative.
  • the isopropyl alcohol acts as a solvent for the ethyl cellulose while the sorbitol acts as a humectant and controls the moisture content.
  • the gluconicacid combines with the tri-isopro- Metal fibers such as copper and 0 panol amine to form a salt in part, the remainder being free acid.
  • compositions are typical but merely illustrative of the scope of this invention.
  • proportions of the chemicals used may vary considerably from the amounts cited above without departing from the spirit of this invention.
  • Certain chemical agents may be substituted for those cited above.
  • arabic, arabonic, xylonic, saccharonic or tri-hydroxy glutaric acids may be substituted for gluconic acid.
  • Any suitable abrasive material such as bentonite, tripoli or rottenstone may be substituted for infusorial earth.
  • Other emulsification bases than diglycol laurate and diglycol stearate may be used.
  • Such emulsification bases are mannide monooleate, mannitan monooleate, diglycol oleate or diethanolamine stearate.
  • wetting agents that may be used in place of the cited alkyl aryl-sulfonates.
  • a few of the preferred ones are sodium dibutyl naphthalene sulfonate, sodium lauryl alcohol sulfate, sodium tetrahydronapthalene sulfonate, the sodium sulfonate of stearyl alcohol, sodium lauryl sulfate and sodium salt of sulfonated myristyl collamide.
  • gum tragacanth India gum or gum arabic are useful. Such gums also may be replaced by water soluble protein materials such as albumin, gelatin or casein.
  • Resin binders such as low polymerized vinyl acetate, or polyvinyl alcohols may be substituted for part or all of the ethyl cellulose, if tackiness is avoided.
  • the present invention is particularly advantageous where it is desired to have a relatively slow dissolving soap as in the case of floating or aerated soaps which tend to dissolve too quickly in water, or where the detergent is combined with a fibrous or abrasive material and tends to dis: solve away from the fibrous material or abrasive too quickly before such fibrous material or abrasive can be thoroughly rubbed upon the object being cleansed.
  • the detergent compositions according to the present application are more resistant to atmospheric changes and will not lose weight or gain water with changesfrom temperate to tropical climates, or
  • the soaps according to the present application may be kept in wet dishes or containers without unduly softening, wasting away or becoming mushy, and where the soap is used in the form of beads, flakes or a powder, there will be decreased tendency toward caking or hardening.
  • the water solubility retarding agent tends to protect the detergent from oxidation.
  • the slow dissolving soaps of the present invention in combinationwith ordinary, relatively quick dissolving soaps or detergents with the soap or deter-'- gent of the present invention constituting an outer layer or a protective surfacing or being mixed with the entire body of the ordinary detergent or soap so that there will be pockets 01' layers of ordinary detergents or soap which will quickly dissolve when exposed while other layers or pockets of slow dissolving soap, as according toithe present invention, will only slowly dissolve.
  • detergents that may be employed are cleaners for metals such as glucono-lactone, ammonium gluconate, trihydroxy glutaric acid, sodium hexametaphosphate, sodium metasilicate; toilet detergents such as sodium, potassium or alkanolamine 'stearates, oleates, laurates, palmitates and myristatesj fatty alcohol detergents, such as sodium lauryl or palmityl or oleyl sulphate, sulphonatedfats, 'oils or fatty acids oralcohols suchias sulfonated castor oil, tea seed oil, olive oil, peanut oil, cottonseed oil, spermaceti, cetyl alcohol, japan wax, fish oils, lard, rice bran oil, and so forth; the sodium salts of sulphonated or sulphated esterified dicarboxylic acids and so forth.
  • the detergent may constitute from 5 to of the composition.
  • the soap and non-soap detergents themselves are not emulsifying agents for the ethyl cellulose or resinous or plastic solubility retarding material and it is necessary to add a material which will emulsify the ethyl cellulose or other solubility retarding material.
  • the ethyl cellulose or other solubility retarding materials may range from 0.1 to 5% by weight, while the emulsifying agents, usually oil active surface agents such as partially fatty acid esterified polyhydric aliphatic alcohols for the solubility retarding materials may range from 0.005% to 2%.
  • Mannide oleate or mannitan oleate permit incorporation of water softening agents, such as tetra sodium pyrophosphate, sodium hexametaphosphate and so forth without these substances crystallizing in the composition.
  • These selfemulsifying plasticizers are usually polyhydric alcohols, one or more of the hydroxy groups of which are combined with high molecular weight fatty acidswith one or more free hydroxy groups. Oils, waxes and fats are added as lubricants and may be used in amounts from to 10%.
  • water soluble or dispersible gums such as methyl cellulose, India gum and dextrin are employed they may be used in amounts ranging from /2 to 5%.
  • organic solvents such as isopropanol, ethylene glycol alkyl ethers, and so forth are employed they are evaporated off and reclaimed.
  • a solid detergent composition formed of a sodium soap of high molecular weight fatty acid and about 0.1% to 5% by weight of a water-insoluble ethyl cellulose to retard ready solution of said soap and from about 0.005% to 2% of a partial high molecular Weight fatty acid ester of a polyhydric aliphatic alcohol.
  • a solid detergent composition formed of a sodium soap of high molecular weight fatty acid and about 0.1% to 5% by weight of a water-insoluble ethyl cellulose to retard ready solution '12 of said soap and from about 0.005% to 2% of a partial high molecular weight fatty acid ester of a polyhydric aliphatic alcohol, the emulsifying agent being mannitan monoleate.
  • a solid detergent composition formed of a sodium soap of high molecular weight fatty acid and about 0.1% to 5% by weight of a water-insoluble ethyl cellulose to retard ready solution of said soap and from about 0.005% to- 2% of a partial high molecular weight fatty acid ester of a polyhydric aliphatic alcohol, the ethyl cellulose containing about 2.5 ethoxy groups per glucose residue.
  • a solid detergent composition formed of a sodium soap of a high molecular weight fatty acid and about 0.1% to 5% by weight of a water-insoluble ethyl cellulose to retard ready solution of said soap and an emulsifying agent consisting of a partial high molecular weight fatty acid ester of a polyhydric aliphatic alcohol in an amount suflicient to emulsify said ethyl cellulose into the soap.

Description

Patented Mar. 4, 1952 UNITED STATES PATENT OFFICE DETERGENT COMPOSITION Louis McDonald, Inyokern, Calif.
No Drawing; Application December 18, 1947, Serial N0. 792,617
4 Claims. (01. 252-130) The present invention relates to detergent compositions and it particularly relates to detergent which will not too quickly dissolve or melt away when utilized with hot or cold soft waters and which will be efiective over longperiods of time with undiminished detergent efliciency; 1
Another object of the present invention is to provide novel detergent compositions which may be incorporated with paper fibers or toweling, steel wool, various abrasives such as emery and sand and which will not tend to dissolve away too quickly from the material with which they are incorporated or by which they are carried before theyhave had the opportunity of being efiectively used for their detergent properties.
Another object of the present invention is to provide novel detergent materials which may be readily' employed either in the home or indus trially and which will retain their effectiveness over long periods of time and which will have high detergent properties even with salt water orwith waters having widely varying degrees of temporary or permanent hardness or having varying temperatures.
Although the fatty soap may be sodium, am
moni-um or potassium oleate, stearate, laurate, 01' palmitate or the various mono, di, or tri-ethanolamine oleates, s'tearates and palmitates, it has also been found possible to employ various sodium,
ammonium'o'r potassium 'saltsof sulphonated or sulfated fatty alcohols, 'lfattyketones. fatty. acids Stilllfurther objects and advantages will ap peari from the more detailed description set forth b'elov'v', it being understood, however, that this more detailed description is given by way of ilyl celluloses.
and hydrocarbons having from 12 to 32 carbon atoms. I
With this combination is preferably combined a water insoluble, plastic material, cellulose ethers, particularly ethyl cellulose, being preferred. Propyl, butyl and amyl celluloses may also be employed as may also benzyl cellulose in lieu of part or all of the ethyl cellulose.
It has also been found quite satisfactory to include in such compositions small amounts of an inorganic crystalloid detergent salt such as sodium carbonate, sodium phosphate or sodium hexametaphosphate.
In the preferred composition it is also desirable to include water thickening agents or protective colloids such as various gums, like gum acacia, gum tragacanth, gum arabic, agar agar, pectin, deXtrin, British gum, gum Shiraz or water soluble cellulose derivatives, such as meth- Methyl celluloses in contrast to ethyl cellulose are usually water soluble. The preferred methyl cellulose has a solubility of 64 grams per 100 ml. at 25 C. with 2.6 methoxy groups per 12 carbon cellulose unit.
These compositions may be mixedwith fillers and/or abrasives, such as powdered sand, infusorial earth, kieselguhr, whiting, or it may be impregnated upon cloth, paper or other fibrous materials, or upon aluminum, steel or other metal wools or upon glass rock, or mineral wool or upon fibrous mattings, such as those made from hemp or artificial fibers.
With the detergent compositions of the present application, it is important that the detergent base have self-emulsifying ethyl cellulose binders which retard the dissolution or emulsification of thedetergent material from the filler or carrier material with which it has been incorporated or onto which it has been impregnated, and where desired, the final composition may be caused to incorporate substantial quantities of air which will cause it to be a floating soap which when floated upon Water will not readily emulsify or dissolve.
Commercial ethyl cellulose is normally Water insoluble and can only be dispersed in .water by way of an emulsion. Such dispersion may be made in the following manner: The ethyl cellulose, for example 50 parts by Weight of ethyl cellulose having 2.5 ethoxy groups per glucose residue, is first dissolved in toluene ethanol mixture (40 parts tolueneparts ethanol by weight) These are mixed in a high speed mixer or colloid mill and then after initial emulsification they are homogenized. The final product is a heavy creamy emulsion containing about ethyl cellulose.
Commercial methyl cellulose containing 2.5 methoxy groups per glucose residue is water soluble and is used as an emulsion stabilizer, as a sizing gum and if mixed with soap or a detergent would not act in any respect as ethyl cellulose. It
is used for example in shaving creams to stabilize lather.
For example whereas ethyl cellulose promotes micelle formation a micelle being a bundle of detergent or soap molecules, methyl cellulose if used in the same quantities as the ethyl cellulose would have no such effect.
Ethyl cellulose slows rate of solution of soap by 50% to 300% depending upon proportionment. Methyl cellulose does not have this effect. Methyl cellulose may be mixed with soap up to 40% directly without substantially decreasing insolubility of the soap. Butethyl cellulose can only be incorporated up to about 2% above which itwould render soap virtually insoluble.
It has been found desirable to include in the composition, in lieu of all or part of the polyethylene glycol esters, small amounts' from 1 to- 50% by weight ofhighly effective surface active agents, such as, for example, normal polymerized alkyl sulphonates, such as of the nature of dibutyl naphthalene sodium sulphonates, or of alkyl esters of di-basic carboxylic acids, such as the dioctyl ester of sulfonsuccinic acid, or sodium fatty alcohol sulfates such as sodium lauryl sulfates.
These materials should preferably be of anionic or non-ionic nature. Cationic agents are less preferable for most applications but may be advantageously used for low pH types of soils.
Among the other surface active materials which may be used are Triton 770, Triton NE, Arctic Syntex M, Igepal CA, Igepon T or other collamids, Tween 20 and Tween 60.
-' The collamids are generally of the formula:
R-CONH-CI-IzCHzSOsNa AIY1(SO3H) 1/0 (CnHZnO) z-CnHZnSOIlH Arctic Syntex M has the general formula:
CH3 (CH2) 12 to 20COOCH2CH(0H) CH2SO4Na Triton and Igepal CA are the same products and consist of polyethylene oxide condensates having (-CCOC-C)nOI-I groupings with molecular weights of 750 to 1000. Triton NE has the following formula:
HOCH2 (CH2'OCH2) nCHgOH where n is 8 to 90 ethylene oxide groups. The
commercially available material contains approximate 12 ethylene oxide groups. 7
Igepal CA is identified by the formula:
CcHs (CH2OCH2) nCHZOH where n represents 1 to 20 ethylene oxide groups.
The commercial material contains about 6 ethyle'ne oxide groups.
Tween 60 is sorbitan monostearate, while fJI EXAMPLE I A metal cleaning detergent composition which may be impregnated on cloth, paper or other wool, rock wool, or fibrous mattings made of hemp, or artificial fibers, may be made up in the following manner:
As batch A, the following composition is prepared with gentle mixing at a temperature of about 40 C.:
Preferred Range Ethyl cellulose 2 1-4 Methyl Cyclohexanone glyceryl acetal hereinafter called Cyclonol 2 0-4 Ethylene glycol monobutylether 10 5-25 Castor oil 4 0-10 Dibutyl phthalate 1 0-2 Prepare batch B from the following: ingredients," with stirring and gentle heating at 40 C.:
Preferred Range Oleic acid .l 20 5-30 Monoethanolamine 7 2-10 Ammonium gluconate 5 0-10 Sodium hexametaphosphate. 10 0-20 Diethanolamine 10 2-15 Whiting (finest bolted). 50-150 Infusorial earth (#200). 50 25-100 Methyl cellulose ether 4 0-50 Isopropyl alcohol 25 0-50 Dibutyl naphthalene sodium sulfonate 35 0-50 Water 300 -600 After each of batch A and batch B hasbeeni thoroughly mixed they are separately warmed to 70 C. and then batch A is poured into batch B with rapid agitation, emulsification taking place immediately.
Then the mass is agitated until it cools to 50" C. and it is transferred to a colloidal mill and homogenized.
The resultant emulsion may be impregnated upon paper or cloth or other fibrous materials, and the impregnated product may be dried under a vacuum or by gentle heating. The finished product may be used for cleaning metals by dampening the impregnated material with warm water and rubbing on the tarnished metal object until all tarnish is removed.
It will be noted thatthe composition only dis solves slowly with hot water and does not; melt too readily. j I
In the composition set forth above, other oils may be utilized in lieu of castor oil and other alkalies or alkaline materials may be used in lieu of the ethanolamines specified.
Dibutyl phthalate is merely a plasticizer'and may be replaced by other plasticizers and in lieu of oleic acid, it is possible to use other fatty acids to combine with the alkali present.
In lieu of the ethyl cellulose utilized, other water insoluble cellulose ether derivatives may be employed as binders to slow up solution of the fatty acid soap compound which is formed.
'In lieu of the infusorial earth; other abrasives 'orfillers may be employed.
EXAMPLE II v Preferred Range Ammonium stearate. 30 50 Mineral o' '10 2-25 Then batch B is made up, consisting ofthe following ingredients:
Preferred Range 10 2-15 50 -75 100 -150 3 %6 Dioetyl ester of sodium sulfosuccinic acid. 30 10-4 ymoL; 0. 5 0-1 Water 400 150-600 Sodium hexametaphosphate 20 5-40 The ingredients of batch B are first mixed in the water at about 30, while the chemicals of batch A are mixed at about C. and poured into batch B with rapid agitation, which agitation is continued until the emulsion cools to 20 C.
The emulsion is then transferred to a colloid mill and homogenized and then used asa detergent as such with or without the addition of filler, or it may be impregnated upon paper, cloth, or
by gentle heating.
In'the composition stated, the ethyl cellulose acts as a binder.
"The sodium hexametaphosphate will act as a I cleansing agent.
EXAMPLE III L To obtain a floating soap composition, /10 gram of benzyl cellulose having 25 benzyloxy groups per glucose residue may be emulsified with grams of diglyool oleate and then to the emulsion there may be added grams of hard soap and 'l /grgrams of sodium laurylsulfonate.
Theentire mass is heated to about C. and
is transferred to a paste mixer, soap remelter or crutcher.
a While the mass is being kneaded in the mixer, 5; grams of water is added. The massis then agitated very rapidly and is then removed to a vacuum oven or soap frames for drying. While drying the mass can be molded into cake form. The
finished cake is a floating detergent which will not rapidly dissolve while floating on water.
. When the cake is rubbed it will, however, reemulsifyand produce a heavy lather.
. The detergent functions satisfactorily in hard water'and the formation of calcium and magnesium soap curd is repressed by the diglycol oleate d'jthe sodium lauryl sulfonate or sulfate. This d i 'i' ent cake is not sensitive to the changes in atmospheric conditions. It does not lose weight in warm, dry weather, nor does it absorb moisture and become soggy in humid weather.
EXAMPLE IV One gram of polyvinyllalcohol is emulsified-j with 5 grams of mannidemonooleate. To this mixture is added 90 grams of kettle soap and the entire mass is transferred to a paste mill. The temperature is brought up to 100 C. and the mass is kneaded. V
Kettle soap is 65% soap and the balance water and glycerin. After a mass of .even consistency is attained, 2 grams of tetrasodium pyrophosphate dissolved in 8 cc. of hot water are added and mixingis continned." The. mass is then transferred to a vac uum .oven and dried and molded into cake form or to soap frames and cooled or molded into cake form. The finished cake is .smooth and has the appearance of conventional soap.
This detergent may be used in hard waterwith complete satisfaction. This composition enables incorporation of a crystalline electrolyte water softening agent which was not previously possible with soap compositions. Instead of polyvinyl alcohol, dimethylol urea having more than 4 mole units'per-molecules, diomeric or triomeric methacrylates, and diomeric or triomeric vinylidene chlorides or acetates may be used. These areall water insoluble and organic solvent soluble resins.
EXAMPLE V steel or metal wool and then dried in a vacuum or two grams of mannitan monooleatetank and is impregnated onto paper toweling in the conventional manner. The product is dried in a vacuum drier or by gentle heating.- The impregnated paper is stable under various climatic conditions and may be rolled or packaged in out form.
The product may be cast or rolled into a film without fibrous backing. i
The paper towelling made with this composition may be dispensed'with ordinary dispensing machines in public wash rooms and may be used to eliminate the inconvenience of liquid, powdered and cake soaps in public wash rooms.
' As the towel is rubbed on the wetted object, the detergent will re-emulsify and cleanse the object with the above composition.
I EXAMPLE VI A bead soap product that is stable in all cli',-
matic conditions and that will not become soggy can be made as follows:
1 gram of ethyl .cellulos'e is emulsified and plasticized with 2 grams of glycerylmonostearate. To this ina'ssis' added amixture of 92.5 grams of kettle" soap and B'gramsof sodium" myristyl collamide... The entire 'massis kneaded-fin a paste mill or a crutcher and when thoroughly kneaded'itis blown into beads in the conventional,
manner.
This detergent product also functions eifejci 1. WW ,A f ak P wd ter-=- gent composition can be made from. the same formula. The. kneaded mass is. dried. and run through a flaker and the product is then ready for distribution.
Ithas been found that the detergent. compositions described above may be impregnated onto paper or other fibrous material in the process. of. manufacture of such. material.
For example, in making. a crepe or tissue paper. the detergent chemicals can. be mixed in the beateralong. with. the. pulp and binding; materials; andwill not be removed with. the wash. water,
The. use of a self-emulsifying: plasticizer for a cellulose ether substance permits .thedetergent" materials to be incorporated into: the fiber the process of manufacture.
EXAMPLE VII Atissue paper which may be used for cleaning. silver and other fine metals: may be made as fol, lows:
Abeater mass is made up with. twentypounds of sulfite. pulp dispersed with 400 lbs. of. water. While the pulp is agitating in the beater, 1.0 pounds of detergent emulsion is made up in Example I or II.
After the entire mass is thoroughly mixed, it is run out on the screen and. from there through the. rollers of a paper making machine inthe conventional. manner.
The drip liquid from the screen can be re-- covered and used again. in the. beater.
- It is possible to use the above: detergent com-- positions for cleaning metal. In compositions for :cleaning metals such as aluminum, gold, silver, tin, brass, copper, nickel, etcwhich are impregnated on metal wools or abrasives or paper or cloth carriers and rubbed on. the. utensil or other metal object that is being. cleaned the composition may desirably include. a polyhydroxy organic. acid, lactone or polyhydroxy organic salt suspended in. an emulsified binder with a polishing; agent. and wetting agent.
The polyhydroxy organic. acids and. lactones such as gluconic acid and gluconodeltalactorie: are preferred. 7 1
The mixture may be impregnated into a. car riersuch as canton flannel or similar textile material, crepe paper toweling or. tissue paper, or a suitable metal wool such as aluminum wool or a fibrous or wool. siliceous.- mass. such. as. mineral wool and rock wool. The cleaner composition. and the fibrous wool. carrier or abrasive maylbe modified for the cleansing and polishing of. ditferent metals, and all the agents used. should benon-toxic and non-irritating to'thee skin. 3;
It is usually desirable to include agents-which act as emollients and prevent. the skin from drying or chafing when the composition. isused.
A composition suitable. for cleaning silver, gold or platinum impregnated into canton flannel or Similar textile material is made up in. two batches of the following ingredients:
. BatcTiA Parafiin 011 (light). 15- Diglycol laurate 30- Diglycol stearate 10 Diethylene glycol-monobutyl-ether acetate. 10 Ethyl cellulose 5' Beeswax 5 Cyclonol or methyl cyclo-hexanone-glycerol acetal Dibutyl phthalateunr. 1
Keryl C20 to C26 or cetyl. benzene sodium sulfonate (100%) 50 Gluconodeltalactone 50 Batches A and B are both mixed while heating to C.
Then batch B is poured into batch rapid: stirring.
Emulsification takes place immediately and; the mass is stirred rapidly until the temperature. drops to 50 C. The mixture is then run through a homogenizer to complete emulsification.
The temperature is then adjusted to 35 to 40 C. and the emulsion is transferred to a tank.
A ribbon of canton flannel or similar textile is run. through the emulsion and the fibres of the textile become impregnated. The excess emulsion is scraped off the bottom of the cloth and the wet impregnated mass is run through a vacuum dryer or is dried by gentle heating.
The finished. impregnated cloth. may be used. for cleaning silver by moistening, the cloth with. a small. amount of warm. water and then rubbing on the tarnished silver. The impregnated. chemicals re-emulsify and are liberated from the cloth to. act on the soil. and. tarnish. After. the tarnish is removed the. silver isrinsed with. warm water and is ready for use.
EXAMPLE IX A similar cleansing, composition may be. made by impregnating crepe of tissue or other soft.
paper with an emulsion formed. of the following ingredients:
A with Batch A Paraffin oil (light) 15 Ethyl cellulose 5 Beeswax 5 Diglycol laurate 30 Diglycol stearate e 40 Diethylene glycol-monobutyl ether acetate 5 Cyclonol Q Dibutyl phthalate 1 Batch B Water i -i 900 Isopropylalcohole. i 25* Methyl cellulose a 4 Sorbitol 2'0 Infusorial earth (-200 mesh) 1100 Phenyl sulfonate ethylene oxide alcohol sulfate (-1 00%) Gluconodeltalactone 50 The emulsion is made in. the same manner as in. Example VII]; and the paper is impregnated. in. the. same manner. as was the cloth.
The dried impregnated paper may be cut into rolled strips and. dispensed in. much the same manner as rolled paper towels. The impregnated. cleaning. paper is torn off from the roll. and used as. needed. The paper is moistened. with warm and rubbed on a tarnished silver article until it is cleaned. Then the soiled paper may be discarded.
' EXAMPLE. Xi For cleaning baser' metals such as almnmunr zinc, copper, steel, tin, nickel, etc. the following composition maybe-used:
, I Batch 11' ;Petrolatum Ethyl cellulose '7 .Beeswax l 5 'Diglycol laurate 30 Diglycol stearate 'Diethylene glycol-monobutyl ether acetate 5 .Cyclonol 6 Dibutyl phthalate 1 -'Isothymol 0.5
" Batch B Water 300 Isopropyl alcohol Methyl cellulose 5 Sorbitol 20 Infusorial earth (200 mesh) Polyethylene oxide alcohcl20 to 90 C2H4O groups (100%) "Gluconic acid (50%) 100 Tri-isopropanol amine 3 An emulsion is made in the same manner as in Example IX. Then the emulsion is impregnated ,into a porous or abrasive mass such as aluminum 'wool, copper wool, mineral wool or rock wool Also, the emulsion may be impregnated into a woven pad made of ordinary cotton fiber and soft metal fibre. aluminum are suitable for this purpose. Strips of woven metal cloth woven from aluminum, copper or other soft-non-corrosive metal wire may be used.
In the above compositions the cyclonol or cyclo hexanone glycerol acetal and the diethylene glycol-monobutyl ether acetate act as high boiling solvents which keep the emulsion at impregnating consistency and also act to plasticize the binder. The cyclonol-also acts as a grease solvent. .Cyclonol also acts as a true non-emulsifying plasticizer for the ethyl cellulose.
- --'The isothymol acts as a preservative.
- The isopropyl alcohol acts as a solvent for the ethyl cellulose while the sorbitol acts as a humectant and controls the moisture content. I The gluconicacid combines with the tri-isopro- Metal fibers such as copper and 0 panol amine to form a salt in part, the remainder being free acid.
The above compositions are typical but merely illustrative of the scope of this invention. The proportions of the chemicals used may vary considerably from the amounts cited above without departing from the spirit of this invention. Certain chemical agents may be substituted for those cited above.
For example, arabic, arabonic, xylonic, saccharonic or tri-hydroxy glutaric acids may be substituted for gluconic acid.
Any suitable abrasive material such as bentonite, tripoli or rottenstone may be substituted for infusorial earth. Other emulsification bases than diglycol laurate and diglycol stearate may be used. Such emulsification bases are mannide monooleate, mannitan monooleate, diglycol oleate or diethanolamine stearate.
There are many wetting agents that may be used in place of the cited alkyl aryl-sulfonates.
A few of the preferred ones are sodium dibutyl naphthalene sulfonate, sodium lauryl alcohol sulfate, sodium tetrahydronapthalene sulfonate, the sodium sulfonate of stearyl alcohol, sodium lauryl sulfate and sodium salt of sulfonated myristyl collamide.
Protective colloids other than methyl cellulose :may be used. Such gums as locust beangum,
gum tragacanth, India gum or gum arabic are useful. Such gums also may be replaced by water soluble protein materials such as albumin, gelatin or casein.
Resin binders such as low polymerized vinyl acetate, or polyvinyl alcohols may be substituted for part or all of the ethyl cellulose, if tackiness is avoided.
The present invention is particularly advantageous where it is desired to have a relatively slow dissolving soap as in the case of floating or aerated soaps which tend to dissolve too quickly in water, or where the detergent is combined with a fibrous or abrasive material and tends to dis: solve away from the fibrous material or abrasive too quickly before such fibrous material or abrasive can be thoroughly rubbed upon the object being cleansed. Moreover, the detergent compositions according to the present application are more resistant to atmospheric changes and will not lose weight or gain water with changesfrom temperate to tropical climates, or
with varying humidity or temperature changes in the same locality. The soaps according to the present application may be kept in wet dishes or containers without unduly softening, wasting away or becoming mushy, and where the soap is used in the form of beads, flakes or a powder, there will be decreased tendency toward caking or hardening.
Moreover, the water solubility retarding agent tends to protect the detergent from oxidation.
Where desired, it is possible to employ the slow dissolving soaps of the present invention in combinationwith ordinary, relatively quick dissolving soaps or detergents with the soap or deter-'- gent of the present invention constituting an outer layer or a protective surfacing or being mixed with the entire body of the ordinary detergent or soap so that there will be pockets 01' layers of ordinary detergents or soap which will quickly dissolve when exposed while other layers or pockets of slow dissolving soap, as according toithe present invention, will only slowly dissolve. Among the detergents that may be employed are cleaners for metalssuch as glucono-lactone, ammonium gluconate, trihydroxy glutaric acid, sodium hexametaphosphate, sodium metasilicate; toilet detergents such as sodium, potassium or alkanolamine 'stearates, oleates, laurates, palmitates and myristatesj fatty alcohol detergents, such as sodium lauryl or palmityl or oleyl sulphate, sulphonatedfats, 'oils or fatty acids oralcohols suchias sulfonated castor oil, tea seed oil, olive oil, peanut oil, cottonseed oil, spermaceti, cetyl alcohol, japan wax, fish oils, lard, rice bran oil, and so forth; the sodium salts of sulphonated or sulphated esterified dicarboxylic acids and so forth. The detergent may constitute from 5 to of the composition.
The soap and non-soap detergents themselves are not emulsifying agents for the ethyl cellulose or resinous or plastic solubility retarding material and it is necessary to add a material which will emulsify the ethyl cellulose or other solubility retarding material.
The ethyl cellulose or other solubility retarding materials may range from 0.1 to 5% by weight, while the emulsifying agents, usually oil active surface agents such as partially fatty acid esterified polyhydric aliphatic alcohols for the solubility retarding materials may range from 0.005% to 2%.
The water soluble, organic solvent soluble,
Mannide oleate or mannitan oleate permit incorporation of water softening agents, such as tetra sodium pyrophosphate, sodium hexametaphosphate and so forth without these substances crystallizing in the composition. These selfemulsifying plasticizers are usually polyhydric alcohols, one or more of the hydroxy groups of which are combined with high molecular weight fatty acidswith one or more free hydroxy groups. Oils, waxes and fats are added as lubricants and may be used in amounts from to 10%.
Where water soluble or dispersible gums, such as methyl cellulose, India gum and dextrin are employed they may be used in amounts ranging from /2 to 5%.
Where organic solvents such as isopropanol, ethylene glycol alkyl ethers, and so forth are employed they are evaporated off and reclaimed.
The present application is a continuation-inpart of application Ser. No. 405,659, filed August 6, 1941, and now abandoned.
Many other changes could be effected in the particular features of detergent compositions described, and in methods of usage set forth, and in specific details thereof, without substantially departing from the invention intended to be defined in the claims, the specific description therein merely serving to illustrate certain elements by which, in one embodiment, the spirit of the invention may be efiectuated.
What is claimed is:
1. A solid detergent composition formed of a sodium soap of high molecular weight fatty acid and about 0.1% to 5% by weight of a water-insoluble ethyl cellulose to retard ready solution of said soap and from about 0.005% to 2% of a partial high molecular Weight fatty acid ester of a polyhydric aliphatic alcohol.
2. A solid detergent composition formed of a sodium soap of high molecular weight fatty acid and about 0.1% to 5% by weight of a water-insoluble ethyl cellulose to retard ready solution '12 of said soap and from about 0.005% to 2% of a partial high molecular weight fatty acid ester of a polyhydric aliphatic alcohol, the emulsifying agent being mannitan monoleate.
3. A solid detergent composition formed of a sodium soap of high molecular weight fatty acid and about 0.1% to 5% by weight of a water-insoluble ethyl cellulose to retard ready solution of said soap and from about 0.005% to- 2% of a partial high molecular weight fatty acid ester of a polyhydric aliphatic alcohol, the ethyl cellulose containing about 2.5 ethoxy groups per glucose residue.
4. A solid detergent composition formed of a sodium soap of a high molecular weight fatty acid and about 0.1% to 5% by weight of a water-insoluble ethyl cellulose to retard ready solution of said soap and an emulsifying agent consisting of a partial high molecular weight fatty acid ester of a polyhydric aliphatic alcohol in an amount suflicient to emulsify said ethyl cellulose into the soap.
LOUIS MCDONALD.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,436,928 Zink Nov. 28, 1922 1,436,929 Zink Nov. 28, 1922 2,027,535 Jacobson Jan. 14, 1936 2,226,075 Rowe Dec. 24, 1940 2,356,168 Mabley Aug. 22, 1944 2,383,610 Morgan Aug. 28, 1945 FOREIGN PATENTS Number Country Date 7,128 Great Britain 1910v 211,294 Great Britain Feb. 21, 1924 340,232 Great Britain Dec. 17, 1930 423,238 Great Britain Jan. 29, 1935 444,165 Great Britain Apr. 1; 1936 473,220 Great Britain Oct. 8, 1937 488,686 Great Britain July 12, 1938 884,116 France Aug. 3, 1943 OTHER REFERENCES Industrial Chemist, June 1932, pp. 223, 224.
Lorand: Article in Ind. and Eng. Chem., May 1938, vol. 30, No. 5,,pp. 527-530.
Hercules, pub. on Ethyl Cellulose Properties and Uses, 1944, pp. 19, 30.

Claims (1)

  1. 4. A SOLID DETERGENT COMPOSITION FORMED OF A SODIUM SOAP OF A HIGH MOLECULAR WEIGHT FATTY ACID AND ABOUT 0.1% TO 5% BY WEIGHT OF A WATER-INSOLUBLE ETHYL CELLULOSE TO RETARD READY SOLUTION OF SAID SOAP AND AN EMULSIFYING AGENT CONSISTING OF A PARTIAL HIGH MOLECULAR WEIGHT FATTY ACID ESTER OF A POLYHYDRIC ALIPHATIC ALCOHOL IN AN AMOUNT SUFFICIENT TO EMULSIFY SAID ETHYL CELLULOSE INTO THE SOAP.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2714093A (en) * 1952-07-02 1955-07-26 Blumenthal Armin Method of preparing detergent compositions
US4100097A (en) * 1977-02-02 1978-07-11 The Hewitt Soap Company, Inc. Low pH detergent bar

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GB191007128A (en) * 1910-03-22 1910-09-08 Alfred Johnson A Shaving Paste.
US1436929A (en) * 1919-07-09 1922-11-28 Arthur O Zink Soap
US1436928A (en) * 1919-07-09 1922-11-28 Arthur O Zink Soap
GB211294A (en) * 1922-12-21 1924-02-21 Grigori Petroff Process for the manufacture of detergent compositions
GB340232A (en) * 1929-08-17 1930-12-17 Ig Farbenindustrie Ag Improved cleansing agents
GB423238A (en) * 1932-07-05 1935-01-29 Ig Farbenindustrie Ag Improvements in washing textiles, and preparations and washing liquors suitable therefor
US2027535A (en) * 1933-02-28 1936-01-14 Klipstein Chemical Processes I Cleaning and polishing composition
GB444165A (en) * 1934-06-08 1936-03-16 Victor Boulez A process of manufacturing soap
GB473220A (en) * 1936-06-04 1937-10-08 Adolf Welter Improvements in and relating to the manufacture of soap
GB488686A (en) * 1936-10-01 1938-07-12 Kalle & Co Ag Manufacture of colloidal urea-aldehyde condensation products
US2226075A (en) * 1938-04-22 1940-12-24 Du Pont Soap product
FR884116A (en) * 1942-07-10 1943-08-03 Alliance Europ Use of cellulose and its derivatives in soap making
US2356168A (en) * 1941-08-16 1944-08-22 Clarence W Mabley Soap leaf
US2383610A (en) * 1943-03-10 1945-08-28 Cities Service Oil Co Hand cleaning composition

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB191007128A (en) * 1910-03-22 1910-09-08 Alfred Johnson A Shaving Paste.
US1436929A (en) * 1919-07-09 1922-11-28 Arthur O Zink Soap
US1436928A (en) * 1919-07-09 1922-11-28 Arthur O Zink Soap
GB211294A (en) * 1922-12-21 1924-02-21 Grigori Petroff Process for the manufacture of detergent compositions
GB340232A (en) * 1929-08-17 1930-12-17 Ig Farbenindustrie Ag Improved cleansing agents
GB423238A (en) * 1932-07-05 1935-01-29 Ig Farbenindustrie Ag Improvements in washing textiles, and preparations and washing liquors suitable therefor
US2027535A (en) * 1933-02-28 1936-01-14 Klipstein Chemical Processes I Cleaning and polishing composition
GB444165A (en) * 1934-06-08 1936-03-16 Victor Boulez A process of manufacturing soap
GB473220A (en) * 1936-06-04 1937-10-08 Adolf Welter Improvements in and relating to the manufacture of soap
GB488686A (en) * 1936-10-01 1938-07-12 Kalle & Co Ag Manufacture of colloidal urea-aldehyde condensation products
US2226075A (en) * 1938-04-22 1940-12-24 Du Pont Soap product
US2356168A (en) * 1941-08-16 1944-08-22 Clarence W Mabley Soap leaf
FR884116A (en) * 1942-07-10 1943-08-03 Alliance Europ Use of cellulose and its derivatives in soap making
US2383610A (en) * 1943-03-10 1945-08-28 Cities Service Oil Co Hand cleaning composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2714093A (en) * 1952-07-02 1955-07-26 Blumenthal Armin Method of preparing detergent compositions
US4100097A (en) * 1977-02-02 1978-07-11 The Hewitt Soap Company, Inc. Low pH detergent bar
US4151105A (en) * 1977-02-02 1979-04-24 The Hewitt Soap Company Inc. Low pH detergent bar

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