laudry soap patent

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United States Patent [19]Wixon

[11][45]

4,304,680Dec. 8, 1981

[54] LAUNDRY SOAP[75] Inventor: Harold E. Wixon, New Brunswick,N.J.[73] Assignee: Colgate-Palmolive Company, NewYork, N.Y.[21] Appl. No.: 841,919[22] Filed: Oct. 13, 1977

Related U.S. Application Data[63] Continuation of Ser. No. 622,570,Oct. 15, 1975,aban-doned, which is a continuation of Ser. No."513,606,Oct. 10, 1974, abandoned, which is a continuation ofSer. No. 329,354,Feb. 5, 1973, abandoned.[51] Int. Cl.3 CllD 1/29; CllD 9/12;CllD 10/04; CllD 17/08[52] U.S. CI. 252/114; 252/109;252/121; 252/122; 252/132; 252/173;

2 52 /1 74 .1 4; 2 52 15 32 ; 252/551; 252/DIG. 14[58] Field of Search 252/109, 110, 111, 117,2521121,532, 551, 173,DIG. 14, 114[56] References Cited

U.S. PATENT DOCUMENTS2,527,075 10/1950 Preston 252/1213,085,982 4/1963 Steer 252/532 X3,179,599 4/1965 Eaton 252/153

3,414,520 12/19683,586,632 6/19713,707,503 12/19723,850,834 11/19743,959,165 5/19764,009,114 2/19774,013,577 3/19774,028,262 6/1977

McDonnell 252/110H e w i t t 252/117K , e r i n e y 252/117Hellsten 252/117Yurko . 252/109Y u r k o 252/109.IWixon 252/109Cheng 252/89FOREIGN PATENT DOCUMENTS945062 12/1963 United Kingdom 252/121

OTHER PUBLICATIONSSchonfeldt, N: "The Action of Various Lime SoapDispersants," J. Am. Oil Chemists' Soc., vol. 45, Feb.1969,pp. 80-82.Primary Examiner-Dennis L. AlbrechtAttorney, Agent, or Firm-:-Kenyon & Kenyon[57] ABSTRACTLaundry soap performance in hard water can be sub-stantially improved by i!lcorporating an alcohol poly-ethoxy sulfate and an alkali metal carbonate, alkalimetal silicate, or mixtures thereof, into the soap formu-lation. Additional builder salts may be added to theformulations. The soap formulations may be either liq-uids or dry formulations,

1 CI~m, No Drawings


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pared. from tallow, hydrogenated. tallow, grease, coco-nut oil, hydrogenated coconut oil; cottonseed. oil, soy-bean oil, corn oil, olive oil, palm oil, peanut oil, and thelike. These soaps usually comprise the water-soluble5 salts of higher fatty acids of about 12 to 20 carbonatoms. Soaps of fatty acids derived from syntheticsources may also be used.The alcohol polyethoxy sulfate used in the laundrysoap compositions of the present invention has the for-10 mula RO(C2H40)nS03M, wherein R is a fatty alkylgroup having from about 10 to 20 carbon atoms, n is anumber from 2 to 6, n being from 1/5 to! of the numberof carbon atoms in R, and M is a solubilizing, salt-form-ing cation such as sodium, potassium, ammonium, loweralkylamino, lower alkanolamino, etc.This anionic de-tergent is mostly readily biodegradable and has betterdetergency when the fatty alkyl group is terminallyjoined to the polyoxyethylene chain which, of neces-sity, is also terminally joined to the sulfur in the sulfategroup. Although a slight amount of branching of thehigher alkyl group may be tolerated, to the extent of not

morethan 10% of the carbon atom content of the alkylnot being in a straight carbon chain, generally even thisminor deviation from linear structure is to be avoided.Also; medial joinder of the alkyl to the ethoxy chainshould be minimal, i.e., less than 10%, and even suchjoinder should preferably be concentrated near the endof the alkyl chain. Within the 10to 20 carbon atom alkylgroups, the preferred alkyls are of 12 to 15 carbonatoms, and those most preferred are the mixed alkylscontaining 12, 13, 14 and 15 carbon atom chains. Themixture is preferably one with at least 10% of eachchain length and no more than 50% of anyone chainlength.The ethylene oxide content of the anionic detergent issuch that n is from 2 to 6 and preferably from 2 to 4 andgenerally averaging about 3, especiallywhen R ismixed12-15 carbon atom alkyl mixture. To maintain a desired40 hydrophilic-lipophilic balance when the carbon contentThe problems associated with use of soap in hard of the alkyl chain is in the lower portion of the 10-20water, namely the formation of soap curd which depos- range, the ethylene oxide content might be reduced soits on clothes, can be largely eliminated by the incorpo- that n is about 2, whereas when R is in the range of fromration of an alcohol polyethoxy sulfate and a suitable 16 to 18 carbon atoms, n may be within the range ofdetergency builder into the soap composition. The alco- 45 from,4 to 6.hols polyethoxy sulfate plus builder salt combination is The salt-forming cation may be any suitable solubiliz-hard water resistant, and therefore substantially im- ingmetal or radical, but will most frequently be anproves soap detergency in hard water, as well as effec- alkali metal cation or an ammonium cation. If alkyla-tively preventing soap curd formation, even in the hard- mine or lower alkanolamine groups are present, alkyls

est water, e.g., 600ppm. hardness. 50 and alkanols thereof usually contain 1to 4 carbon atomsIn the broadest sense, the laundry soap composition and the amines and alkanolamines may be mono-, di-, orof the present invention comprises from about 20 to tri-substituted, i.e., monoethanolamine, diisopropanol-80% of a water-soluble soap, from about 3 to about 30% amine, trimethylamine, etc.of a higher fatty alkylpolyethoxy sulfate of the formula Choice of the proper alcohol polyethoxy sulfate isRO(C2H40hS03M, wherein R is a fatty alkyl group of 55 important in obtaining maximum detergency from thefrom 10 to 20 carbon atoms, n is a number from 2 to 6, instant laundry soap compositions. Even within then being from 1/5 to 1/3 of the number of carbon atoms preferred range of alcoholpolyethoxy sulfates, an im-in R, and M is a solubilizing, salt-forming cation such as provement in detergency is noted for compositionsalkali metal, ammonium, lower alkylamino or lower which include a mixed 12-15 carbon atoms alcoholalkanolamino; and from about 5% to about 40% by 60 polyethoxy sulfate when compared to other higherweight of a builder selected from alkali metal carbon- alkyl ethoxy sulfates such as a mixed 14-15 carbonates and alkali metal silicates, as well.as soluble silicates, atoms polyethoxy sulfate of the same ethoxy chainoxydiacetates, iminodiacetates, polycarboxylates, etc. length. The preferred detergent is available from ShellThe instant laundry soap compositions may be pre- Chemical Company and identified by them as Neodolpared using any type of soap, including mixtures offatty 65 25-3S, the sodium salt normally sold as a 60% activeacid soaps. Suitable soaps include the water-soluble material including about 40% of the aqueous solventsoaps such as sodium, potassium, and other suitable medium, of which a minor proportion is.ethanol. Al-alkali metal and ammonium soaps which may be pre- though this material is the sodium salt, the potassium

14;304,680

LAUNDRY SOAPThis is a continuation of application Ser. No. 622,570filed Oct. IS , 1975;which is a continuation of applica-tion Ser. No. 513,606 filed Oct. 10, 1974; which is acontinuation of application Ser. No. 329,354 filed Feb.

5, 1973all now abandoned.BACKGROUND OF THE INVENTIONThe present invention relates to soap formulationswhich do not form a scum in hard water.The oldest, best known, or by far the most importantsurface active agents are soaps. The salient disadvan-tage of the soaps is their instability toward heavy-metal 15ions, particularly the calcium and magnesium ionsfound in hard water, asthe calcium and magnesium saltsof the fatty acids are quite insoluble in water. Soap,however, has at least two major points of superiority,i.e., low cost and high detergent powers in most of the 20cleaning operations encountered practically.Fatty acid soaps inmoderately hard water are knownto provide excellent soil removal and very good suspen-sion of soil in the wash cycle of laundering if sufficientquantities of soap are used. However, in the subsequent 25step of rinsing, a smaller amount of residual soap, whichcannot be totally extracted from the laundry items,comes into contact with a relatively large amount ofhard water cations. This rinsing step can reprecipitatelime soap, carrying with it small but ultimately visible 30amounts of insoluble dirt and other "color bodies".Thus, in hard water, soap is less economical to usethan detergents because a much higher concentration ofsoap is required to titrate the hardness. Soap is alsopoorly soluble in cool water, making it undesirable for 35

use inwashing many delicate synthetic fabrics aswell assome colored fabrics, the colors of which may bleed inhot water.SUMMARY OF THE INVENTION

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3 4,304,680and other suitable soluble saIts may be utilized either inpartial or complete substitution for the sodium salt.Examples of the higher alcohol polyethoxy sulfateswhich may be utilized in the laundry soap compositionsof the present invention include: mixed C12.15normal 5primary alkyl triethenoxy sulfate, sodium salt; myristyltriethenoxy sulfate, potassium salt; n-decyl diethenoxysulfate, diethanolarnine salt; lauryl-diethenoxy sulfate,ammonium salt; palmityl tetraethenoxy sulfate, sodiumsalt; mixed C14-15normal primary alkyl mixed tri- and 10tetraethenoxy sulfate, sodium salt; stearyl pentae-thenoxy sulfate, trimethylamine salt; and mixed CIO-18normal primary alkyl triethenoxy sulfate, potassiumsalt. Minor proportions of the corresponding branchedchain and medially alkoxylated detergents, such as 15those described above but modified to have ehtoxyla-tion at a medial carbon atom, e.g., one located fourcarbons from the end of the chain, may be employed,but the carbon atom content of the higher alkyl groupwill be the same. Similarly, the joinder of a normal alkyl 20group may be at a secondary carbon atom one or twocarbon atoms removed from the end of the chain. Ineither case, only the minor proportions previously men-tioned will be present.The composition of the present invention also in- 25eludes at least one builder selected from the following:alkali metal silicates, carbonates, citrates, oxydiacetates,polycarboxylates, hydroxyethyl iminodiacetates, andmixtures thereof, and preferably silicates and carbon-ates. The builders are used in the compositions of the 30present invention to enhance detergency in hard wateras well as in cool water.The water-soluble silicates which may be utilized asbuilders in the present composition are alkaline materi-als which also function as anti-corrosion or protective 35additives and are particularly helpful in removing par-ticulate soil from the laundry and preventing harm toceramic, porcelain, vitreous, aluminum, and steel partsof washing machines, similar equipment, and laundereditems.Although various soluble silicates may be utilizedproviding that their alkalinities are sufficient to aid inbuilding and anti-corrosion functions, those which aremost effective and readily available are the alkali metalsilicates, especially those wherein the Na20:Si02 or 45K20:Si02 ratios are within the range of 1:1.5 to 1:2.5.Particularly useful as the alkali metal silicates, i.e., so-dium silicates, wherein the ratios are 1:1.6 or 1:2.35. Itwill be apparent that the lower the ratio the higher thealkalinity of the silicate and, therefore, when it is de- 50sired to raise the alkalinity, the average Na20:Si02ratiowill be increased. Other silicates within the describedbroad range may be utilized either alone or in mixturesdepending on the particular soap compositions and thecompatibility of the various other constituents. AI- 55though silicates having ratios outside the 1:1.5to 1:2.5range may be utilized, such as those of ratios of 1:1 and1:3, generally the proportions of such silicates will beminor, being generally less than 10% of the total con-tent. Both the sodium and potassium silicates are useful 60as building agents in the laundry soap compositions ofthe present invention.The carbonates utilized may be utilized either in theirusual hydrated form or as soda ash; when a lower pH isdesired, the bicarbonates may be utilized. The carbon- 65ates, in addition to contributing to the detergency of theformulation, aid in saponifying fatty acid soils, thusaiding in removal of such soils. The carbonates also tie

4up the hardness ions of Ca+2 and Mg+2 present in thewash water.Where carbonates are used as builders in the instantlaundry soap compositions, it is desirable to have goodsuspension of the resulting calcium carbonate precipi-tate in the wash water, in order to minimize adsorptionof calcium carbonate onto fabric substrates and thusdecrease fabric "boardiness": Calcium carbonate pre-cipitates can be retarded during the normal wash cycleif an optimal weight of carbonate to citrate isemployed,Itwas found that this ratio isideally equal to or less than2 under average hard water washing conditions ofwater of 150 ppm. hardness at 40 C. The necessaryratio will decrease with increases in temperature andwater hardness. A relatively lower level of citrate, e.g.,between about 5% and about 15% sodium citrate, wasfound to delay calcium carbonate precipitation until thelater stage of the washing cycle and not to complete theprecipitation during the washing cycle. It can also domuch to improve the suspension of calcium carbonatewhich does precipitate (its particle size becomes fineand its surface charge increases). These functions willdecrease the adsorption of calcium carbonate onto laun-dered fabric.The preferred oxydiacetate salt for use in the instantsoap composition is monosodium oxydiacetate, al-though other water-soluble salts of oxydiacetic acid canalso be used. Examples thereof are disodium oxydiace-tate, other alkali metal and ammonium salts of oxydia-cetic acid, and alkylolamine salts of oxydiacetic acid.Monosodium oxydiacetate isof particular value in theinstant soap compositions because of its sequesteringability, which is the removal of an ion without precipi-tation or adsorption. From a practical point of view, thesequestering action of monosodium oxydiacetate is simi-lar to that of the condensed polyphosphates, and inmany cases the two substances produce substantiallythe same effect. Monosodium oxydiacetate has onegreat advantage over the condensed phosphates in that40 it does not tend to decompose or hydrolyze in aqueoussolution, and therefore can be used sucessfully as aningredient in aqueous formulations.Laboratory tests indicate that monosodium oxydiace-tate isless corrosive to copper and galvanized steel thansodium tripolyphosphate and trisodium nitrilotriace-tate. Results of biodegradation tests show that monoso-dium oxydiacetate can be oxidized readily by microor-ganisms.Other builders that can be used in the soap composi-tions of the present invention include alkali metal bo-rates, phosphates, polyphosphates, and bicarbonates.Specific examples of such salts are sodium and potas-sium tetraborates, bicarbonates, tripolyphosphates, py-rophosphates, orthophosphates, and hexarnetaphos-phates.Examples of suitable organic alkaline detergencybuilder salts which can be used include water-solubleaminopolycarboxylates (e.g., sodium and potassiumethylenediaminetetraacetates, nitrilotriacetates, and N-(2-hydroxyethyl)-nitrilo diacetates); water-soluble saltsof phytic acid; water-soluble salts of ethane-l-hydroxy-l, l-diphosphonate; water-soluble salts of methylenediphosphonic acid; water-soluble salts of substitutedmethylene diphosphonic acids; water-soluble salts ofpolycarboxylate polymers and copolymers (e.g., awater-soluble salt of a polymeric aliphatic polycarbox-ylic acid having the following structural relationships asto the position of the carboxylate groups and possessing


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5 4,304,680 6the following physical characteristics: a minimum mo- ally in amounts ranging from about 5% to about 25% bylecular weight of about 350 calculated as to the acid weight of the composition.form; an equivalent weight of about 50 to about 80 Organic solvents are present in the liquid soap com-calculated as to the acid form; at least 45 mole percent positions of the present invention to work in conjunc-of the monomeric species having at least two carboxyl 5 tion with the hydrotrope insolubilizing the active ingre-radicals separated from each other by not more than dients. The organic solvents help to impart a clear,two carbon atoms; the site of attachment to the polymer readily-flowing property to the soap compositions.chain of any carboxyl-containing radical being sepa- Among the organic solvents found to be particularlyrated by not more than three carbon atoms along the beneficial in the formulations of the present inventionpolymer chain from the site.of attachment of the next 10 are ethanol, propanol, isopropanol, propylene glycol,carboxyl-containing radical. Specific examples are pol- and the like. The solvents provide for improved physi-ymers of itaconic add, aconitic acid, maleic acid, mes- .cal .properties such as a.lower. cloud point, improvedaconic acid, fumaric acid, methylene malonic acid, and low temperature aging.modified viscosity, and the like.citraconic acid and copolymers with themselves and The suitable amount of solvent which may be employedother compatible monomers such as ethylene). 15 varies with the particular formulation, as an excessiveWhere a liquid formulation is desired, it is preferred amount tends to result in separation of the product intoto use potassium soaps arid potassium builder salts, two or more phases. The organic solvents are generallywhich are more soluble in water. Depending on the present in amounts ranging from about 5% to aboutproportions of soap, alcohol polyethoxy sulfate, and 25%, and preferably from about 10% to about 15%.solubilizers and hydrotropes used, a' clear liquid, an 20 Where a more viscous liquid soap formulation is de-opaque liquid, ora multi-phase liquid may be obtained. sired, it is possible to add a synthetic polymer typeThe preferred soaps for use in liquid detergent com- anti-redeposition agent to the formulation. Sodium car-boxymethylcellulose is by far the best known and mostpositions according to the present invention are potas- widely used anti-redeposition agent; it usually has asium oleate, potassium taIIowate, and potassium coco- 25 substitution value of 0.6toO.7, i.e., approximately twoate. Potassium oleate is the soap of preference because etherified hydroxyl groups are present for every threeof its greater water solubility. The concentration of anhydroglucose units. Many other hydrophilic coIIoids,soap in the liquid formulations can range from about particularly those which are polyelectrolytes, are useful100% to about 50%. as soil-suspending agentsin the soap formulations of theThe alcohol polyethoxy sulfates for use in the liquid 30 present invention, in the dry formulations as well as incompositions of the present invention are the same ones the liquid formulations. .The alginates, Irish moss, andas used in the dry formulations. The alcohol polyethoxy the various vegetable gums have a valuable soil-sus-sulfates are present in the liquid soap products in pending action. Carboxyethylcellulose, prepared byamounts ranging from about 1.0% to about 20%. adding acrylonitrile to alkali cellulose and hydrolyzingThe preferred builders for use in the liquid composi- 35 the nitrile group, has been found useful as a soil-sus-tions are mixtures of the alkali metal silicates having a pending agent, as well as several other cellulose deriva-Na20:Si02 ratio ranging from about 1:1.15 to about tives which are known to be emulsifying agents and1:2.5, and the alkali metal carbonates, including alkali protective colloids as well. Among these materials aremetal bicarbonates, and alkali metal sesquicarbonates. sulfoethylcellulose (made by adding vinylsulfonic acidThe silicates and the carbonates are each present in the 40 to alkali 'cellulose), hydroxyethylcellulose, and methyl-liquid soap compositions inamounts ranging from about cellulose. Carboxymethyl ethers of starch aswell as theI% to about 15%. Additional builders, as described for water-soluble methyl andhydroxyethyl ethers of starchdry soap compositions of the present invention, may be can also be used as soil-suspending agents in the formu-present in amounts ranging from about 1% to about lations of the present invention. Carboxymethyl starch15%. 45 can be prepared by treating starch with chloroaceticThe inclusion of a water-soluble hydrotropic sub- acid and sodium hydroxide in aqueous methanol. Poly-stance is effective in promoting the compatibility of the vinyl alcohols, 'polyvinylpyrrolidones, andpolyethyl-ingredients so as to form a homogeneous liquid product. ene glycols are among the synthetic polymers useful asSuitable materials are the alkali metal organic sulfo- antiredeposition agents" in the present formulations.nated (including sulfated) salts having a lower alkyl 50 Polyvinylpyrrolidones of molecular weight of 15,000 togroup of up to about sixcarbon atoms. It is preferred to 40,000 are very effective 'Whereas the higher polymersemploy an alkyl aryl sulfate having up to six carbon of molecular weightof 50;000 and upwards have veryatoms in the lower alkyl group such as the sodium and little soil-suspending action. Polyethylene glycols ofpotassium xylene, toluene, ethylbenzene, and isopropyl molecular weight of 6,000 or higher are very effective,benzene sulfonates. Sulfonates made from xylene in- 55 although the soil-suspending effect decreases with de-elude orthoxylenesulfonates, metaxylene sulfonate, crease in the molecular weight. Among the polyvinylparaxylene sulfonate, and ethylbenzenesulfonate as the alcohols the products of lower molecular weight andmain ingredient. Analyses of typical commercial prod- low degree of hydrolysis (77% hydrolyzed from theucts show about 40-50% metaxylene sulfonate, 10-35% polyvinylacetate starting material) are much more ef-orthoxylene sulfonate, and 15-30% paraxylene sulfo- 60 fective soil-suspending agents than the higher molecularnate, with 0-20% ethylbenzene sulfonate. Any suitable weight, fully hydrolyzed materials.isomeric mixture may be employed; however, sodium The liquid soap formulations of the present inventionand potassium alkyl naphthalene sulfonates having up to exhibit many desirable characteristics with regard tosix carbon atoms in the lower alkyl group may also be both physical properties and performance in use. As toused. Suitable lower alkyl sulfate salts having about fix 65 physical properties, the formulations are pourable andto sixcarbon atoms inthe alkyl group may be employed free-flowing from' the container as manufactured andalso, such as the alkali metal n-amyl and n-hexyl .sul- after aging. They exhibit a high degree of stability uponfates. The hydrotropic materials are employed gener- storage at normal room temperature of the order of


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7about 700 F. over a period of many months without anyappreciable precipitation. As a result, the consumer canutilize them conveniently by addition of small portionsto a dishpan or laundering bath and the formulation willbe present in constant composition in each portion.While adjuvant materials may be added which renderthe final solution transparent or opaque as desired, therequirement for a clear solution of the main ingredientsinsures that effective washing power will be obtainedwith each portion, and promotes the stability and homo-geneity of the product. The liquid may be packaged inany suitable container of packaging material such asmetal, plastic, or glass in the form of bottles, bags, cans,or drums.Various adjuvant materials may be added to the soap 15formulations of the present invention, including opticalbrighteners, bleaches, germicides, fungicides, bacteri-cides, colorants, perfumes, etc., which do not interferewith the detergency of the formulation.In performance, the products of the present invention 20exhibit a particularly high level of washing power dur-ing dishwashing, laundering, and other cleaning opera-tions.

DESCRIPTION OF THE PREFERREDEMBODIMENTSThe following examples are further illustrative of thepresent invention, and it will be understood that theinvention is not limited thereto.

Example IA laundry soap was prepared from the followingingredients:

4,304,680 8The results of the tests are shown in the followingtable:5 Research CenterSpangler Soil Particulate Bandy Black

Composition Ll.Rd' Post-Wash Rd' Clay. Ll.Rd'A 11.5 58.6 6.2B 15.8 57.3 7.0C 19.9 58.7 10.6

10 D 20.5 75.5 14.1whitencss as measured on a Gardner Color Difference Meierof a combination of soap and polyethoxy alcohol sulfateto even increased concentrations of soap in moderatelyhard water.

EXAMPLE IIA laundry soap was prepared from the followingingredients:

percent by weightSodium soap, 83% Tallow/17% CocoAlcohol polyethoxy sulfate'. sodiumsaltSodium carbonate

25 Sodium silicate. 1:2.35 Na20:Si02Optical brightenersPerfumeSodium sulfate

30.0015.0010.0015.001.050.1518.8010.00Water

30 'C12-CIS alcohol. ethoxylated with 3 moles of ethylene oxideA O.IS% concentration this soap composition foamsvery well in water up to at least 600 ppm. hardness atboth room temperature and 1200 F. with no curd forma-

35 tion. Spangler particulate soil detergency is satisfactory---------------------- in water at both room temperature and at 1200 F.percent by weightSodium soap, 83% Tallow/17% CocoAlcohol polyethoxy sulfate' ,sodium saltSodium carbonateSodium silicate, 1:2.35 Na20:Si02Optical brightenersPerfumeSodium sulfateWater

40.0010.00 AI10.0010.001.050.1518.8010.00

C12-CI5 alcohol, ethoxylated with 3 moles of ethylene oxide.

The efficacy of this composition was demonstrated inthe following Tergotometer detergency tests, usingthree soils. The products tested were used at O.lS%product concentration in water of ISOppm. hardness at 501200 F.The soiled swatches used were prepared as follows:Spangler Synthetic sebum/particulate soil was ap-plied to 100% cotton swatches from a water emulsionand allowed to dry. Piscataway, New Jersey, Research 55Center Particulate (sieved top soil) was applied dry to aSO% polyester/SO% cotton blend with a permanentpress finish. Bandy Black clay, obtained from H. C.Spinks Co., was applied to cotton from a water suspen-sion and dried.The cleaning products used were the following:A-40% soap, 10% sodium carbonate, 10% sodiumsilicate, QS H20B-SO% soap, 10% sodium carbonate, 10% sodiumsilicate, QS H20C-6S% soap, 10% sodium carbonate, 10% sodiumsilicate, QS H20D-Soap formulation of Example I

EXAMPLE IIIA test was performed to compare the soap composi-

40 tion of the present invention with laundry soap alone.The two formulations compared were as follows:A: Soap (83% Tallow, 17% Coco)

Sodium carbonateSodium silicateFillers, waterSoap (83% Tallow, 17% Coco)Alcohol polyethoxy sulfate(Cl2-CI5 alcohol, ethoxylated with3 moles of ethylene oxide)Sodium carbonateSodium silicateFillers. water

10%10%10%q.s.

4565%10%10%q.s.40%B:

A clean load of all dark fabrics was placed into aGeneral Electric washer, water was added, and theproduct was dispensed via the washer's filter tray. In allcases the wash water temperature was 1200 F., and thecleaner concentration was O.lS%. Water having hard-ness of ISOppm. and 2S0 ppm. as well as Piscataway,60 N.J. tap water having hardness of about 100 ppm. wasused for the tests. The fabrics were then examined forsoap residues. The results are tabulated below:

Water Hardness65 Wash # Rinse Temp. ResidueProductPiscataway.New JerseyTap 80' F.

66'HeavyNone

AB


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North Daxlight45 Product A Product B No Preferencepercent by weight Cotton 69 19 12Potassium soap, 83% Tallow/17% Coco 15.00 Easy Care 79 16 5Alcohol polyethoxy sulfate', Totals 72 18 10potassium salt 10.00 Incandescent LightPotassium sesquicarbonate 15.00 50Potassium silicate, 1:2.10K20:Si02 10.00 Product A Product B No PreferenceIsopropanol 10.00 Cotton 67 13 20Potassium xylene sulfonate 8.00 Easy Care 69 15 16Optical brighteners 1.05 Totals 68 14 19Perfume 0.15 55Water 30.80 The conventional laundry soap, Product B, gave aclassic example of "tattle tale gray." It is obvious fromthe foregoing that the soap compositions of the present60 invention give superior cleaning power in hard water,and do so at a much lower cost.A variety of soap compositions were compared fortheir cleaning ability in water of both 100ppm. and 150

ppm. hardness against three types of soil on both allpercent by weight 65 cotton and easy-care (polyester/cotton) fabrics. All-P-ot-a-ss-iu-m-ol-e-at-e--------...;.-.;_--4-5.;..OO-.....::;;-~ compositions were used at 0.15% concentration at 1200Alcohol polyethoxy sulfate', F. The results are. shown in terms of Rd reflectancepotassium salt 15.00 values; a measure of whiteness:

9-continued

Water Hardness Wash # Product Rinse Temp. Residue66' Moderate80' Very slight90' Very heavy65' None65' Very heavy87' None85' Very heavy66' None70' Moderate90' None

150PPMABABABABAB

250 PPM2

The data presents conclusive evidence that the com-position of the present invention is superior to plainlaundry soap with builders. Generally, no residue wasfound, despite the various rinse temperatures and waterhardnesses.

EXAMPLE IVA liquid soap formulation ismade up from the follow-ing ingredients:

percent by weightPotassium oleateAlcohol polyethoxy sulfate',potassium saltPotassium carbonatePotassium silicate 1:2.10K20:Si02

20.005.0010.00 .10.00

Trisodium citrate 10.00Ethanol 5.00Potassium xylene sulfonate 5.00Optical brighteners 1.05Carboxymethylcellulose 1.00Perfume 0.15Water 32.80CIZ-CIS alcohol, ethoxylated with 3 mol es of ethylene oxid e

EXAMPLE VA liquid soap composition is formulated as follows:

eI2-CI5 alcohol, ethcxylated with 3 moles o f ethy lene oxide

EXAMPLE VIA liquid soap composition is formulated from the

following ingredients:

4,304,680 10-continued

percent by weightPotassium silicate, 1:2.10K20:Si02

5 Monosodium oxydiacetateEthanolPotassium xylene sulfonateOptical brightenersCarboxymethylcellulose

5.005.005.002.001.051.000.1515.80

Perfume10 Water

'CIl-CIS alcohol, ethoxylated with 3 moles of ethylene oxide

A :. bundle test was performed to compare the perfor-15 mance of the soap compositions of the present inventionwith a conventional laundry soap formulation. Theformulations tested are as follows:

20 percent by weightProduct A: Soap (83% Tallow, 17% Coco)Alcohol polyethoxy sulfate'Sodium carbonateSodium silicateBrightenersWater, fillers, etc.Soap (83% Tallow, 17% Coco)Sodium carbonateSodium silicate .BrightenersWater, fillers, etc.

40.0010.0010.0010.001.05q.s.65.0010.0010.001.05q.s.

25Product B:

30'CIZ-CI5 alcohol ethoxylated with 3 moles of ethylene oxide

The products were used at 0.15% concentration inwater of 150 ppm.. hardness at 1200 F. The laundry35 bundles, weighing eight pounds each, were composedof cotton and easy care fabrics (polyester/cotton andnylon). The fabrics were dryer-dried and compared forcleanness under simulated north daylight and incandes-cent light (Mac Beth Examolite). The preferences of 1040.panelists are tabulated below in terms of percent ofvotes.


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11 4,304,680 12Research cu.Particulate Soil Bandy BlackSpangler Soil, 50% cotton, Clay Soil,Cotton 50% polyester Cotton~ Rd Post-Wash Rd ~ Rd

Composition' 100 ppm 150 ppm 100,ppm 150 ppm 100 ppm IS O ppm(I) 65/0/10/10 23.1 19.9 79.4 58.7 15.3 10.6(2) 5010/10/10 22.1 15.8 62.2 57.3 11.8 7.0(3) 5010/10/25 23.1 20.5 69.4 69.5 12.8 11.5(4) 10/212133 22.2 23.0 84.3 84.0 15.8 15.0(5) 40/0/10/10 21.6 11.5 58.6 58.6 9.6 6.2(6) 4010110/25 22.1 13.1 64.2 li8.4 11.6 11.8(7) 40/10/10110 23.5 20.5 73.3 75.5 14.3 14.1(8) 40/10/10/25 23.0 20.9 78.2 79.4 14.9 14.6'Soap/Alcohol PolyethoxySulfate(Ct2-Ct5alcoholethoxylatedwith 3 molesof ethyleneoxidej/.Sodium Carbonate/Sodium Sil icate

Further tests were conducted using one and threeProduct A Product B No Preference wash cycles. Each General Electric washer contained-C-ot-to-n-L-a-u-n-d-ry---""';'':'':'';46''':'':'''';';'''''''';'':'':'';16:';;':'';';;;'-''':'':''';''';''';':3';';8;';':':':':':''-40 two white cotton terrycloth towels and two 4"X6"

Easy-Care Laundry 25 7 67 EMPA soil swatches. The wash cycles were for a dura-tion of twleve minutes using tap water having a hard-ness of l00ppm. at 120 F. One towel and one swatchwere removed after one wash; one towel and oneswatch were removed after three washes.The laundry products used were as follows:

Softness tests were conducted to compare the soapformulation of the present invention with a conven-tional detergent formulation. Bundles of clothing werewashed in General Electric washers in water having a 20hardness of 150 ppm. at a temperature of 120 F. for tenminutes. The clothes were rinsed, dryer-dried and com-pared for softness by a panel of 10 persons. The prod-ucts were used at a concentration of 0.15%.The following products were compared:

Product A: 40% soap (83% Tallow/17% Coco)10% alcohol polyethoxy sulfate10% sodium carbonate10% sodium silicate10% linear tridecyl benzene sulfonate2% ethoxylated alcohol1% soap33% tripolyphosphate7% sodium silicate (1:2.35 Na20:Si02)

Product B:

The softness preferences are tabulated below:Softness Preferences (%)

One-towel tests were conducted to compare the soft-ness of towels washed in the soap formulation of the 45present invention with conventional laundry formula-tions. The products tested were as follows:

A. Soap (83% Tallow/17% 'Coco) 40 g.Alcohol polyethoxy sulfate' 5 g.Sodium carbonate 10 g.B. Soap (83% Tallow/17% Coco) 40 g.Alcohol polyethoxy sulfate' 5 g.Sodium carbonate 30 g.C. Soap (83% Tallow/17% Coco) 65 g.Sodium carbonate 10 g.Sodium silicate 10 g.D. Soap (45% Tallow/45% Grease/lO% Coco) 65 g.Sodium carbonate 10 g.Sodium silicate 10 g.E. Linear tridecyl benzene sulfonate 10 g.Ethoxylated alcohol 2 g.Soap 2 g.Sodium tripolyphosphate 33 g.Sodium silicate 7 g.F. Linear tridecyl benzene sulfonate 10 g.Sodium tripolyphosphate 35 g.

eI2-CIS alcohol ethoxylated with 3 moles of ethyl ene ox ide

One white cotton terrycloth towel was washed in aGeneral Electric washer with the above amounts of the

above-described products. The washing cycle was for aduration often minutes inwater of 150 ppm. hardness at120 F. After two rinsings, the towels were air-driedand rates for softness on a scale of 1-10, 10being maxi-mum softness. Towel yellowness was measured also,using b scale of the Garner Color Difference Meter25 (without brightener, values are +b; with brightener,values are - b; about 0.5 b unit difference is significantvisually). The results arefabulated below.

30 Product Softness Yellowness FactorA 8 +3.7B 6 +3.4C 6 -3.2 brightenersD 5 -4.2 ) were added toE 1 -5.0 these formula-tionsF +3.3

35

A. Soap (83% Tallow/17% Coco) 40 grams50 Alcohol polyethoxy sulfate' 10 gramsSodium carbonate 10 gramsSodium silicate 1:2.35Na20:Si02 10 gramsB. Soap (83% Tallow/17% Coco) 40 gramsSodium carbonate 10 gramsSodium silicate 1:2.35Na20:Si02 10 grams55 C. Soap (83% Tallow/17% Coco) 65 gramsSodium carbonate 10 gramsSodium silicate 1:2.35Na20:Si02 10 grams

D. 100grams of:Linear tridecyl benzene sulfonate 10 gramsEthoxylated alcohol 2 gramsSoap 2 grams60 Sodium tripolyphosphate 33 gramsSodium silicate 7 gramsCI2-CISalcoholethoxylatedwith3molesof ethyleneoxide

The results are tabulated below. Softness is rated on a65 scale of 1-10, 1o being the highest degree of softness, aswell as on yellowness factor. The Rd reflectance asmeasured on a Gardner reflectometer of the EMPAswatches is also tabulated:


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13 4,304,680

One Wash Three WashesSoft- Yellowness Rd Yellowness Rdness Factor EMPA Softness Factor EMPA 5A 6 +3.6 35.5 5 +3.5 44.8

B 5 +4.3 22.3 5 +4.1 30.0C 4 +3.4 43.5 3 +3.0 51.0D 1 +2.5 39.5 1 +2.5 50.3

It can be seen from the foregoing examples that the 10soap formulations of the present invention provide ef-fective cleaning with acceptable softness at a cost corn-parable to or lower than conventional laundry prod-ucts. The formulations of the present invention requirethe use of a minimum amount of soap for cleaning, 15resulting in a lower amount of soap flowing into sewagesystems and a consequent saving of our natural re-sources. Thus, there is no waste of soap to compensatefor water hardness in the soap formulations of the pres-ent invention. 20The present soap formulations exhibit improved de-tergency and virtually eliminate the problem of soapcurd formation, particularly during rising. Cool watersolubility of the product is good, allowing its use fordelicate fabrics and colors. 25While the soap formulations of the present inventionare excellent compositions for all types of cleaning op-erations, they are extremely effective for the cleaning oftextiles in a conventional laundry or washing machine.Thus, the soap formulations of the present invention can 30be effectively used for laundering fabrics in water hav-ing a temperature of from about 600 F. to about 2120 F.,the soap formulations of the present invention exhibit-ing unusually effective detergency characteristics in 3 5

14both cold and hot water. Preferably, the washing step ofthe invention is followed by rinsing and drying of thefabric. The soap formulation concentration in the washsolution should range ftorn about 0.05 percent to about0.5 percent by total weight.In washing fabrics, the addition of the fabrics and thedetergent compositions can be conducted in any suit-able conventional maimer. Thus, for example, the fab-rics can be added to the container or washer eitherbefore or after the washi~g solution is added. The fab-rics are then agitated in the soap solution for variedperiods of time, a wash cycle of from 8 to 15 minutesbeing generally used in the washing cycle of an auto-matic agitator type washer; As stated above, followingthe washing of the fabrics, the soap solution is drainedoff and the fabrics are rinsed in substantially pure water.Here again, as a matter of choice, the fabrics can be .rinsed as many times as desired. After the fabrics are'rinsed, they are dried, first by spinning, and then bycontact with air as in iI conventional hanging of' thefabrics on a clothesline, or in an automatic dryer typesystem.What is claimed is:1.A clear pourable homogeneous liquid laundry soapconsisting essentially of potassium oleate, 45% byweight; alcohol polyethoxy potassium sulfate, said alco-hol having from 12to 15carbon atoms, and ethoxylatedwith three moles of ethylene oxide, 15% by weight;potassium carbonate, 5% by weight; potassium silicate,5% by weight; monosodium oxydiacetate, 5% byweight; ethanol, 5% by weight; potassium xylene sulfo-nate 2% by weight; the balance of said formulationbeing substantially water.* * * * *

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UNITED STATES PATENT AND TRADEMARK OFFICECERTIFICATE OF CORRECTION4,304,680December 8, 1981Harold Eugene Wixon PATENT NO.DATEDINVENTOR(S) Page 1 of 2

It is ce rtif ied tha t e rro r appea rs in the above -iden tif ied pa ten t and tha t sa id Le tte rs Pa ten tis h ere by co rre cte d a s sh ow n b elo w:

Col. 1, line 46, before "po1yethoxy" change "ho1s" to --ho1--.Col. 3, line 16, after "have" change "ehtoxy1a-" to --ethoxy1a--.Col. 3, line 47, after "useful" change "as" to --are--.

Col. 5, line 29, change "100%" to --10%--.Col. 5, line 52, change "sulfate" to --su1fonate--.Col. 6, line 60, change "higher"to --high--.

Col. 6., line 68, change "tiempez'atrure" to --temperatures--.Col. 7, line 12, after "container" change "of" to -~or--.Col. 8, lines 11-12, before "of a combination" insert:

--The above results show the superiority including power--.Col. 12, line 22, change "rates" to --rated--.

t


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UNITED STATES PATENT AND TRADEMARK OFFICECERTIFICATE OF CORRECTION

PATENT NO. : 4,304,680DATED December 8, 1981INVENTOR(S): Harold Eugene Wixon

It is ce rtified tha t e rro r appears in the above-iden tified pa ten t and tha t sa id Le tte rs Paten tis h ere by c orre cte d a s s hown b elow :

Page 2 of 2

Col . 12, line 24, after "using" insert --the--.Col. 12, line 24, change "Garner" to --Gardner--.Col. 12, line 62, before "c -C " insert --*--12 15 . Col. 13, line 23, after "during" change "rising" to --rinsing--.Col. 14, line 7, change "compositions" to --composition.,..-.

S igned and Sca led th isSlxtH!lth D ay 0f MlUCh1911

ISEAllAtt.t:

GERALD J. MOSS INGHOFFCommissioner of Patents and Trademarks

laudry soap patent

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