US2607740A - Liquid anionic-dialkylolamide detergent composition - Google Patents
Liquid anionic-dialkylolamide detergent composition Download PDFInfo
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- US2607740A US2607740A US159854A US15985450A US2607740A US 2607740 A US2607740 A US 2607740A US 159854 A US159854 A US 159854A US 15985450 A US15985450 A US 15985450A US 2607740 A US2607740 A US 2607740A
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- dialkylolamide
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
- C11D1/655—Mixtures of sulfonated products with alkylolamides of carboxylic acids
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
- C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/07—Organic amine, amide, or n-base containing
Definitions
- the a'nionic sulfate and sulfonate detergents herein referred may be even solids at normal temperatures; 'In the. molten state, they are usually highly viscous 2.
- Selective soZvnt.'-The l iquid media which maybe employed must ne'cessarilybe selectivein action. It should be somewhatimiscible or soluble with Water; render'ahigh degree 'of fluidity to the composition; havesolubili'zing eflfeots on'thedetergents, permit adequate concentration-"of solids,
- Foaming The compositionishould yield a good volume of foam with a high-degree of'ifoam stability i during washing operations.
- The' foam should be ofgo'od creaminess Of'COIlSi'SlJEllCYfllOll large measure due to the amount of soil removed.
- Grease emulsificati-on.-It shouldpossess the ability'to' 'emulsify readily' fats, oils, greases-land the like in order. to facilitate removal of the same washing operations, particularly dishWa-sh-ing.
- Soil 'removalr-The detersive eificiency islin "Thecomposition-should exhibit a high level; of soil removal'power, particularlyin Washing o'tfine fabrics, dishwashing,v andthe like.
- composition should preferablypossess such solubility characteristics that a-concentratedsolution may ordinarilygbe 1 preparedwfornuse whereby v a relatively small .-amount may lac-conveniently utilized. by the con- .su'mer and yet beadequate .for many uses.
- the incorpoif a" suitable synthetic deteranionic sulfated 'and sulfon'ated detergentsare efiective" to achieve a significant and'synergistic present invention comprises a liquid detergent composition consistingi'essentiallyr of" the-water soluble anionic fs'ulfated' or sulfonate'd detersive alkylolamide eifective'to enhance the action of the detergent composition in aqueous solution, and a solubilizing diluent.
- the enhancing additives of the'.present invention are characterized by their weakly polar 112w.
- the hydroxyalkyl groups may be monoor polyhydroxy alkyl.
- suitable additives are N,N'bis (2 hydroxyethyl) laur- 'amide, N,N bis (2 hydroxyethyl) myristamide,
- dialkylolamides may be prepared in any "suitable manner and numerous processes for their production are well known in the art.
- a convenient and economical mode of synthesis involves the condensation of the higher fatty acylating compounds (e. g. lauric acid, lauric acid halide, etc.) with a suitable amino compound to produce a reaction product having the desired amide structure.
- the higher fatty acylating substances may be derived from pure, impure or commercial grades ofcapric, lauric or myristic acids and the like. More particularly, these acids may be produced from fatty oils, fats, greases, and other natural sources or be of synthetic origin as derived from the oxidation of hydrocarbons. According to its origin and the degree and manner of purification, capric, lauric and myristic acids may be commonly admixed or associated with other fatty acids of higher and lower molecular weight. It is within the scope of the invention that the capryl,
- lauroyl and myristoyl compounds may be associated with other fatty substances and the like provided the character and amount of such'other materials are not sufllcient to substantially neutralize or materially affect the enhancing power of the additives in the relationship set forth.
- the commercially pure capric, lauric and myristic acids having a concentration of such acids of about 90% and above.
- a typical composition of commercially pure lauric acid may be 90% lauric acid, 9% myristic acid, 1% unsaturated acids,
- Another suitable fatty acid mixture is topped coconut oil fatty acids produced by the removal of a low-boiling fraction
- dialkylolamines may be utilized in pure, impure, or commercial form.
- dialkylolamide According to the circumstances of manufacture of the dialkylolamide, it may be chemically and/or physically associated with other materials .such .as soap, free alkylolamine, piperazine type derivatives, etc. The presence of varying amountsof such materials and the like in admix- .ture with dialkylolamide is contemplated within r the scope of the present invention, provided the same are not significant enough to materially neutralize or substantially adversely affect the desired improvements to be accomplished with the combination of the anionic detergent and the dialkylolamide additive.
- reaction product of the higher fatty acylating substance and the dialkylolamine comprising the desired dialkylolamid-e-and other derivatives as produced under certain conditions may be utilized with marked success as additives in'the novel compositions of the present invention.
- the product is to be produced by the condensation of the suitable'higher fatty acids or their equivalent with an "equivalent or an excess of dialkylolamine, the molar ratio being from about 1 :1 to about lzl-O but preferably up to about 1:5 and usually from about 1': 2 ⁇ to about 1:3, at from about 100 C. to about 200' C., and
- a typical suitable reaction mixture cited for illustrative purposes and resulting from the condensation of commercially distilled lauric acid in purity and commercial diethanolamine contains the following components on a solids basis: diethanolamide about (35 diethanolamine soap about 10%, free amine, diethanolpiperazine and minor amounts of possibly other substances
- diethanolamide about (35 diethanolamine soap about 10%, free amine, diethanolpiperazine and minor amounts of possibly other substances
- aliphatiq agentsh such -asthe l aliphatic, acyl containing compounds wherein the acyl radical has about 8 to about 22 carbon atoms, and more particularly, the, aliphatic carboxylic ester type, containing. at least about 10 and preferably about 12;;to; about 26 carbon atoms. to the molecule.
- the aliphatic detersive compounds it is particularly preferred that the aliphatic detersive compounds, it
- propylene may be polymerized to the tetrarnen and Icondensed with :henzene in the.
- Eriedelecraitsszi catalyst-to- I yield essentially the dode'cy-l benzene derivatiyawhich is is'uitable .fonlisulionaticziv torthegtidesired sulfat. a typarticularly, it. is, preferred to, use the. mono,-
- suitable .solvent may be employed as the liquidrmedium Itshould possess several. essential characteristics:sincelit functions necessarily. as,ian .,integral part, of the composition. Beside its..chemical.inertness, itniust have .a. solubiliz; ing. aetionflon the solids. It should'possess a.
- a liquid. solvent medium may.
- The. alcohols shouldpreferably bethe saturated aliphatic type ⁇ they. may. be, monoor polyhydric. in character, and.may. contain inert .solubilizing. groups, suchlasetherlinkages. suitable. exampl e ethyl alc h -s' nrl alcohol, isopropylalcohol, nebutylfalcoholl. In. comparison. tovv ethyl alcohol and. the I like,.'..the. higher alcohols such, as butanol andthellike-arenot prei'erred since. the latter Qhafye in general. a comparatiyelyfundesirable. odor. andlessv semi; bility inwater.
- Additional suitable solventsgqf. the polyhydric alcohol type arev ethylene. glycol, propyl e l c l. lycero e a Alcoho po s sse ing,ether linka es are monomethyl ether. ofethylene glycol,v monoethyl ether vof. ethylene glycol, diethylene glycol, diethyleneglyeol mono ⁇ . ethyl ether. monobutyl ether of diethyleneelycol, monomethyli ether of,.die thylene-, glycol, dioxan. etc. It is preferred to, uselwater,thealiphatic. monohydric alcoholsand the dih'ydric alcohols. bfll t 3w.
- Thegdialkylolamide maybe incorporatedw the anionic detergent atahlt. point, during. the. manufacturing process, atmv'vhi ch subsequent. op.-.- er ations will not. adversely modify the properties; of the detergent compositions.
- cedures are the, meltil of. the, dialkylolaojn an rinait into 'a;',, r. W r. t r ne. alcohol, or alcQholsolut-ion of thedetergen -orlf the dissolvingoithe additive. in alcohol or water and: stirring themixturelinto. the. anionic .de-
- the anionic detergent should be from about 30% to about 90% depending upon the solvent power, and preferably. at least about 40%. More particularly, it is preferred that the anionic detergent be at least about 30 and generally from about 40-60%, with the concentration of dialkylolamide usually at least about 10% and preferably from about 10 to about 20%. Where these solids are not sufficiently soluble in water alone for example, their solubility may be appropriately improved by the use of a mixed solvent medium, e. g. water and ethyl alcohol. While'it is preferred to prepare these compositions in the form of a concentrated solution as indicated above whereby the consumer may utilize the same conveniently and economically, it is within the scope of the invention that these compositions may be further diluted and be useful for many purposes, e. g. window, walls, woodwork, car washing, etc.
- the novel compositions of the present invention are characterized by increased stability of the foam produced in washing operations in comparison to the foaming effects produced by the compositions without the dialkylolamide.
- the foam of the compositions containing an 'anionic-dialkylolamide combination have good creaminess and consistency, do not readily break down by evaporation, have in general a long drainage time and contain an increased amount of liquid.
- the rate of foam decrease is consideraby slower ethanolamine salto'f dodecyl benzene sulfonate' with a minor amountof triethanolamine sulfate,
- composition II consists of,
- Composition III cnotains the desired combination of I and II, namely', 52 parts anionic active ingredient, 13 parts 'l'a'uroyl diethanolamide, and the remainder being the water-ethyl alcohol solvent. The tests are conducted in soft water at'11'5 F.
- compositionI Composition Per Cent I Triethanolamine salt of dodecyl benzene sulionate (52 parts) Lauroyl diethanolamide (13 parts) III Triethanolamine salt of dodecyl benzene sulfonate (52 parts) +lauroy1 diethanolamide (13 parts)
- compositions of the present invention '(e. g. composition III) is evident fromthe data. It is clear that the combinationachieves a sy ergistic enhancement in foam duration and resistance to greasy soil in comparison to the effects obtained by the individualuse of identical amounts of the components. f
- Table IIH indicates the results obtained in similar dishwashing operations in hard water (300 p. p. m.) at 115 F. of Composition III above containing the anionic detergent-qdialkylolamide.
- exhib t cloud point erosionas appmximate y yields ahighl level of 'creaminessiandlioam st 6036) I n-"proionged-chiiiirig and a; clear point ii bility infcorriparison to the relativelyrfiimsy sud of afb'out 35 -Cori slow warming; The stability mg power exhibitedi .by; the.
- compositions by means of a foam conof a 60% solution of thesame anionic detergent sistency test
- this test consists of the I withontiadded dialkylolamidat various indicated fdfmvaiiiofl'ofia f am' y'f fi aidi f t j' totai condentrationsof the detergent.compositions of 500 cc'fof adetergent'at 110F.'ina twoquart in distil'ldiwaterf v unsihfered' Dewar flaskg The' foani formed after TabZelV..-
- the deh Synergistic QR PVQIWWPSZP detergency grees through which the spring may be twisted ilgeg ip the 9 the mixed anionic-dibefore the paddle startsto move in the foam may a aide qqme ea en 1 g a hica ly rev siee v; be readily determined.
- An indicator needle is r em hemdata attachedito .the top of" the paddle-shaitand 1a .cir-j 1 Example. :7
- Example IV An impr v di u d j n h t deter eh so positionisjprenared by, ,r' iiiingtkie ingredient o g
- Example "I" Withth' modificationthata r I P61 g; q fli' 'sj acid diethanolaminereactionniixture gprepa ed
- Toppedffcooonut oil fatty. acids are e ir'i t- 7?5'.
- n i Composition anionic dialkylolamide detergent composition '75 aslow cooling process which involves cooling tfi 11 mixture with water at 120 F. circulating in a jacket, the mixture being agitated during this time, When the mixture reaches about 120 F.
- Example V The process of Example III is repeated with the modification that the dialkylolamide reaction mixture is made in accordance with the following procedure.
- Commercial lauric acid is melted and commercial diethanolamine is added with agitation till a 1 :2 molar ratio is reached.
- the reaction mixture is heated at 140-160 C. under vacuum. At this temperature, distillation of water occurs until the acid or soap content has been reduced to a value equivalent to 4.35%, calculated as diethanolamine laurate.
- the reaction product is rapidly run out of the reactorwith cooling and permitted to cool gradually.
- Example VI Per cent Triethanolamine salt of lauryl sulfate 25 Triethanolamine salt of dodecyl benzene sulfonate 25 N,N bis (2,3 dihydroxypropyl) myristamide 15 Water 15 Ethyl alcohol 20
- Example VII I Per cent Ammonium salt of higher fatty acid monoglyceride sulfates derived from coconut oil 50 Myristoyl and lauroyl diethanolamide -(1:1)
- a concentrated liquid detergent composition consisting essentially of water-soluble detergent selected from the class consisting of water-soluble salts of anionic sulfated and sulfonated de tergents having a long aliphatic chain of 8 to 22 carbon atoms, and adialkylolamide compound represented by the formula:
- R-CO is a fatty acyl radical of 10 I to 14 carbon'atoms, and R and R.” are hydroxyalkyl groups of up to about 5 carbon atoms each, the ratio of said dialkylolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said dialkylolamide and anionic detergent together being at least about 30% by weight in .a selective liquid solvent therefor.
- a concentrated liquid detergent composition consisting essentially of water-soluble salt of higher alkyl mononuclear aryl sulfonate detergent, said higher alkyl group having 8 to 22 carbon atoms, and a dialkylolamide compound represented by the formula:
- R-CO- is a fatty acyl radical of 10 to 14 carbon atoms
- R and R are hydroxyalkyl groups of up to about 5 carbon atoms each, the ratio .of said dialkylolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said dialkylolamide and anionic detergent together being at least about 30% by Weight in a selective liquid solvent therefor.
- a concentrated liquid detergent composition consisting essentially of water-soluble salt of higher alkyl, benzene sulfonate detergent, said higher alkyl group having 8 to 22 carbon atoms. and a diethanolamide compound represented by the formula:
- R,CO is a saturated fatty acyl radical of 10 to 14 carbon atoms, the ratio of said diethanolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said diethanolamide and anionic detergent together being at least about 40% by 'weight'in a selective liquid solvent therefor.
- a concentrated liquid detergent composition consisting essentially of anionic detergent selected from the class consisting of water-soluble salts .of anionic sulfated and sulfonated detergents having a; long aliphatic chain of 8 to 22 carbon atoms, and a dialkylolamide compound represented by the formula:
- RCO is a fatty acyl radical of 10 to 14 carbon atoms, and R and R, are hydroxyalkyl groups of up to about carbon atoms each,
- fatty acyl radical is myristoyl and the hydroxalkyl groups have 2 to 3 carbon atoms each.
- a concentrated liquid detergent composition consisting essentially of anionic detergent selected from the class consisting of water-soluble salt of anionic sulfated and sulfonated detergents having a long aliphatic chain of 8 to 22 carbon atoms, and a diethanolamide compound represented by the formula:
- Rr-CO is a saturated fatty acyl radical of to 14 carbon atoms, the ratio of said diethanolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said diethanolamide and anionic'detergent together being at least about 40% by weight in a selective liquid solvent therefor comprising a low molecular weight aliphatic alcohol.
- a concentrated liquid detergent composition consisting essentially of water-soluble salt of higher alkyl benzene sulfonate detergent, said higher alkyl group having 8 to 22 carbon atoms,
- Rr-CO-' is a saturated fatty acyl radical of 10 to 14 carbon atoms, the ratio of said diethanolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said diethanolamide and anionic detergent together being at least about 40% by weight in a selective liquid solvent therefor comprising a low molecular weight aliphatic alcohol.
- a concentrated liquid detergent composition consisting essentially of a solution of a mixture of anionic detergent selected from the class consistin of water-soluble salts of anionic sulfated and sulfonated detergents having a long aliphatic chain of 8 to 22 carbon atoms, and a dialkylolamide compound represented by the formula:
- RCO is a saturated fatty acyl radical of 10 to 14 carbon atoms
- R and R" are hydroxyalkyl groups of up to about 5 carbon atoms each, the ratio of said dialkylolaminde compound to anionic detergent being from about 1:7 to about 1:1 by weight, and said dialkylolamide and anionic detergent together being at least about 30% by weight in a selective liquid solvent phase therefor comprising water and an aliphatic saturated lower monohydric alcohol.
- a concentrated liquid detergent composition consisting essentially of a solution of a mixture of anionic detergent selected from the class consisting of Water-soluble salts of anionic sulfated and sulfon-ated detergents having a long aliphatic chain of 8 to 22 carbon atoms, and a diethanolamide compound represented by the formula:
- RCO is a saturated fatty acyl radical of 10 to 14 carbon atoms, the ratio of said diethanolamide compound to anionic detergent being from about 1:10 to about 2:1 :by weight, and said diethanolamide and anionic detergent together being at least about 40% by weight in a selective liquid solvent phase therefor comprising water and an aliphatic saturated lower monohydric alcohol mixture.
- a concentrated liquid detergent solution in accordance with claim 11 which contains sodium salt of said water-soluble anionic detergent.
- a concentrated liquid detergent solution in accordance with claim 11 which contains an ethanolamine salt of said water-soluble anionic detergent.
- a concentrated liquid detergent solution in accordance with claim 11 which contains ammoizium salt of said water-soluble anionic deteren PETER T. VITALE. RALPH SPENCER LEONARD.
Abstract
Dialkylolamides of fatty acids which contain 10 to 14 carbon atoms are prepared by condensing fatty acylating compounds such as the acid, its ester, acid anhydride or acyl halide with a dialkylolamine, the latter reactant being preferably in excess. Suitable molar ratios of acylating compound to dialkylolamine lie bebetween 1 : 1 and 1 : 10, preferably about 1 : 2 to about 1 : 3, the reaction being carried out between about 100 DEG C. and about 200 DEG C. A complex mixture of products is formed, and in order to obtain an equilibrium mixture containing an effective proportion of the dialkylolamide the product may be cooled relatively slowly or held at a slightly elevated temperature for a period of time. A typical reaction mixture from lauric acid (90 per cent pure) and diethanolamine may contain 65 per cent diethanolamide, 10 per cent diethanolamine soap and 25 per cent diethanol-piperazine and other substances including water. The fatty acylating substances may be derived from pure, impure or mixtures of capric, lauric, and myristic acids. Mixtures of these acids derived from natural sources and containing acids of higher and lower molecular weight may also be used, such as "topped" coconut oil fatty acids. Suitable dialkylolamines for the reaction include, besides diethanolamine, N,N - bis - (2,3 - dihydroxypropyl) - amine, dipropanolamine, N,N - bis - (2-hydroxylpropyl) - amine and dibutanolamine. Dialkylolamides specified include N,N-bis-(2-hydroxyethyl) - lauramide, N,N - bis - (2-hydroxyethyl) - capramide, N,N - bis - (2-hydroxyethyl) - myristamide, N,N - bis - (2,3-dihydroxypropyl) - lauramide, N,N - bis - (2,3-dihydroxypropyl) - myristamide, N,N - bis - (3-hydroxypropyl) - lauramide, N,N - bis - (3-hydroxypropyl) - capramide, N,N - bis - (2-hydroxypropyl) - myristamide, and N,N - bis-(4-hydroxybutyl)-lauramide. The dialkylolamides may be incorporated in detergent compositions (see Group III).ALSO:A liquid detergent composition comprises a water-soluble anionic sulphated or sulphonated detergent containing an aliphatic chain of at least 8 carbon atoms, a dialkylolamide of a fatty acid which contains 10 to 14 carbon atoms and a solvent for the detergent and the dialkylolamide. Suitable solvents include the low molecular weight hydroxyl containing solvents, particularly water, saturated aliphatic alcohols or aqueous saturated aliphatic alcohols. Specified alcohols include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, propylene glycol, glycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Dioxan may also be used. It is preferred to use water, mono- or di-hydric alcohols containing 2 to 4 carbon atoms in the molecule, lower (i.e. C1-C5) alkyl ethers of these dihydric alcohols and mixtures of these solvents The dialkylolamide may be of general formula RCO-NR1R11, where RCO represents a fatty acyl radical containing 10 to 14 carbon atoms and R1 and R11 are the same or different hydroxyalkyl groups of 1-5 carbon atoms. These hydroxyalkyl groups may be mono-or polyhydroxy in character. Specific dialkylolamide additives include N,N - bis - (2 - hydroxyethyl) lauramide, H,N-bis-(2-hydroxyethyl) capramide, N1N-bis-(2-hyroxyethyl) myristamide, N,N-bis-(2, 3-dihydroxypropyl) lauramide, N,N-bis-(2, 3-dihydroxypropyl) myristamide, N,N-bis-(3-hydroxypropyl) lauramide, N,N-bis- (3-hydroxypropyl) capramide, N,N-bis-(2-hydroxypropyl) myristamide and N,N - bis - (4-hydroxybutyl) lauramide. Diethanolamide compounds are preferred. (For preparation of these dialkylolamides see Group IV (b)). Impurities such as soap, free alkylolamine and piperazine type derivatives may result as by-products during the manufacture of the dialkylolamides, and provided that these impurities are not present in such amounts as to interfere with the detergent action of the final composition, the dialkylolamide product containing them may be used without further purification. The sulphated or sulphonated detersive compound may be an aliphatic acylcontaining compound containing 8 to 22 carbon atoms in the acyl group such as the sulphated or sulphonated aliphatic carboxylic esters containing 10 to 26 carbon atoms in the molecule. Other specified detergents include the sulphuric acid esters of polyhydric alcohols incompletely esterified with higher (i.e. at least 8 carbon atoms) fatty acids such as coconut oil monoglyceride monosulphate or tallow diglyceride monosulphate; pure or mixed higher alkyl sulphates such as lauryl sulphate, cetyl sulphate and fatty alcohol sulphates derived from reduced coconut oil fatty acids; the hydroxy sulphonated higher fatty acid esters such as the higher fatty acid esters of 2, 3-dihydroxypropane sulphonic acid; the higher fatty acid esters of lower alkylol sulphonic acids such as the oleic acid ester of isethionic acid; the higher fatty acid ethanolamide sulphates; and the higher fatty acid amides of amino alkyl sulphonic acids, e.g. lauric acid tauride. The higher alkyl-aryl sulphonates may also be used. The aromatic nucleus may be mononuclear or polynuclear in structure, and may be derived from benzene, toluene, xylene, phenol, cresols or naphthalene. The alkyl substituent may be straight or branched-chain in structure; specified alkyl groups include decyl, dodecyl, keryl, pentadecyl, hexadecyl and mixed alkyl groups containing at least 8 carbon atoms derived from long-chain fatty materials, cracked paraffin wax olefins or polymers of olefins such as propylene tetramer. The alkyl group may have 8 to 22 carbon atoms, and preferably 12-18. The detergents may be used as their water-soluble amine, alkali-metal or alkaline-earth metal salts, preferably the alkylolamine (especially mono-, di- and triethanolamine) salts. The ratio of dialkylolamide to anionic detergent may be between about 1 : 10 to about 2 : 1 by weight, preferably from about 1 : 7 to about 1 : 1 by weight. Depending on the solvent power of the selected solvent, the amount of total solids in the composition may be from about 30 per cent. to about 90 per cent., preferably at least 40 per cent. The amount of anionic detergent may be 40-60 per cent. and that of dialkylolamide 10-20 per cent. The dialkylolamide may be incorporated in the detergent at any stage of the manufacturing process, but it is preferred to add the molten dialkylolamide to a warm water, aqueous alcohol or alcohol solution of the detergent or to dissolve the dialkylolamide in alcohol or water and add the so formed solution to the detergent. Further dilution to the desired concentration may be necessary. In an example (all parts by weight) 13 parts of lauric diethanolamide, 44.7 parts of the triethanolamine salt of dodecyl benzene sulphonate, 7.5 parts of triethanolamine sulphate, 22.3 parts of water and 12.5 parts of ethyl alcohol are mixed to form a detergent composition.
Description
Patented Aug. 19, 1952 UNITED ,sTAT
VSPATENTIOFF 2,607,740 ICE LIQUID ANIONIC-DIALKYLOLAMIDE DETERGENT COMPOSITION Peter'Tc VitaleyBrooklyn, 4N: Y and Ralph Spencer Leonard, East Orange, N. .L, assignors te: Colgate-Palmolive Peet Company, Jersey A City, N. J .5 ajcorporation of Delaware I V no Drawing; Application May a, 1950,
- -'Serial'No.15 9,854
. lsfclaims. (01. 252452) ,properties and thelike involved in the action. of.
1 adetergenti compositionincluding suspension, in- --terfacialtension,- micellar structure, dispersion, foam -stabi-lity, etcland the'general difilculty'usually :ine'determiningthe particular mechanism which is being altered. by changes in the formula- -tion of detergent compositions. v
During recentlyears, synthetic detergents of the; type of the! Torganic sulfates and sulfonates have beendeveldrid which in general have cer- ,;tain properties which render them more, suitable than soaps for'certain uses. -By virtue of the di- Jverse nature of such synthetic detergentsincomeparison to soap, and consequently the fact that 5 they have extre'mely diflerent properties in aqueous-solution, e; g. thenon-formation of insolufibleprecipitates in hard1 water, there has been uncovered a .large field for researchanddevelopfment. (In general, the exploration for suitable additives'or. builder's forjsynthetic detergent composition'si'of the type of the'anionic sulfates and :sulfonatesfhasbeen directed by the requirements fof increased foaming and/or detersive power. iWhile the exact. relationship, if any, between ffo'ja'mingi'and detergency isnot known, it is highly d esirable'that these detergent compositions 'ex- ,hibit excellent foaming properties, in addition to ."ahigh levelof detersiveefficiency; particularly for consumer appear and'certain home andindustrial f.u 'ses. ."In .viewpf the complex nature of both the foam! and, lietfirgency phenomena, the character 7 'o such non-soap synthetic detergents, and the m yfotherjvariablesi in detergent compositions, ."acfld tivesin fgene'ral exhibit a certain degree of 'f'spec fici y.of act o V H ".In j general, because of technical iacility of jmagnuf actpre, and relative ease 1 of solution in tentmost of thesesynthetic detergents are producedjand sold inparticulate form. "Although 'fjgenerally;moresatisfactory in the form of solid ticles formany uses these products do have dva ntages. -Amo'ng"these are the preso a; enamjpropcrnon cranes Wh'ichmay e ufficient be irritative as a' dust nuisance, lkiness} pds'sibledeyelopment of tackiness, "cakvital considerations are set forth helow individuan but it is ,to be noted of co urse that'the de- .velopment of afsuitable liquid detergent composi- -tion. necessarilyfinvolves an integration of "the inter relationship among such factors 1."'V,i siiosity. The composition should benind to such an'extent that it maybe pourable from and tacky moreover;
a'conta'iner with ease. In general, the a'nionic sulfate and sulfonate detergents herein referred may be even solids at normal temperatures; 'In the. molten state, they are usually highly viscous 2. Selective soZvnt.'-The l iquid media which maybe employed must ne'cessarilybe selectivein action. It should be somewhatimiscible or soluble with Water; render'ahigh degree 'of fluidity to the composition; havesolubili'zing eflfeots on'thedetergents, permit adequate concentration-"of solids,
rate into different" phases 1 or solidify; and. ideas imaintain 'prferably a high degree ofsparkland 'clarityo'f solution. V
4. Foaming.--The compositionishould yield a good volume of foam with a high-degree of'ifoam stability i during washing operations. The' foam should be ofgo'od creaminess Of'COIlSi'SlJEllCYfllOll large measure due to the amount of soil removed.
break down'rea'dil'y" in the presence 0f-soil,-etc.
5; Grease emulsificati-on.-It shouldpossess the ability'to' 'emulsify readily' fats, oils, greases-land the like in order. to facilitate removal of the same washing operations, particularly dishWa-sh-ing. 6: Soil 'removalr-The detersive eificiency islin "Thecomposition-should exhibit a high level; of soil removal'power, particularlyin Washing o'tfine fabrics, dishwashing,v andthe like.
' 7. concentratiomeilhe, composition should preferablypossess such solubility characteristics that a-concentratedsolution may ordinarilygbe 1 preparedwfornuse whereby v a relatively small .-amount may lac-conveniently utilized. by the con- .su'mer and yet beadequate .for many uses.
8. Non-.z'rritatz'va-L-The solution shouldbe nonirritative to thegeneralpublic as much as'pos- .sibleand possessa desirable feel to the hands.
*Other yi t al considerations will be; apparent from the following description.
. It has npwheen discovered that the incorpoif a" suitable synthetic deteranionic sulfated 'and sulfon'ated detergentsare efiective" to achieve a significant and'synergistic present invention comprises a liquid detergent composition consistingi'essentiallyr of" the-water soluble anionic fs'ulfated' or sulfonate'd detersive alkylolamide eifective'to enhance the action of the detergent composition in aqueous solution, and a solubilizing diluent.
The enhancing additives of the'.present invention are characterized by their weakly polar 112w.
ture and may be represented by the formula: I
*more particularly, from'about'2 to about carbon atoms. The hydroxyalkyl groups may be monoor polyhydroxy alkyl. Examples of suitable additives are N,N'bis (2 hydroxyethyl) laur- 'amide, N,N bis (2 hydroxyethyl) myristamide,
N,N bis (2 hydroxyethyl) capramide, N,N bis (2,3 dihydroxypropyl) lauramide, N,N bis (2,3 dihydroxypropyl) myristamide, N,N bis (3-hydroxypropyl) lauramide, N,N bis. (3 hydroxy-- propyl) capramide, N,N bis (2 hydroxypropyl) 'myristamide, N,N bis (4 hydroxybutyl) flauramide, etc. Because of the excellent results obtained it is preferred to use the diethanolamide compounds and the additives possessing a fatty acyl radical of 12-14 carbon atoms.
These dialkylolamides may be prepared in any "suitable manner and numerous processes for their production are well known in the art. A convenient and economical mode of synthesis involves the condensation of the higher fatty acylating compounds (e. g. lauric acid, lauric acid halide, etc.) with a suitable amino compound to produce a reaction product having the desired amide structure.
The higher fatty acylating substances may be derived from pure, impure or commercial grades ofcapric, lauric or myristic acids and the like. More particularly, these acids may be produced from fatty oils, fats, greases, and other natural sources or be of synthetic origin as derived from the oxidation of hydrocarbons. According to its origin and the degree and manner of purification, capric, lauric and myristic acids may be commonly admixed or associated with other fatty acids of higher and lower molecular weight. It is within the scope of the invention that the capryl,
. lauroyl and myristoyl compounds may be associated with other fatty substances and the like provided the character and amount of such'other materials are not sufllcient to substantially neutralize or materially affect the enhancing power of the additives in the relationship set forth.
Thus, there may be suitably employed for the preparation of the dialkylolamide additives the commercially pure capric, lauric and myristic acids having a concentration of such acids of about 90% and above. A typical composition of commercially pure lauric acid may be 90% lauric acid, 9% myristic acid, 1% unsaturated acids,
-trace capric acid. Another suitable fatty acid mixture is topped coconut oil fatty acids produced by the removal of a low-boiling fraction,
(2 hydroxyprop'yl) amine, dibutanolamine, etc. It is to be understood that the dialkylolamines may be utilized in pure, impure, or commercial form.
. According to the circumstances of manufacture of the dialkylolamide, it may be chemically and/or physically associated with other materials .such .as soap, free alkylolamine, piperazine type derivatives, etc. The presence of varying amountsof such materials and the like in admix- .ture with dialkylolamide is contemplated within r the scope of the present invention, provided the same are not significant enough to materially neutralize or substantially adversely affect the desired improvements to be accomplished with the combination of the anionic detergent and the dialkylolamide additive.
It is a particular feature of this invention that the reaction product of the higher fatty acylating substance and the dialkylolamine comprising the desired dialkylolamid-e-and other derivatives as produced under certain conditions may be utilized with marked success as additives in'the novel compositions of the present invention.
' 'More particularly, the product is to be produced by the condensation of the suitable'higher fatty acids or their equivalent with an "equivalent or an excess of dialkylolamine, the molar ratio being from about 1 :1 to about lzl-O but preferably up to about 1:5 and usually from about 1': 2{to about 1:3, at from about 100 C. to about 200' C., and
preferably from about 120 C. to 180C.,'and
achieving a reaction mixture equilibrium comprising an effective amount of the dialkylolamide. With the fatty acids, an excess of dialkylolamine will usually be used, preferably up [to about 3:1. Using fatty acids or anhydride's illustratively as reactants, as the water is distilled off or otherwise removed during the reaction, the acid number falls indicating formation of amides. Thereaction is to be continued until thedesired'amount of water has been removed, e. g. not substantially in excess of 15% acid or soap and preferably up to about 10% as determined by the acid value resulting from titration of the reaction mixture with potassium hydroxide. With the use of methyl esters and the like as reactants, the amount of alcohol liberated is an index of completion of the reaction. In the case of the acid chlorides and the like as reactants, formation of chloride ion or its equivalent may be determined also. This condensation reaction between the higher fatty acids and the alkylolamines or theirequivalents is highly complex and produces a variety of products in addition to the desired, di-alkylolamide, Accordingly, it is necessary to achieve an equilibrium of the reaction mixture containing an effective proportion of the dialkylolamide. This equilibrium maybe achieved usually by permitting the reaction mixture to cool relatively slowly or maintaining the reaction mixture at slightly elevated temperatures for a suflicient period of time. The optimum equilibrium of the reaction mixture however achieved may be determined by routine tests such as hereinafter set forth wherein the novel liquid detergent compositions are subjected to practical washing operations. A typical suitable reaction mixture cited for illustrative purposes and resulting from the condensation of commercially distilled lauric acid in purity and commercial diethanolamine contains the following components on a solids basis: diethanolamide about (35 diethanolamine soap about 10%, free amine, diethanolpiperazine and minor amounts of possibly other substances The novel compositions of the present inlQ iMQ nslua e ated; or sulfonated;
therein: are the aliphatiq agentsh such -asthe l aliphatic, acyl containing compounds wherein the acyl radical has about 8 to about 22 carbon atoms, and more particularly, the, aliphatic carboxylic ester type, containing. at least about 10 and preferably about 12;;to; about 26 carbon atoms. to the molecule. Among the aliphatic detersive compounds, it
is-preferred to use- -thesulfated-- aliphatic comt s; he hi her. atty. cid. amid o a no. lsylfiilli n ei si s a auncam de oftaurine... mii ithe i a; j
' ambit. I". he invent on a e his at'e d ter entsalsol T se, re: math; ulionated tereent a e. also. know in th art; There may be mononuclearor pplynuclear n. r1 ,ctu M p rt cular y. the. aromat c uc us. max 'befler y d. from. n en toluene... Xylene.) p nol. r solsna h hal ne. c..- The QJKXL Sl bstifiuent. 9n. hejar mat nu leus a ry, Widely, s; ens. the des red a. eter ent. powe of. l h qacti e n rs i nt,v s; p served, ie uns resent. usual haye .one, mssent to eserv asmuchami s. 1e. be enqebetw en. -e h drqnll lic an hydrophobic portions'of'the molecule.
. id; thehi er; a ty acid. hano a ide l:
ruseitheh shen alkyl benzene sulfonates wherein the higher alkyl group is about. r22? to. 16 carbon atoms. Eon-example, propylene may be polymerized to the tetrarnen and Icondensed with :henzene in the.
presencemofia: Eriedelecraitsszi catalyst-to- I yield essentially the dode'cy-l benzene derivatiyawhich is is'uitable .fonlisulionaticziv torthegtidesired sulfat. a typarticularly, it. is, preferred to, use the. mono,-
ethanolamine, diethanolaniine, trieth a nolamine salts andmixtures thereof because-of theexc'ellent resultstattainedwith their use, particularly y with the. higher alkyl benzene sulfonates, the
higheraIkyI sulfates, and the higher fattywacid; monoglycerides sulfates. (and mixtures thereof} asgthe active ingredients.
suitable .solvent may be employed as the liquidrmedium Itshould possess several. essential characteristics:sincelit functions necessarily. as,ian .,integral part, of the composition. Beside its..chemical.inertness, itniust have .a. solubiliz; ing. aetionflon the solids. It should'possess a.
substantial solubility for the. anionic. detergent-1 and the dialli'ylolamid'e additivejointly; it stoma; be. water miscible or watersoluble in View of th'efact that the present compositions are designed at least in partfor use, in aqueous.. solutions; it.
should possess a relatively low, viscosity in order 7 containing solvent, may be suitably employed.
Moreparticplarly, a liquid. solvent medium may.
be selected, from thegroup consisting offvvateig, low molecular weight alcohols. and mixtures.
thereon The. alcohols shouldpreferably bethe saturated aliphatic type} they. may. be, monoor polyhydric. in character, and.may. contain inert .solubilizing. groups, suchlasetherlinkages. suitable. exampl e ethyl alc h -s' nrl alcohol, isopropylalcohol, nebutylfalcoholl. In. comparison. tovv ethyl alcohol and. the I like,.'..the. higher alcohols such, as butanol andthellike-arenot prei'erred since. the latter Qhafye in general. a comparatiyelyfundesirable. odor. andlessv semi; bility inwater. Additional suitable solventsgqf. the polyhydric alcohol type, arev ethylene. glycol, propyl e l c l. lycero e a Alcoho po s sse ing,ether linka es are monomethyl ether. ofethylene glycol,v monoethyl ether vof. ethylene glycol, diethylene glycol, diethyleneglyeol mono}. ethyl ether. monobutyl ether of diethyleneelycol, monomethyli ether of,.die thylene-, glycol, dioxan. etc. It is preferred to, uselwater,thealiphatic. monohydric alcoholsand the dih'ydric alcohols. bfll t 3w. ho-9 1, C bon em a nd r' we r allryl ethers of said dihydric .alcohpls,.,and; In turesthereof. h h j v Thegdialkylolamide maybe incorporatedw the anionic detergent atahlt. point, during. the. manufacturing process, atmv'vhi ch subsequent. op.-.- er ations will not. adversely modify the properties; of the detergent compositions. Ereferredgprole, ceduresare the, meltil of. the, dialkylolaojn an rinait into 'a;',, r. W r. t r ne. alcohol, or alcQholsolut-ion of thedetergen -orlf the dissolvingoithe additive. in alcohol or water and: stirring themixturelinto. the. anionic .de-
tr ent. Thereafter, them-ixturemay be further.
p e etqe et eime -wee e d tes ap tv' nd/f r in atte -1 Q=P QP- i I1Li h hlyw le eee eine ee-t espe fic te i lsdissolve and liquefy the solid components. The amount of total solids in such liquid compositions is variable and is limited chiefly by the degree of solubility in the liquid medium. For
optimum effects, the amount of total solids,
should be from about 30% to about 90% depending upon the solvent power, and preferably. at least about 40%. More particularly, it is preferred that the anionic detergent be at least about 30 and generally from about 40-60%, with the concentration of dialkylolamide usually at least about 10% and preferably from about 10 to about 20%. Where these solids are not sufficiently soluble in water alone for example, their solubility may be appropriately improved by the use of a mixed solvent medium, e. g. water and ethyl alcohol. While'it is preferred to prepare these compositions in the form of a concentrated solution as indicated above whereby the consumer may utilize the same conveniently and economically, it is within the scope of the invention that these compositions may be further diluted and be useful for many purposes, e. g. window, walls, woodwork, car washing, etc.
The following data and examples are additionally illustrative of the nature of the invention and it will be understood that the invention is not limited thereto.
From the viewpoint of foaming generally, the novel compositions of the present invention are characterized by increased stability of the foam produced in washing operations in comparison to the foaming effects produced by the compositions without the dialkylolamide. The foam of the compositions containing an 'anionic-dialkylolamide combination have good creaminess and consistency, do not readily break down by evaporation, have in general a long drainage time and contain an increased amount of liquid.
It has also been found that this combination tends to increase the tolerance of the detergent composition for the assimilation or holding in suspension of a maximum amount of dirt, grease, etc. with less foam loss than is found without the use of the dialkylolamide additives.
In practical dish pan tests wherein a small amount of the liquid detergent is added to a dishpan of water and greased dishes are washed by,
hand, it can beshown that the anionic detergentdialkylola'mide combination exhibits superior foaming properties; ,As increasing numbers of greased plates are washed the foam decreases.
The rate of foam decrease is consideraby slower ethanolamine salto'f dodecyl benzene sulfonate' with a minor amountof triethanolamine sulfate,
and 48 parts solvent consisting of water and ethyl alcohol mixture. Composition II consists of,
13 'p'arts' 'lauro'yl diethanolamide with the same diluent'as the'rem'ainder. Composition III cnotains the desired combination of I and II, namely', 52 parts anionic active ingredient, 13 parts 'l'a'uroyl diethanolamide, and the remainder being the water-ethyl alcohol solvent. The tests are conducted in soft water at'11'5 F. with the number of greased plates washed by the anionic detergent alone (compositionI) before'expiration Table I Foam Enduranoe in Dishwashing 1 Composition Per Cent I Triethanolamine salt of dodecyl benzene sulionate (52 parts) Lauroyl diethanolamide (13 parts) III Triethanolamine salt of dodecyl benzene sulfonate (52 parts) +lauroy1 diethanolamide (13 parts) The unusual effects obtained by the compositions of the present invention '(e. g. composition III) is evident fromthe data. It is clear that the combinationachieves a sy ergistic enhancement in foam duration and resistance to greasy soil in comparison to the effects obtained by the individualuse of identical amounts of the components. f
It may be added moreover, that the combination gave a high volume of foam of good consistency and relatively small bubbles. The anionic synthetic detergent alone gave a satisfactory volume of foam but of quite light consistency and composed of relatively large bubbles. The dialkylolamide exhibits a relatively poor volume of foam which is also of light consistency and large bubbles. I
The grease adhering to the dishes appeared to be satisfactorilyemulsified and removed for the duration of washing with the anionic detergent alone and with the anionic-dialkylolamide combination. The fact must be noted however. that over twice as many greased dishes were washed by the combination in the above relationship.
On the other hand, the grease was unsatisfac-.
torily emulsified using the dialkylolamide alone after only a very minor proportion of dishes were I washed.
Table IIHindicates the results obtained in similar dishwashing operations in hard water (300 p. p. m.) at 115 F. of Composition III above containing the anionic detergent-qdialkylolamide.
combination in comparison to a standard detergent composition consisting of a solution ofthe same anionic detergent. The .dishwashing operations were continued until both the foam.
. hadexpired and unemulsified grease appeared on anionic-dialkylolamide 'combination 100' The unusual results effected by the combination is evident from-thedata. rue fact that the testmg conditions weresevere (water 'of 300 p. p. m. hardness) and'gthat the standard composition contains 60 ariionic 'detergent incompa'rison to" the use of 52% in th'e novel compositions renders the results all the more striking. I I I In additionfthe liquid'detergent composition containing the combination indicated above 913 10:. exhib t cloud point erosionas appmximate y yields ahighl level of 'creaminessiandlioam st 6036) I n-"proionged-chiiiirig and a; clear point ii bility infcorriparison to the relativelyrfiimsy sud of afb'out 35 -Cori slow warming; The stability mg power exhibitedi .by; the. anionic:"detergent1; of -the composition-under= such marked adverse-' alone conditions-ishighly-desirable -for the prodntion Theiiefiectziorifdetergencyion 'compositionslofx of a successful liquid detergent compositionh the present invention may be:indicated. byiia:
It hasbeemfonnd moreover-;'-that thel substi standard soil removal test. This testing procedure tutionfof -paimitoyl -diethanoiamide fo'r the' involves the uniform soiling washing with par lauroyl omoonnd nanecompositions of the} tioular detergentcompositionsin distilled water present-inventionis u'nsucce'ssf-iil to {produce-de at 11Qf{ E ifanddryinggof a mg sired} results 5- i! The relatively greater insol-iibi-lity otyvoolen swatchesi {thewhitenessfofthelvari5i1s""' ofthe palmitoyl-diethano1amide'-is suc-h -that the tes't watches a l r flea sii r jbiiHiinterlreflec compositions cannot satisfactorilybe prpared-as v The its ofsoillfemovedfmay be' fc a sufiiciently concentrated-'- solutions inanefficie'nt later}: sub'tr thiavigg yrefieetmtyo y and economical manneri; Dishwashingexperiunwashed control; .sam nfsfrrom ."that 1 of'if ments-in soft'f wa'terwith 'paimitoyl diethanola washed swatches. midein coinhiriation with thesa'me anid'niti de-f Table IVi d1 a tergent a sl-t lsed above ina wand- 2:10 mushy weight discloses that theffoax n -vo1ume -andr' its stability-orresistance to g reasy soil is consistently 1; poorer than the effectsfi obtai-ned by use-ofi the-l anionic detergent alone.
In addition, the eifects on the foaming charwater! ndethyl alcfoholfmiiiture ..inf'conipa I g acteristics can be studied'quantitativdy for a to the standard'dtergentboiniiosition'consistiiigli'.
given composition by means of a foam conof a 60% solution of thesame anionic detergent sistency test Briefly this test consists of the I withontiadded dialkylolamidat various indicated fdfmvaiiiofl'ofia f am' y'f fi aidi f t j' totai condentrationsof the detergent.compositions of 500 cc'fof adetergent'at 110F.'ina twoquart in distil'ldiwaterf v unsihfered' Dewar flaskg The' foani formed after TabZelV..-
a 10 minutesegitati'on 'perio'd' is "then-measured" with aconsis'tometefafte stan dingjfor 5; 10and H 15minutes.j The"readings are"'amindication of g d; mb id the j b qif g- Total Concentration 01 Detergent Composition 33513)? it/Eg comparative basis, higher readings representim (Per Cent) Anionic-Dialkproved consistency orbody of the foam. 4 Ylolamide I position .ThlS consistometer 1s'ameans ior'measur ng v minimumitomue n ce ry for rotation of a i paddlel'ofany standard"sizejjthrougha if oa I This. device applies the torque jioymkaans of COiI SfJIifig 'which' hasgji'fi sji n fiel"lid 'attfihedfiq v a paddle shaft and the'outer end attachedtoa" circular plate whichoan be rotated. The deh Synergistic QR PVQIWWPSZP detergency grees through which the spring may be twisted ilgeg ip the 9 the mixed anionic-dibefore the paddle startsto move in the foam may a aide qqme ea en 1 g a hica ly rev siee v; be readily determined. An indicator needle is r em hemdata attachedito .the top of" the paddle-shaitand 1a .cir-j 1 Example. :7
freely- F a 1 Comparativefoam I consistency; tests:are;con1-.-: ducted in distilled watereusing :asz; a; standard; 1 triethanolamine salt of dodecyl benzene sulfonate; in comparison' to.adetergentcomposition con- Yr V U sisting of a mixtureaof 'thegsulfonate salt and, The composition of Example-I -isreproduced lauroyi diethanolamidegme rati'o' of anioniczderilsingthe lithiiim saltof"the anioifimd e nfi amp tergent to diethanolamideJoeing,6.66. to.;1.1 :The. in plae or thetriethanolamin'e' 'sa1f ;1 results' are set" iorth .1 m -Table III; the consistometer readings representing the avera'gegiat. 55 W I'EPZQUI...
10 and 15 minnte intervals. ThecompositiorrofiExample-I is-reproduced usingthe triethanolaiz'iiiie salt of-laurylf sulflte- L TqhZeiI II M as the anionic detergent. 7
Example IV An impr v di u d j n h t deter eh so positionisjprenared by, ,r' iiiingtkie ingredient o g Example "I "Withth' modificationthata r I P61 g; q fli' 'sj acid diethanolaminereactionniixture gprepa ed Anionic'Detersent a: -.--'-1-- 1; 220 '70 as follows'is substituted'for the"1auroy'1dieth s imiic-nign yio'aniid i l nolamide. Toppedffcooonut oil fatty. acidsare e ir'i t- 7?5'. 1???? a d hc ifi ro l dithaiioiam eim are j y Y ratio atlaboutf". c. unti1 "theacidlyalne ma s 1 5 evident irorn theldataljthatfthe,mixed'f. H ebo ti,,l-flhe r t nm t r is finis ed.
n i Composition anionic dialkylolamide" detergent composition '75 aslow cooling process" which involves cooling tfi 11 mixture with water at 120 F. circulating in a jacket, the mixture being agitated during this time, When the mixture reaches about 120 F.,
the agitation is stopped and the mixture allowed to stand overnight during which time further slow cooling takes place.
' Example V The process of Example III is repeated with the modification that the dialkylolamide reaction mixture is made in accordance with the following procedure. Commercial lauric acid is melted and commercial diethanolamine is added with agitation till a 1 :2 molar ratio is reached. The reaction mixture is heated at 140-160 C. under vacuum. At this temperature, distillation of water occurs until the acid or soap content has been reduced to a value equivalent to 4.35%, calculated as diethanolamine laurate. The reaction product is rapidly run out of the reactorwith cooling and permitted to cool gradually.
The following formulations are also productive of a high level of foaming and detersive properties:
Example VI Per cent Triethanolamine salt of lauryl sulfate 25 Triethanolamine salt of dodecyl benzene sulfonate 25 N,N bis (2,3 dihydroxypropyl) myristamide 15 Water 15 Ethyl alcohol 20 Example VII I Per cent Ammonium salt of higher fatty acid monoglyceride sulfates derived from coconut oil 50 Myristoyl and lauroyl diethanolamide -(1:1)
Monoethanolamine salt of higher fatty acid monoglyceride sulfates derived from coconut 'oil Lauroyl diethanolamide 12 Water 13 Monomethyl ether of ethylene glycol 20 Example IX Per cent Triethanolamine salt of kerylbenzene sulfonate 45 Commercial lauroyl acid diethanolamide con- 7 1 densate containing 65% diethanolamide, 10% soap, 25% diethanolamine and byproducts 31 Water 17 Monoethyl ether of diethylene glycol 7 Example X Per cent I-I igherfatty acid amides of taurine derived from coconut oil-triethanolamine salt 1 40 Capryl and lauroyl diethanolamide (1:1) .20 Water Ethyl alcohol 25 The term consisting essentially of as used in the definition of the ingredients present in the composition claimed is intended to exclude the presence of other materials in such amounts as to interfere "substantially with the properties to afiect said properties and characteristics ad-f versely.
Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications can be substituted therefor without departing from the principles and true spirit of the invention.
Having described the invention what is desired to be secured by Letters Patent is; I
1. A concentrated liquid detergent composition consisting essentially of water-soluble detergent selected from the class consisting of water-soluble salts of anionic sulfated and sulfonated de tergents having a long aliphatic chain of 8 to 22 carbon atoms, and adialkylolamide compound represented by the formula:
wherein R-CO is a fatty acyl radical of 10 I to 14 carbon'atoms, and R and R." are hydroxyalkyl groups of up to about 5 carbon atoms each, the ratio of said dialkylolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said dialkylolamide and anionic detergent together being at least about 30% by weight in .a selective liquid solvent therefor. I
2. A concentrated liquid detergent composition consisting essentially of water-soluble salt of higher alkyl mononuclear aryl sulfonate detergent, said higher alkyl group having 8 to 22 carbon atoms, and a dialkylolamide compound represented by the formula:
wherein R-CO-is a fatty acyl radical of 10 to 14 carbon atoms, and R and R are hydroxyalkyl groups of up to about 5 carbon atoms each, the ratio .of said dialkylolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said dialkylolamide and anionic detergent together being at least about 30% by Weight in a selective liquid solvent therefor.
3. A concentrated liquid detergent composition consisting essentially of water-soluble salt of higher alkyl, benzene sulfonate detergent, said higher alkyl group having 8 to 22 carbon atoms. and a diethanolamide compound represented by the formula:
wherein R,CO is a saturated fatty acyl radical of 10 to 14 carbon atoms, the ratio of said diethanolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said diethanolamide and anionic detergent together being at least about 40% by 'weight'in a selective liquid solvent therefor.
4. A concentrated liquid detergent composition consisting essentially of anionic detergent selected from the class consisting of water-soluble salts .of anionic sulfated and sulfonated detergents having a; long aliphatic chain of 8 to 22 carbon atoms, and a dialkylolamide compound represented by the formula:
wherein RCO is a fatty acyl radical of 10 to 14 carbon atoms, and R and R, are hydroxyalkyl groups of up to about carbon atoms each,
in accordance with claim 4 wherein the fatty acyl radical is myristoyl and the hydroxalkyl groups have 2 to 3 carbon atoms each.
7. A concentrated liquid detergent composition consisting essentially of anionic detergent selected from the class consisting of water-soluble salt of anionic sulfated and sulfonated detergents having a long aliphatic chain of 8 to 22 carbon atoms, and a diethanolamide compound represented by the formula:
wherein Rr-CO is a saturated fatty acyl radical of to 14 carbon atoms, the ratio of said diethanolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said diethanolamide and anionic'detergent together being at least about 40% by weight in a selective liquid solvent therefor comprising a low molecular weight aliphatic alcohol.
8. A concentrated liquid detergent composition in accordance with claim 7 wherein said solvent comprises an alcohol selected from the group consisting of aliphatic monohydric and dihydric alcohols of about 2' to 4 carbon atoms, and the lower alkyl ethers of said dihydric alcohols.
9. A concentrated liquid detergent composition consisting essentially of water-soluble salt of higher alkyl benzene sulfonate detergent, said higher alkyl group having 8 to 22 carbon atoms,
and a diethanolamide compound represented by the formula:
wherein Rr-CO-' is a saturated fatty acyl radical of 10 to 14 carbon atoms, the ratio of said diethanolamide compound to anionic detergent being from about 1:10 to about 2:1 by weight, and said diethanolamide and anionic detergent together being at least about 40% by weight in a selective liquid solvent therefor comprising a low molecular weight aliphatic alcohol.
10. A concentrated liquid detergent composition consisting essentially of a solution of a mixture of anionic detergent selected from the class consistin of water-soluble salts of anionic sulfated and sulfonated detergents having a long aliphatic chain of 8 to 22 carbon atoms, and a dialkylolamide compound represented by the formula:
.R RCON/ wherein RCO is a saturated fatty acyl radical of 10 to 14 carbon atoms, and R and R" are hydroxyalkyl groups of up to about 5 carbon atoms each, the ratio of said dialkylolaminde compound to anionic detergent being from about 1:7 to about 1:1 by weight, and said dialkylolamide and anionic detergent together being at least about 30% by weight in a selective liquid solvent phase therefor comprising water and an aliphatic saturated lower monohydric alcohol.
11. A concentrated liquid detergent composition consisting essentially of a solution of a mixture of anionic detergent selected from the class consisting of Water-soluble salts of anionic sulfated and sulfon-ated detergents having a long aliphatic chain of 8 to 22 carbon atoms, and a diethanolamide compound represented by the formula:
wherein RCO is a saturated fatty acyl radical of 10 to 14 carbon atoms, the ratio of said diethanolamide compound to anionic detergent being from about 1:10 to about 2:1 :by weight, and said diethanolamide and anionic detergent together being at least about 40% by weight in a selective liquid solvent phase therefor comprising water and an aliphatic saturated lower monohydric alcohol mixture.
12. A concentrated liquid detergent solution in accordance with claim 11 wherein said anionic detergent is essentially water-soluble higher alkyl benzene sulfonate salt.
13. A concentrated liquid detergent solution in accordance with claim 11 wherein said anionic detergent is essentially water-soluble higher alkyl sulfate salt.
14. A concentrated liquid detergent solution in accordance with claim 11 wherein said diethanolamide is at least about 10% by weight.
15. A concentrated liquid detergent solution in accordance with claim 11 wherein said alcohol is ethyl alcohol.
16. A concentrated liquid detergent solution in accordance with claim 11 which contains sodium salt of said water-soluble anionic detergent.
17. A concentrated liquid detergent solution in accordance with claim 11 which contains an ethanolamine salt of said water-soluble anionic detergent.
18. A concentrated liquid detergent solution in accordance with claim 11 which contains ammoizium salt of said water-soluble anionic deteren PETER T. VITALE. RALPH SPENCER LEONARD.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,173,448 Katzman et a1. Sept. 19, 1939 2,383,737 Richardson Aug. 28, 1945
Claims (1)
1. A CONCENTRATED LIQUID DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF WATER-SOLUBLE DETERGENT SELECTED FROM THE CLASS CONSISTING OF WATER-SOLUBLE SALTS OF ANIONIC SULFATED AND SULFONATED DETERGENTS HAVING A LONG ALIPHATIC CHAIN OF 8 TO 22 CARBON ATOMS, AND A DIALKYLOLAMIDE COMPOUND REPRESENTED BY THE FORMULA:
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US23840D USRE23840E (en) | 1950-05-03 | Liquid anionic-dialkylolamide | |
BE502985D BE502985A (en) | 1950-05-03 | ||
US159854A US2607740A (en) | 1950-05-03 | 1950-05-03 | Liquid anionic-dialkylolamide detergent composition |
FR1035745D FR1035745A (en) | 1950-05-03 | 1951-03-03 | Synthetic detergent compositions and their manufacturing process |
GB9063/51A GB708000A (en) | 1950-05-03 | 1951-04-18 | Improvements relating to liquid synthetic detergent compositions |
CH300865D CH300865A (en) | 1950-05-03 | 1951-05-02 | Liquid detergent. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US159854A US2607740A (en) | 1950-05-03 | 1950-05-03 | Liquid anionic-dialkylolamide detergent composition |
Publications (1)
Publication Number | Publication Date |
---|---|
US2607740A true US2607740A (en) | 1952-08-19 |
Family
ID=22574364
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US23840D Expired USRE23840E (en) | 1950-05-03 | Liquid anionic-dialkylolamide | |
US159854A Expired - Lifetime US2607740A (en) | 1950-05-03 | 1950-05-03 | Liquid anionic-dialkylolamide detergent composition |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US23840D Expired USRE23840E (en) | 1950-05-03 | Liquid anionic-dialkylolamide |
Country Status (5)
Country | Link |
---|---|
US (2) | US2607740A (en) |
BE (1) | BE502985A (en) |
CH (1) | CH300865A (en) |
FR (1) | FR1035745A (en) |
GB (1) | GB708000A (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2768957A (en) * | 1956-10-30 | Detergent purification | ||
US2831815A (en) * | 1952-12-17 | 1958-04-22 | Colgate Palmolive Co | Detergent compositions |
US2846400A (en) * | 1951-04-23 | 1958-08-05 | Lever Brothers Ltd | Detergent compositions |
US2864770A (en) * | 1956-10-03 | 1958-12-16 | Procter & Gamble | Liquid detergent composition |
US2870091A (en) * | 1955-09-01 | 1959-01-20 | Stepan Chemical Co | Detergent composition |
US2877186A (en) * | 1956-06-29 | 1959-03-10 | Procter & Gamble | Liquid detergent composition |
US2908651A (en) * | 1954-05-07 | 1959-10-13 | Colgate Palmolive Co | Liquid detergent composition |
US2920045A (en) * | 1955-09-06 | 1960-01-05 | Colgate Palmolive Co | Heavy duty liquid detergent compositions |
US2927081A (en) * | 1956-01-31 | 1960-03-01 | Lever Brothers Ltd | Detergent composition containing n-tris (methylol) methyl amides |
US2947702A (en) * | 1957-01-23 | 1960-08-02 | Procter & Gamble | Liquid detergent compositions |
US2969329A (en) * | 1956-04-12 | 1961-01-24 | Monsanto Chemicals | Detergent compositions |
US2970964A (en) * | 1957-04-16 | 1961-02-07 | Procter & Gamble | Opaque liquid detergent composition |
US2978416A (en) * | 1955-07-14 | 1961-04-04 | Allied Chem | Concentrated aqueous detergent composition |
US2980625A (en) * | 1959-05-11 | 1961-04-18 | Sterling Drug Inc | Dispersions of benzimidazolylstilbene whitening and brightening agents and production thereof |
US2992993A (en) * | 1957-01-23 | 1961-07-18 | Procter & Gamble | Liquid detergent compositions |
US3001949A (en) * | 1957-01-24 | 1961-09-26 | Colgate Palmolive Co | Shampoo composition |
US3001944A (en) * | 1957-07-12 | 1961-09-26 | Colgate Palmolive Co | Controlling viscosity of synthetic detergent-soap shampoos |
US3017363A (en) * | 1962-01-16 | Detergent composition | ||
US3021284A (en) * | 1958-10-30 | 1962-02-13 | Atlantic Refining Co | Liquid detergent compositions |
US3023168A (en) * | 1958-11-25 | 1962-02-27 | Atlantic Refining Co | Heavy duty liquid detergent |
US3029205A (en) * | 1958-05-05 | 1962-04-10 | Lever Brothers Ltd | Light duty liquid detergent |
US3052635A (en) * | 1960-12-14 | 1962-09-04 | Colgate Palmolive Co | Liquid laundering compositions |
US3066104A (en) * | 1958-02-10 | 1962-11-27 | Diamond Alkali Co | Heavy duty liquid synthetic detergent composition |
US3072580A (en) * | 1957-08-07 | 1963-01-08 | Gillette Co | Shampoo composition |
US3101324A (en) * | 1960-12-12 | 1963-08-20 | Colgate Palmolive Co | Liquid detergent composition |
US3150098A (en) * | 1959-06-01 | 1964-09-22 | Lever Brothers Ltd | Liquid detergent |
US3169930A (en) * | 1962-03-20 | 1965-02-16 | Procter & Gamble | Built liquid detergent |
US3179599A (en) * | 1961-07-03 | 1965-04-20 | Procter & Gamble | Detergent composition |
US3179595A (en) * | 1960-10-28 | 1965-04-20 | Colgate Palmolive Co | Aqueous shampoo compositions |
US3179598A (en) * | 1961-07-03 | 1965-04-20 | Procter & Gamble | Detergent composition |
US3190836A (en) * | 1962-07-03 | 1965-06-22 | Atlantic Refining Co | Water-soluble liquid detergent compositions |
US3223186A (en) * | 1962-05-23 | 1965-12-14 | Pan American Corp | Method of drilling with air or gas |
US3226331A (en) * | 1962-07-03 | 1965-12-28 | Atlantic Refining Co | Oil-soluble liquid detergent compositions |
US3232880A (en) * | 1961-04-10 | 1966-02-01 | Ultra Chemical Works Inc | Liquid detergent composition |
US3239468A (en) * | 1961-05-26 | 1966-03-08 | Colgate Palmolive Co | Hard surface cleaning compositions |
US3250718A (en) * | 1961-11-24 | 1966-05-10 | Swift & Co | Process for preparing a liquid detergent composition |
US3313735A (en) * | 1963-09-25 | 1967-04-11 | Procter & Gamble | Shampoo composition |
US3325416A (en) * | 1963-10-01 | 1967-06-13 | Colgate Palmolive Co | Synthetic gum dispersions |
US3391985A (en) * | 1963-02-08 | 1968-07-09 | Geigy Ag J R | Process for pad-dyeing and printing wool and synthetic textile fibers in carrier compositions |
US3903008A (en) * | 1972-05-01 | 1975-09-02 | Lanvin Charles Of The Ritz Inc | Cleansing bar |
US3951596A (en) * | 1972-10-13 | 1976-04-20 | Colgate-Palmolive Company | Soap curd dispersant |
US4179414A (en) * | 1978-10-23 | 1979-12-18 | Mobil Oil Corporation | Fatty acid diethanol amide-containing general purpose cleaner in paste form |
US4338211A (en) * | 1980-06-30 | 1982-07-06 | The Procter & Gamble Company | Liquid surfactant skin cleanser with lather boosters |
US4438025A (en) | 1981-12-30 | 1984-03-20 | Lion Corporation | Detergent compositions |
US4919838A (en) * | 1988-09-30 | 1990-04-24 | Hubert M. Tibbetts | Bar shampoo and skin soap |
US20080072477A1 (en) * | 2006-09-21 | 2008-03-27 | Colucci William J | Alkanolamides and Their Use as Fuel Additives |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE541262A (en) * | 1954-09-30 | |||
US2943058A (en) * | 1956-10-15 | 1960-06-28 | Diamond Alkali Co | Liquid detergent compositions |
US2859182A (en) * | 1956-11-02 | 1958-11-04 | Lever Brothers Ltd | Heavy duty liquid detergent composition |
BE569765A (en) * | 1957-07-25 | |||
US2994665A (en) * | 1959-04-15 | 1961-08-01 | Lever Brothers Ltd | Heavy duty liquid detergent compositions containing a pair of cellulosic soil suspending agents |
US3229777A (en) * | 1961-03-22 | 1966-01-18 | Swift & Co | Method of transporting water from a well as a substantially stable foam |
GB1143702A (en) * | 1965-03-18 | |||
US3441510A (en) * | 1965-10-12 | 1969-04-29 | Vego Chem Corp | Detergent composition |
US3549544A (en) * | 1966-10-03 | 1970-12-22 | Swift & Co | Liquid synthetic detergent |
US3451957A (en) * | 1967-02-03 | 1969-06-24 | George A Pritchard | Impregnating and coating compositions and articles and products treated therewith |
JPS518644B2 (en) * | 1972-07-19 | 1976-03-18 | ||
US4246131A (en) * | 1978-11-20 | 1981-01-20 | Inolex Corporation | Low-irritant surfactant composition |
FR2735495B1 (en) * | 1995-06-14 | 2003-03-07 | Rhone Poulenc Chimie | REDUCED IRRITATING COMPOSITION CONTAINING ANIONIC SURFACTANTS |
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US2173448A (en) * | 1937-05-17 | 1939-09-19 | Emulsol Corp | Preparation of alkylolamine derivatives |
US2383737A (en) * | 1942-02-18 | 1945-08-28 | Procter & Gamble | Detergent composition |
-
0
- BE BE502985D patent/BE502985A/xx unknown
- US US23840D patent/USRE23840E/en not_active Expired
-
1950
- 1950-05-03 US US159854A patent/US2607740A/en not_active Expired - Lifetime
-
1951
- 1951-03-03 FR FR1035745D patent/FR1035745A/en not_active Expired
- 1951-04-18 GB GB9063/51A patent/GB708000A/en not_active Expired
- 1951-05-02 CH CH300865D patent/CH300865A/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2173448A (en) * | 1937-05-17 | 1939-09-19 | Emulsol Corp | Preparation of alkylolamine derivatives |
US2383737A (en) * | 1942-02-18 | 1945-08-28 | Procter & Gamble | Detergent composition |
Cited By (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2768957A (en) * | 1956-10-30 | Detergent purification | ||
US3017363A (en) * | 1962-01-16 | Detergent composition | ||
US2846400A (en) * | 1951-04-23 | 1958-08-05 | Lever Brothers Ltd | Detergent compositions |
US2831815A (en) * | 1952-12-17 | 1958-04-22 | Colgate Palmolive Co | Detergent compositions |
US2908651A (en) * | 1954-05-07 | 1959-10-13 | Colgate Palmolive Co | Liquid detergent composition |
US2978416A (en) * | 1955-07-14 | 1961-04-04 | Allied Chem | Concentrated aqueous detergent composition |
US2870091A (en) * | 1955-09-01 | 1959-01-20 | Stepan Chemical Co | Detergent composition |
US2920045A (en) * | 1955-09-06 | 1960-01-05 | Colgate Palmolive Co | Heavy duty liquid detergent compositions |
US2927081A (en) * | 1956-01-31 | 1960-03-01 | Lever Brothers Ltd | Detergent composition containing n-tris (methylol) methyl amides |
US2969329A (en) * | 1956-04-12 | 1961-01-24 | Monsanto Chemicals | Detergent compositions |
US2877186A (en) * | 1956-06-29 | 1959-03-10 | Procter & Gamble | Liquid detergent composition |
US2864770A (en) * | 1956-10-03 | 1958-12-16 | Procter & Gamble | Liquid detergent composition |
US2992993A (en) * | 1957-01-23 | 1961-07-18 | Procter & Gamble | Liquid detergent compositions |
US2947702A (en) * | 1957-01-23 | 1960-08-02 | Procter & Gamble | Liquid detergent compositions |
US3001949A (en) * | 1957-01-24 | 1961-09-26 | Colgate Palmolive Co | Shampoo composition |
US2970964A (en) * | 1957-04-16 | 1961-02-07 | Procter & Gamble | Opaque liquid detergent composition |
US3001944A (en) * | 1957-07-12 | 1961-09-26 | Colgate Palmolive Co | Controlling viscosity of synthetic detergent-soap shampoos |
US3072580A (en) * | 1957-08-07 | 1963-01-08 | Gillette Co | Shampoo composition |
US3066104A (en) * | 1958-02-10 | 1962-11-27 | Diamond Alkali Co | Heavy duty liquid synthetic detergent composition |
US3029205A (en) * | 1958-05-05 | 1962-04-10 | Lever Brothers Ltd | Light duty liquid detergent |
US3021284A (en) * | 1958-10-30 | 1962-02-13 | Atlantic Refining Co | Liquid detergent compositions |
US3023168A (en) * | 1958-11-25 | 1962-02-27 | Atlantic Refining Co | Heavy duty liquid detergent |
US2980625A (en) * | 1959-05-11 | 1961-04-18 | Sterling Drug Inc | Dispersions of benzimidazolylstilbene whitening and brightening agents and production thereof |
US3150098A (en) * | 1959-06-01 | 1964-09-22 | Lever Brothers Ltd | Liquid detergent |
US3179595A (en) * | 1960-10-28 | 1965-04-20 | Colgate Palmolive Co | Aqueous shampoo compositions |
US3101324A (en) * | 1960-12-12 | 1963-08-20 | Colgate Palmolive Co | Liquid detergent composition |
US3052635A (en) * | 1960-12-14 | 1962-09-04 | Colgate Palmolive Co | Liquid laundering compositions |
US3232880A (en) * | 1961-04-10 | 1966-02-01 | Ultra Chemical Works Inc | Liquid detergent composition |
US3239468A (en) * | 1961-05-26 | 1966-03-08 | Colgate Palmolive Co | Hard surface cleaning compositions |
US3179599A (en) * | 1961-07-03 | 1965-04-20 | Procter & Gamble | Detergent composition |
US3179598A (en) * | 1961-07-03 | 1965-04-20 | Procter & Gamble | Detergent composition |
US3250718A (en) * | 1961-11-24 | 1966-05-10 | Swift & Co | Process for preparing a liquid detergent composition |
US3169930A (en) * | 1962-03-20 | 1965-02-16 | Procter & Gamble | Built liquid detergent |
US3223186A (en) * | 1962-05-23 | 1965-12-14 | Pan American Corp | Method of drilling with air or gas |
US3190836A (en) * | 1962-07-03 | 1965-06-22 | Atlantic Refining Co | Water-soluble liquid detergent compositions |
US3226331A (en) * | 1962-07-03 | 1965-12-28 | Atlantic Refining Co | Oil-soluble liquid detergent compositions |
US3391985A (en) * | 1963-02-08 | 1968-07-09 | Geigy Ag J R | Process for pad-dyeing and printing wool and synthetic textile fibers in carrier compositions |
US3313735A (en) * | 1963-09-25 | 1967-04-11 | Procter & Gamble | Shampoo composition |
US3325416A (en) * | 1963-10-01 | 1967-06-13 | Colgate Palmolive Co | Synthetic gum dispersions |
US3903008A (en) * | 1972-05-01 | 1975-09-02 | Lanvin Charles Of The Ritz Inc | Cleansing bar |
US3951596A (en) * | 1972-10-13 | 1976-04-20 | Colgate-Palmolive Company | Soap curd dispersant |
US4179414A (en) * | 1978-10-23 | 1979-12-18 | Mobil Oil Corporation | Fatty acid diethanol amide-containing general purpose cleaner in paste form |
US4338211A (en) * | 1980-06-30 | 1982-07-06 | The Procter & Gamble Company | Liquid surfactant skin cleanser with lather boosters |
US4438025A (en) | 1981-12-30 | 1984-03-20 | Lion Corporation | Detergent compositions |
US4919838A (en) * | 1988-09-30 | 1990-04-24 | Hubert M. Tibbetts | Bar shampoo and skin soap |
US20080072477A1 (en) * | 2006-09-21 | 2008-03-27 | Colucci William J | Alkanolamides and Their Use as Fuel Additives |
EP1903092A3 (en) * | 2006-09-21 | 2010-10-06 | Afton Chemical Corporation | Alkanolamides and their use as fuel additives |
US8444720B2 (en) | 2006-09-21 | 2013-05-21 | Afton Chemical Corporation | Alkanolamides and their use as fuel additives |
US9017430B2 (en) | 2006-09-21 | 2015-04-28 | Afton Chemical Corporation | Alkanolamides and their use as fuel additives |
Also Published As
Publication number | Publication date |
---|---|
FR1035745A (en) | 1953-08-28 |
CH300865A (en) | 1954-08-31 |
GB708000A (en) | 1954-04-28 |
USRE23840E (en) | 1954-06-15 |
BE502985A (en) |
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