US3285856A - Low foaming compositions having good detersive properties - Google Patents

Low foaming compositions having good detersive properties Download PDF

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US3285856A
US3285856A US352974A US35297464A US3285856A US 3285856 A US3285856 A US 3285856A US 352974 A US352974 A US 352974A US 35297464 A US35297464 A US 35297464A US 3285856 A US3285856 A US 3285856A
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foam
detergent
nonionic
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carbon atoms
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Henry Y Lew
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Chevron USA Inc
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/32Amides; Substituted amides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0026Low foaming or foam regulating compositions

Definitions

  • compositions of the present invention not only do not foam excessively, but in addition, have better detersive properties.
  • compositions of the present invention contain as essential components an anionic surfactant which can be an organic sulfate or organic sulfonate, a nonionic surfactant, and an amide foam-suppressing agent, all more particularly defined below.
  • the nonionic surfactant cooperates with the foam-suppressing agent to reduce foam, and all three components cooperate to produce a superior detergent, as will hereinafter be shown.
  • the foam reducing component herein contemplated is an amide compound which can be represented by the formula:
  • R is a straight-chain saturated alkyl radical of 13 to 21, preferably 15 to 17 carbon atoms, and R is hydrogen or a hydrocarbyl radical of 1 to 22 carbon atoms or an N-methylene amide radical of the formula R -iiNHoII wherein R is an alkyl radical of 13 to 21 carbon atoms.
  • the effective amount of this foam suppressor may range from about 2 to about 35% by weight, based on the active organic sulfate and/ or sulfonate in the detergent formulation, the preferred range being from about 5% to 15% by weight.
  • the anionic detergent component of the invention falls within the class of normally high foaming surface active materials which are the water-soluble salts of organic sulfonic acids and water-soluble salts of aliphatic sulfuric acid esters.
  • synthetic detergents are contemplated which normally tend to produce much foaming before treatment and are the salts of organic sulfuric reaction products having in the molecular structure either a sulfonic or sulfuric ester radical.
  • sodium and potassium salts are used for the purposes of laundering and dishwa-shing.
  • ammonium and magnesium salts are preferred in certain specialized applications.
  • the water-soluble salts of alkyl benzene sulfonates particularly those in which the alkyl group is a polypropylene radical or other carbon-containing chain, e.g., a straight-chain radical, having an average of 8 to 15 carbon atoms; the water-soluble salts of alkyl surfuric acid, having 8 to 20 carbon atoms in the alkyl group; the water-soluble salts, such as the alkali metal salts of sulfuric acid esters of primary normal aliphatic alcohols containing 10 to 18 carbon atoms, such as lauryl and oleyl alcohol; secondary alkyl sulfates having pronounced detergent power and obtained from secondary alcohols or olefins.
  • the alkyl group is a polypropylene radical or other carbon-containing chain, e.g., a straight-chain radical, having an average of 8 to 15 carbon atoms
  • the water-soluble salts of alkyl surfuric acid having 8 to 20 carbon atoms in the alky
  • the synthetic detergent components include the sulfuric acid esters which are the water-soluble salts of sulfuric acid esters of polyhydric alcohols incompletely esterified with high molecular weight soap-forming carboxylic acids, such as the water-soluble salts of sulfuric acid esters of higher molecular weight fatty acid monoglycerides, more specific examples being sodium glyceryl monolaurate sulfate and potassium glyceryl monopalmit-ate sulfate.
  • anionic detergents are alkyl aryl sulfonates of 10 to 20 carbon atoms in the alkyl group, the alkyl benzene sulfonates containing an average from 9 to about 15 carbon atoms in the alkyl chain, and, in particular, the polypropylene benzene sulfonates of the kind described by A. H. Lewis in his US. Patent No. 2,477,383, being particularly satisfactory.
  • benzene sulfonates such as keryl benzene sulfonates and the essentially straight-chain alkyl benzene sulfonates obtained by the alkylation of benzene with monochlorinated normal paraffins or with straight-chain olefins, can likewise be employed for the preparation of satisfactory low foam formulations.
  • organic sulfate detergents are both primary and secondary alcohol sulfates, in which the' alkyl group contains from 10 to 20 carbon atoms.
  • the alkyl group of these sulfates is usually a mixture of alkyl groups having from 10 to 20 carbons present.
  • Typical secondary sulfates are readily prepared by the reaction of an olefin and concentrated sulfuric acid, as disclosed, for example, in US. Patent 2,5 87,990.
  • Primary sulfates are prepared by the reaction of a primary alcohol and concentrated sulfuric acid, for example, as described in US. Patent No. 2,452,943.
  • M is an alkali metal.
  • a typical example is the sodium salt of lauryl ether of ethylene glycol monosulfuric acid.
  • detergents are the water-soluble salts of monosulfuric acid esters of the monoethers of high molecular weight aliphatic alcohols and glycerine. These compounds have the general formula:
  • M is generally an alkali metal.
  • a typical example is the sodium salt of monolauryl ether of rglycerine monosulfuric acid.
  • sulfuric acid ester synthetic detergents are water-soluble salts of sulfated higher fatty acid alkanolamides, such as the sodium salt of sulfated coconut oil fatty acid ethanolamide, and the potassium salt of sulfated lauric isopropanolamide.
  • the nonionic surfactant component of the invention is well known and may be defined as the reaction product of ethylene oxide with a hydrophobic compound con- .taining a carbox-yl, mercapto, amido, amino or hydroxyl group.
  • the properties of a nonionic can be modified by a simple change in proportions of ethylene oxide used. For example, the condensation products of ethylene oxide and C -C al-kyl phenol having fewer than about eight ethylene oxide units per molecule are more oil soluble, whereas those containing ten or more of such units are more water soluble.
  • R is a hydrophobic radical such as a long paraffin chain of 8 to 20 carbon atoms, an alkylated aromatic group having a total of 12 to 20 carbon atoms, a long chain acyl group of 10 to 24 carbon atoms, or a polypropyleneoxy group;
  • X is O, N or NH or S;
  • m a numeral from 1 to 50, and
  • n is 1 or 2.
  • Another class of nonionics is the type derived from a fatty acid, a polyhydric alcohol and ethylene oxide.
  • nonionics are tripropylphenoxynonaethoxyethanol, tetrapropylphenoxyundecaethoxyethanol, diisobutylphenoxyheptaethoxyethanol, C (straightchain) alkylphenoxynonaethoxyethanol, dodecylphenoxyp-entaethoxyethanol, n dodecoxyundecaethoxyethanol, n-octadecylaminodi(heptaethoxyethanol), t-dodecylmercaptononaethoxyethanol, polyethylene glycol 600 monostearate, polyoxyethylated sorbitan trilaurate, polyoxyethylated sorbitan monooleate, N-polyoxyethylated tetradecanamide, N,N-di(polyoxyethylated) docosanamide, polyoxyethylated tall oil fatty acids, polyethoxypolypropox'ypoly
  • the amount of nonionic surfactant that can be present in compositions of the present invention ranges from about to 75%, preferably -25, by weight, based on anionic surfactant and nonionic combined.
  • the present compositions may also contain auxiliary detergent agents, such as soap in amounts of, for example, 2 to 50% based on detergent components and amide.
  • auxiliary detergent agents such as soap in amounts of, for example, 2 to 50% based on detergent components and amide.
  • the fatty acid soap auxiliary detergent component may be any one of the several higher molecular weight saturated fatty acids, for example, sodium or potassium salts of fatty acids containing 14 to 22 carbon atoms.
  • inorganic salt detergent builders such as various water-soluble inorganic polyphosphates, sulfates, silicates, borates and carbonates, does not adversely affect the (foaming and detergent properties.
  • These builders the total amount of which may range by weight, based on finished com position, from about 45% to as high as 95%, but more usually between 75% and 85%, contribute their different specific effect toward a more satisfactory washing treatment Olf soiled clothing, dishes, etc.
  • small amounts usually less than 5% by weight, based on final composition, of well known minor additives, such as toluene or xylene sulfonates, carboxymethyl cellulose, methyl cellulose, optical bleach and perfume.
  • phosphate builders are used in their commercially available anhydrous form, obtained by the high-temperature dehydration of the orthophosphates-tripolyphosphates, from a mixture of disodium orthophosphate and monosodium orthophosphate; tetrasodi um pyrophosphates, lfrom disodium orthophosphates; and sodium polymetaphosphates, from orthophosphate.
  • the various condensed phosphates can be used singly or in admixture. As is known in the detergent art, the proportions of the various phosphates are frequently altered in practice, and similar practice can prevail here. Generally, good results are obtained when tripolyphosph'ate is essentially the sole condensed phosphate, or is admixed with the other condensed phosphates, for example, tripolyphosphate and 20% pyrophosphate.
  • the mixing of the ingredients to obtain the compositions of the invention is not critical.
  • One way is to mix foam-suppressing amide agent and nonionic, followed by heating to obtain a homogeneous mixture.
  • This homogeneous mixture is then incorporated with the anionic surfactant.
  • the mixture of nonionic and amide is added to a slurry of the anionic so as to ensure intimate admixture.
  • alkyl benzene sulfonate alkyl benzene sulfonic acid is mixed with caustic and a slurry is produced.
  • a slurry is produced.
  • Various inorganic salt detergent builders such as the phosphates, can then be incorporated in conventional manner.
  • detergent compositions containing the foam suppressor were prepared by mixing the synthetic detergents and amide in the specified amounts. Unless otherwise indicated, the compositions contained in addition tetrasodium pyrophosphate (45% commercial grade N sodium silicate (8%), sodium car-boxymethyl cellulose (1% water (4%), and the bal ance, where required to bring the total weight to being sodium sulfate.
  • foam heights were observed and measured in a :bench foam test. Foam level and detergency were also measured under simulated household-use conditions in a tumbler-type washing machine test.
  • oetadecanamide was used in formulations made up as described above, namely 17% sodium polypropylene benzene snlfonate, 3% nonionic, 45% tetrasodium pyrophosphate, 8% sodium silicate, 1% carboxymethyl cellulose, 4% water, and su! lic1ent sodim sulfate to bring the total weight up to 100%.
  • the nonionic was prepared from 13 mols of ethylene oxide and 1 mol of polypropylene phenol having an average molecular weight of 276.
  • the washing machine test above and in the following tables was carried out in the following manner: To a tumbler-type washing machine is charged 26 liters of water (50 ppm. hardness) at 120 F., containing 0.25%, by weight, of the test formulatlon. Then six pounds of shop towels, ten polyethylene sheets, several small soiled cotton swatches (for detergency measurements) and 1 gram of lard oil are added. The machine is started and the foam height, as viewed through the door window, is measured periodically over a 10 minute wash cycle.
  • a failure is shown by any formulation having too much foam leading to a foam height greater than one-half of the height of
  • the hardness of water as employed herein is defined in parts per million of calcium and magnesium, calculated as calcium carbonate and magnesium carbonate, in a weight ratio of 2: 1.
  • Percent soil removal (A B (C B X 100 wherein A is reflectance of soiled swatch after washing and B is reflectance of soiled swatch before washing, and C is reflectance of swatch before soiling (see J. C. Harris, Detergency Evaluation and Testing, Interscience Publishers, Inc., New York, 1954, page 79).
  • PPABS (348) is sodium polypropylene benzene sulfonate of 348 average molecular weight.
  • Nonionic A is water-soluble nonionic prepared from 13 mols of ethylene oxide and 1 mol of polypropylene phenol having an average molecular weight of 276.
  • PPABS (368) is sodium polypropylene benzene sulfonate of 368 average molecular weight.
  • Nonionic B is water-soluble nonionic prepared from 12 mols of ethylene oxide and 1 mol of dodecyl phenol.
  • Nonionic E is a condensation product of t-dodecy mercaptan with about 12 ethylene oxide units.
  • C1040 secondary sulfate is a sodium sulfate prepared from an approximately equimolar mixture of straightchain l-olefins of 10 through 20 carbon atoms and sulfuric acid.
  • Nonionic F is lauryl alcohol condensed with about 2.3 ethylene oxide units.
  • C alkylsulfonate is sodium-l-dodecyl sul-fonate.
  • Nonionic G is a commercial product (Sterox-CD) obtained by condensing tall oil fatty acids with ethylene oxide.
  • Nonionic H is a water-soluble nonionic prepared from 8 to 9 mols of ethylene oxide and alkyl phenol in which the alkyl group is an unbranched .hydrocarbyl radical of 7 through 11 carbon atoms.
  • Nonionic I is oil-soluble nonionic prepared from 6 mols of ethylene oxide and 1 mol of polypropylene phenol having an average molecular weight of 276.
  • Nonionic I is an ester of octadecanoic acid and polyethylene glycol of 600 average molecular weight.
  • Nonionic K is a polyether formed from polypropylene glycol having an average molecular weight of 1500-1 800 condensed with ethylene oxide to give a molecule containing about 80% ethylene oxide. 4
  • SCABS is sodium alkylbenzene sulfonate in which the alkyl group is an unbranched hydrocarbyl radical of 10 through 14 carbon atoms.
  • Nonionic C is water-soluble nonionic prepared from i 8 to 9 mols of ethylene oxide and alkyl phenol in which -the alkyl group is an unbranched hydrocarbyl radical of mixture of hexadecyl and octadecyl and amine and 15 mols of ethylene oxide.
  • C1043 SCABS is sodium alkylbenzene sulfonate in which the alkyl group is an unbranched hydrocarbyl radi- 60 cal of 10 through 13 carbon atoms.
  • anionic surfactant alone gives too much foam and poor soil removal (Test No. 1).
  • Anionic surfactant with amide gives low foam but poor soil removal (Test No. 2).
  • Nonionic alone or with amide gives low foam but poor soil removal (Tests Nos. 6 and 7).
  • Anionic and nonionic without foam suppressor gives too high foam (Test No. 5).
  • the presence of all three essential components gives satisfactory results (Tests Nos. 3, 4, 8 and 9). The results compare favorably with a commercial low foaming product based on nonionic (Test No. 10).
  • Table II illustrates the range of effective carbon chain length in the amide.
  • a satisfactory amide compound is one containing at least 14 carbon atoms in the alkyl group.
  • Dodecanamide has too few carbon atoms and, hence, is unsatisfactory (Test No. 11).
  • Tetradecanamide and anionic without nonionic are unsatisfactory (Test No. 12A compared with Test No. 12).
  • the higher amides are satisfactory (Tests Nos. 13, 14 and 15).
  • the proportion of foam-suppressing amide is in the range of 2 to 35% by weight of the anionic surfactant component. This is illustrated in Table III.
  • the improved detergent formulations of this invention are suitable for use in dilute aqueous solutions in a variety of washing appliances, such as rotary drum or tumblertype washers, top-loading agitator washers, bottle washers, etc. When so employed, little or no foam is formed, without any adverse effect on the detergency characteristics, in operating at temperatures from about 65 to 140 F., as commonly used in washing practice.
  • This suppression of suds in accordance with the invention permits employing a larger concentration of the active detergent in the preparation of washing solutions, as compared with the concentrations heretofore considered permissible maxima for tumbler-washer operations. A greater wash ing efliciency can therefore be achieved. Furthermore, the tendency to froth upon rinsing .is substantially obviated.
  • the effectiveness of the low foaming detergent formulations of the present invention can be used in tumblertype washers, as well as in any other washing equipment which utilizes strongly foaming organic detergent materials from the group of sulfates and sulfonates.
  • these formulations can be employed to reduce foaming in a number of solutions and emulsions, which, upon agitation, produce unduly high suds, causing spillage, pumping difliculties and interfering with a satisfactory filling of containers.
  • a detergent composition having good detersive properties and characterized by a low degree of foaming in agitated dilute aqueous solutions thereof consisting essentially of a nonionic surfactant, a normally high foaming anionic detergent component selected from the group consisting of water-soluble salts of organic sulfonic acids and water-soluble salts of sulfuric acid alkyl esters, and to suppress foaming of said detergent component about 2 to 35%, by weight, of said detergent of a foamsuppressing agent of the formula:
  • R is a saturated alkyl radical of 13 to 21 carbon atoms, and R is selected from the group consisting of hydrogen, a hydrocarbyl radical of 1 to 22 carbon atoms, and N-methyleneamide radicals, the alkyl group in the last-mentioned amide radical having 13 to 21 carbon atoms, the nonionic surfactant being present in an amount of to 75% by weight based on it and anionic detergent component.
  • composition according to claim 1 wherein the foam-suppression agent is present in an amount of 5 to by weight based on the anionic detergent component.
  • composition according to claim 2 wherein the anionic detergent component is an alkaryl sulfonate having 9 to carbon atoms in the alkyl group.
  • composition according to claim 2 wherein the anionic detergent component is alkyl sulfate having 10 to 20 carbon atoms.
  • a detergent composition having good detersive properties and characterized by a low degree of foaming in agitated dilute solutions thereof consisting of (l) a normally high foaming anionic detergent component selected from the group consisting of water-soluble salts of organic sulfonic acids and water-soluble salts of sulfuric acid alkyl esters, (2) a nonionic surfactant, (3) to suppress foaming of said detergent about 2 to 35%, by weight, of said detergent of a foam-suppressing agent having the formula:
  • R is a saturated alkyl radical of 13 to 21 carbon atoms, and R is selected from the group consisting of hydrogen, a hydrocarbyl radical of 1 to 22 carbon atoms, and Nmethyleneamide radicals, the alkyl group in the last-mentioned amide radical having 13 to 21 carbon atoms, and (4) inorganic detergent salt builders in an amount of 45 to by weight, based on said inorganic detergent builders and detergent component, the amount of nonionic surfactant being present in an amount of 5 to 75%, by weight, based on it and anionic detergent component.
  • composition according to claim 5 wherein the nonionic surfactant is present in an amount of 10 to 25%.
  • composition according to claim 5' wherein the anionic detergent component is an alkylaryl sulfonate having 9 to 20 carbon atoms in the alkyl group.
  • composition according to claim 5 wherein the anionic detergent component is alkyl sulfate having 10 to 20 carbon atoms.
  • composition according to claim 5 wherein the foam-suppressing agent is present in an amount of 5 to 15 weight percent based on the anionic detergent component.

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Description

United States Patent 3,285,856 LOW FOAMING COMPOSITIONS HAVING GOOD DETERSIVE PROPERTIES Henry Y. Lew, El Cerrito, Calif, assignor to Chevron Research Company, a corporation of Delaware No Drawing. Filed Mar. 18, 1964, Ser. No. 352,974 Claims. (Cl. 252152) The present invention relates to detergent compositions, aqueous solutions of which are characterized by good detersive properties and by a very low degree of foam formation under conditions of vigorous and continuous agitation.
Although the formation of abundant foam has been considered a desirable property of a washing agent as an indication of lasting detergent power, it is also recognized that copious suds formation is not necessarily a measure of detergent effectiveness. In fact, with certain household and commercial applicances and apparatus, production of copious suds is a handicap and not an advantage. Compositions of the present invention not only do not foam excessively, but in addition, have better detersive properties.
The compositions of the present invention contain as essential components an anionic surfactant which can be an organic sulfate or organic sulfonate, a nonionic surfactant, and an amide foam-suppressing agent, all more particularly defined below. The nonionic surfactant cooperates with the foam-suppressing agent to reduce foam, and all three components cooperate to produce a superior detergent, as will hereinafter be shown.
The foam reducing component herein contemplated is an amide compound which can be represented by the formula:
wherein R is a straight-chain saturated alkyl radical of 13 to 21, preferably 15 to 17 carbon atoms, and R is hydrogen or a hydrocarbyl radical of 1 to 22 carbon atoms or an N-methylene amide radical of the formula R -iiNHoII wherein R is an alkyl radical of 13 to 21 carbon atoms.
Some typical compounds that perform as very effective foam suppressors are N-alkyl acyl amides, e.g., N-methyl hexadecanamide, N-methyl octadecanamide, N-ethyl hexadecanamide, N-propyl heptadecanamide, N-octadecyloctadecanamide, N-phenyl hexadecanamide; the methylene-bis-amides, e.g., methylene-bis-octadecanamide, methylene-bis-hexadecanamide; the mixed methylene diamides, e.=g., those prepared from hydrogenated tallow acid amides and formaldehyde; acyl amides, e.g., tetradecanamide, hexadecanamide, heptadecanamide, octadecanamide, docosanamide; the mixed amides, e.g., hydrogenated tallow acid amides and hydrogenated fish acid amides.
The effective amount of this foam suppressor may range from about 2 to about 35% by weight, based on the active organic sulfate and/ or sulfonate in the detergent formulation, the preferred range being from about 5% to 15% by weight.
The anionic detergent component of the invention falls within the class of normally high foaming surface active materials which are the water-soluble salts of organic sulfonic acids and water-soluble salts of aliphatic sulfuric acid esters. In other words, synthetic detergents are contemplated which normally tend to produce much foaming before treatment and are the salts of organic sulfuric reaction products having in the molecular structure either a sulfonic or sulfuric ester radical. Ordinarily, for the purposes of laundering and dishwa-shing, sodium and potassium salts are used. On the other hand, ammonium and magnesium salts are preferred in certain specialized applications.
As more specific examples of satisfactory synthetic detergents, there can be mentioned the water-soluble salts of alkyl benzene sulfonates, particularly those in which the alkyl group is a polypropylene radical or other carbon-containing chain, e.g., a straight-chain radical, having an average of 8 to 15 carbon atoms; the water-soluble salts of alkyl surfuric acid, having 8 to 20 carbon atoms in the alkyl group; the water-soluble salts, such as the alkali metal salts of sulfuric acid esters of primary normal aliphatic alcohols containing 10 to 18 carbon atoms, such as lauryl and oleyl alcohol; secondary alkyl sulfates having pronounced detergent power and obtained from secondary alcohols or olefins. Other examples of the synthetic detergent components include the sulfuric acid esters which are the water-soluble salts of sulfuric acid esters of polyhydric alcohols incompletely esterified with high molecular weight soap-forming carboxylic acids, such as the water-soluble salts of sulfuric acid esters of higher molecular weight fatty acid monoglycerides, more specific examples being sodium glyceryl monolaurate sulfate and potassium glyceryl monopalmit-ate sulfate.
Specific types of anionic detergents are alkyl aryl sulfonates of 10 to 20 carbon atoms in the alkyl group, the alkyl benzene sulfonates containing an average from 9 to about 15 carbon atoms in the alkyl chain, and, in particular, the polypropylene benzene sulfonates of the kind described by A. H. Lewis in his US. Patent No. 2,477,383, being particularly satisfactory.
Other similar benzene sulfonates, such as keryl benzene sulfonates and the essentially straight-chain alkyl benzene sulfonates obtained by the alkylation of benzene with monochlorinated normal paraffins or with straight-chain olefins, can likewise be employed for the preparation of satisfactory low foam formulations.
Specific types of organic sulfate detergents are both primary and secondary alcohol sulfates, in which the' alkyl group contains from 10 to 20 carbon atoms. For pracical reasons and for improved deter-gency, the alkyl group of these sulfates is usually a mixture of alkyl groups having from 10 to 20 carbons present. Typical secondary sulfates are readily prepared by the reaction of an olefin and concentrated sulfuric acid, as disclosed, for example, in US. Patent 2,5 87,990. Primary sulfates, on the other hand, are prepared by the reaction of a primary alcohol and concentrated sulfuric acid, for example, as described in US. Patent No. 2,452,943.
Also contemplated are the water-soluble salts of sulfuric acid esters of the hydroxy ethers resulting from the reaction of an aliphatic alcohol and ethylene oxide. These compounds have the general formula:
wherein 21:8 to 20, x=1 to 6, preferably 3 to 6, and M is an alkali metal. A typical example is the sodium salt of lauryl ether of ethylene glycol monosulfuric acid.
Other types of detergents are the water-soluble salts of monosulfuric acid esters of the monoethers of high molecular weight aliphatic alcohols and glycerine. These compounds have the general formula:
wherein 12:8 to 20 and M is generally an alkali metal. A typical example is the sodium salt of monolauryl ether of rglycerine monosulfuric acid.
Still additional examples of sulfuric acid ester synthetic detergents are water-soluble salts of sulfated higher fatty acid alkanolamides, such as the sodium salt of sulfated coconut oil fatty acid ethanolamide, and the potassium salt of sulfated lauric isopropanolamide.
The nonionic surfactant component of the invention is well known and may be defined as the reaction product of ethylene oxide with a hydrophobic compound con- .taining a carbox-yl, mercapto, amido, amino or hydroxyl group. The properties of a nonionic can be modified by a simple change in proportions of ethylene oxide used. For example, the condensation products of ethylene oxide and C -C al-kyl phenol having fewer than about eight ethylene oxide units per molecule are more oil soluble, whereas those containing ten or more of such units are more water soluble.
A broad class of nonionics suitable in the practice of the present invention can be represented by the formula:
in which R is a hydrophobic radical such as a long paraffin chain of 8 to 20 carbon atoms, an alkylated aromatic group having a total of 12 to 20 carbon atoms, a long chain acyl group of 10 to 24 carbon atoms, or a polypropyleneoxy group; X is O, N or NH or S; m, a numeral from 1 to 50, and n is 1 or 2. An example of another class of nonionics is the type derived from a fatty acid, a polyhydric alcohol and ethylene oxide.
Some specific examples of nonionics are tripropylphenoxynonaethoxyethanol, tetrapropylphenoxyundecaethoxyethanol, diisobutylphenoxyheptaethoxyethanol, C (straightchain) alkylphenoxynonaethoxyethanol, dodecylphenoxyp-entaethoxyethanol, n dodecoxyundecaethoxyethanol, n-octadecylaminodi(heptaethoxyethanol), t-dodecylmercaptononaethoxyethanol, polyethylene glycol 600 monostearate, polyoxyethylated sorbitan trilaurate, polyoxyethylated sorbitan monooleate, N-polyoxyethylated tetradecanamide, N,N-di(polyoxyethylated) docosanamide, polyoxyethylated tall oil fatty acids, polyethoxypolypropox'ypolyethoxyethanol and dodecylphenoxytriacont-aethoxytetracontapropoxypropanol.
The amount of nonionic surfactant that can be present in compositions of the present invention ranges from about to 75%, preferably -25, by weight, based on anionic surfactant and nonionic combined.
In addition to the above detergent active materials, the present compositions may also contain auxiliary detergent agents, such as soap in amounts of, for example, 2 to 50% based on detergent components and amide. The fatty acid soap auxiliary detergent component may be any one of the several higher molecular weight saturated fatty acids, for example, sodium or potassium salts of fatty acids containing 14 to 22 carbon atoms.
The presence of conventional amounts of inorganic salt detergent builders, such as various water-soluble inorganic polyphosphates, sulfates, silicates, borates and carbonates, does not adversely affect the (foaming and detergent properties. These builders, the total amount of which may range by weight, based on finished com position, from about 45% to as high as 95%, but more usually between 75% and 85%, contribute their different specific effect toward a more satisfactory washing treatment Olf soiled clothing, dishes, etc. The same is true of the presence of small amounts, usually less than 5% by weight, based on final composition, of well known minor additives, such as toluene or xylene sulfonates, carboxymethyl cellulose, methyl cellulose, optical bleach and perfume.
Particularly useful are the phosphate builders. They can be used in their commercially available anhydrous form, obtained by the high-temperature dehydration of the orthophosphates-tripolyphosphates, from a mixture of disodium orthophosphate and monosodium orthophosphate; tetrasodi um pyrophosphates, lfrom disodium orthophosphates; and sodium polymetaphosphates, from orthophosphate. The various condensed phosphates can be used singly or in admixture. As is known in the detergent art, the proportions of the various phosphates are frequently altered in practice, and similar practice can prevail here. Generally, good results are obtained when tripolyphosph'ate is essentially the sole condensed phosphate, or is admixed with the other condensed phosphates, for example, tripolyphosphate and 20% pyrophosphate.
The mixing of the ingredients to obtain the compositions of the invention is not critical. One way is to mix foam-suppressing amide agent and nonionic, followed by heating to obtain a homogeneous mixture. This homogeneous mixture is then incorporated with the anionic surfactant. Preferably, the mixture of nonionic and amide is added to a slurry of the anionic so as to ensure intimate admixture. For example, in the preparation of alkyl benzene sulfonate, alkyl benzene sulfonic acid is mixed with caustic and a slurry is produced. To the slurry there can then be added the mixture of nonionic and amide, and the whole dried. Various inorganic salt detergent builders, such as the phosphates, can then be incorporated in conventional manner.
Inthe examples tabulated below, detergent compositions containing the foam suppressor were prepared by mixing the synthetic detergents and amide in the specified amounts. Unless otherwise indicated, the compositions contained in addition tetrasodium pyrophosphate (45% commercial grade N sodium silicate (8%), sodium car-boxymethyl cellulose (1% water (4%), and the bal ance, where required to bring the total weight to being sodium sulfate.
To determine the degree of foam inhibition and the detergent efiicacy of the compositions, foam heights were observed and measured in a :bench foam test. Foam level and detergency were also measured under simulated household-use conditions in a tumbler-type washing machine test.
In a representative bench test series, soft water (50 p.p.m. solutions of 0.25% concentration of test formulations were prepared, and aliquots of 1000 ml. were tested at temperatures of i10 F. This test consisted of mechanically stirring the test solution in a 2000 ml. beaker for one minute, and then measuring the foam height in mm. at 0, 1 and 10 minutes after the stirring was stopped. Foam heights of 7 mm. or less at 10 minutes are considered satlsfactory as shown by the following experiments and in the tables.
COMPARATIVE FOAM TEST Wt. Percent Bench Foam Washing Machine Ex. No. Oetadec- Height, mm. l oam anamiue l 3 0 No foam. 2 2 0 D0. 3 1 3 Little foam. 4 0.5 7 Maximum foam permissible. 0.2 13 Too much foam.
*In these experiments the indicated amounts of oetadecanamide were used in formulations made up as described above, namely 17% sodium polypropylene benzene snlfonate, 3% nonionic, 45% tetrasodium pyrophosphate, 8% sodium silicate, 1% carboxymethyl cellulose, 4% water, and su! lic1ent sodim sulfate to bring the total weight up to 100%. The nonionic was prepared from 13 mols of ethylene oxide and 1 mol of polypropylene phenol having an average molecular weight of 276.
The washing machine test above and in the following tables was carried out in the following manner: To a tumbler-type washing machine is charged 26 liters of water (50 ppm. hardness) at 120 F., containing 0.25%, by weight, of the test formulatlon. Then six pounds of shop towels, ten polyethylene sheets, several small soiled cotton swatches (for detergency measurements) and 1 gram of lard oil are added. The machine is started and the foam height, as viewed through the door window, is measured periodically over a 10 minute wash cycle. A failure is shown by any formulation having too much foam leading to a foam height greater than one-half of the height of The hardness of water as employed herein is defined in parts per million of calcium and magnesium, calculated as calcium carbonate and magnesium carbonate, in a weight ratio of 2: 1.
Percent soil removal: (A B (C B X 100 wherein A is reflectance of soiled swatch after washing and B is reflectance of soiled swatch before washing, and C is reflectance of swatch before soiling (see J. C. Harris, Detergency Evaluation and Testing, Interscience Publishers, Inc., New York, 1954, page 79).
The results of the tests are tabulated below.
In the tables below, identification of components used is as follows:
PPABS (348) is sodium polypropylene benzene sulfonate of 348 average molecular weight.
Nonionic A is water-soluble nonionic prepared from 13 mols of ethylene oxide and 1 mol of polypropylene phenol having an average molecular weight of 276.
PPABS (368) is sodium polypropylene benzene sulfonate of 368 average molecular weight.
Nonionic B is water-soluble nonionic prepared from 12 mols of ethylene oxide and 1 mol of dodecyl phenol.
Nonionic E is a condensation product of t-dodecy mercaptan with about 12 ethylene oxide units.
C1040 secondary sulfate is a sodium sulfate prepared from an approximately equimolar mixture of straightchain l-olefins of 10 through 20 carbon atoms and sulfuric acid.
Nonionic F is lauryl alcohol condensed with about 2.3 ethylene oxide units.
C alkylsulfonate is sodium-l-dodecyl sul-fonate.
Nonionic G is a commercial product (Sterox-CD) obtained by condensing tall oil fatty acids with ethylene oxide.
Nonionic H is a water-soluble nonionic prepared from 8 to 9 mols of ethylene oxide and alkyl phenol in which the alkyl group is an unbranched .hydrocarbyl radical of 7 through 11 carbon atoms.
Nonionic I is oil-soluble nonionic prepared from 6 mols of ethylene oxide and 1 mol of polypropylene phenol having an average molecular weight of 276.
Nonionic I is an ester of octadecanoic acid and polyethylene glycol of 600 average molecular weight.
Nonionic K is a polyether formed from polypropylene glycol having an average molecular weight of 1500-1 800 condensed with ethylene oxide to give a molecule containing about 80% ethylene oxide. 4
In Table I there is shown the desirability of the con joint presence of anionic surfactant, nonionic surfactant and foam suppressor.
TABLE L-FOAM AND DETERGENT EFFECTS OF ANIONIC-NONIONIC-AMIDE SYSTEMS Anionic Surfactant N onionic Surfactant Washing Ma hin Test Bench Foam No. Foam Suppressant Percent Height mm.
Name Percent Name Percent Foam Soil Removal,
Percent PPABS (348)- Too much 1 PPABS (348). 0.7 PPABS (348). 1 PPABS (348) PPABS (348) Octadecanamide; 1 None None do Octadecanamide 2 PPAB S (348) do 0. 5 PPABS (348) A commercial detergent with about 10% nonionic.
C1044 .SCABS is sodium alkylbenzene sulfonate in which the alkyl group is an unbranched hydrocarbyl radical of 10 through 14 carbon atoms.
Nonionic C is water-soluble nonionic prepared from i 8 to 9 mols of ethylene oxide and alkyl phenol in which -the alkyl group is an unbranched hydrocarbyl radical of mixture of hexadecyl and octadecyl and amine and 15 mols of ethylene oxide.
C1043 SCABS is sodium alkylbenzene sulfonate in which the alkyl group is an unbranched hydrocarbyl radi- 60 cal of 10 through 13 carbon atoms.
In Table I it is shown that for maximum effect it is essential that all three components of anionic surfactant, nonionic surfactant and amide be present.
Thus, anionic surfactant alone gives too much foam and poor soil removal (Test No. 1). Anionic surfactant with amide gives low foam but poor soil removal (Test No. 2). Nonionic alone or with amide gives low foam but poor soil removal (Tests Nos. 6 and 7). Anionic and nonionic without foam suppressor gives too high foam (Test No. 5). The presence of all three essential components gives satisfactory results (Tests Nos. 3, 4, 8 and 9). The results compare favorably with a commercial low foaming product based on nonionic (Test No. 10).
Table II illustrates the range of effective carbon chain length in the amide.
TABLE II.EFFECT OF VARYING CARBON CHAIN LENGTH OF AMIDE Anionic Surfactant Nonionic Surfactant Washing Machine Test Bench Foam No. Foam Suppressant Percent Height, mm.
Name Percent Name Percent Foam Soil Removal,
percent 11 Dodecanamide 3 PPABS (348) 18 l2 Tetradecanamide. 3 PPABS (348)-. 18 12A 0.- 3 PPABS (348) 18 13 Hexadecanamide 3 PPABS (348) 17 4. Ocatadecanamide 1 PPAB S (348) 15 Very little 14 Docosanamide 3 PPABS (348) 17 15 Octadecanamide, 2 PPABS (349) 18 Sat1sfactory 29 Hexadecanamide, 22%; Octadecenamide, 3%.
In Table II it is shown that a satisfactory amide compound is one containing at least 14 carbon atoms in the alkyl group. Dodecanamide has too few carbon atoms and, hence, is unsatisfactory (Test No. 11). Tetradecanamide and anionic without nonionic are unsatisfactory (Test No. 12A compared with Test No. 12). As shown already in Table I (Test No. 4), the higher amides are satisfactory (Tests Nos. 13, 14 and 15).
As indicated, the proportion of foam-suppressing amide is in the range of 2 to 35% by weight of the anionic surfactant component. This is illustrated in Table III.
An amount of amide below about 2% based on anionic surfactant gives poor foam results (Test No. 19). An amount of amide above 2% (Test No. 18) up to about 30% is shown to give good results (Tests Nos. 16, 17 and 20).
As already indicated, the type of anionic surfactant and 5 ture, as well as nonionics of various types, fall within the purview of the invention (Tests Nos. 4 and 21-30). Alkyl sulfates and alkyl sulfonates are also operative (Tests Nos. 31-36).
A number of amide compounds as described herein- 10 above can be used in the practice of the invention, as
demonstrated in Table V.
In Table V, compounds which do not fall within the formula for amide component are shown to be ineffective 15 (Tests Nos. 40-42).
Additional test results and data for different nonionic components are given in Table VI.
TABLE III.EFFECT OF CONCENTRATION OF AMIDE Anionic Surfactant N onionie Surfactant Test N0. Foam Suppressant Percent Bench Foam Height, mm. Name Percent Name Percent 16 Octadecanamide, 75%; 5 PPABS (348) 17 A 3 Hexadecanamide, 22%; Octadeeenamide 3'7 d 2 PPABS (348) 17 A 3 0 0.5 PPABS (348)- A 3 7 0. 2 PPABS (348) 17 A 3 13 IPABS (348) 35 A 3 1 TABLE IV.EFFECT OF VARYING ANIONIC AND NONIONIO DETERGENT Anionic Surfactant N onionic Surfactant Washing Machine Test Bench Foam N 0. Foam Suppressant Percent Height, mm.
Name Percent Name Percent Foam Soil Removal,
Percent 4 Octadecanamide 1 PPABS (348) 15 3 1 Very little. 30 2 PPABS (368).-- 15 3 Satisfactory 32 2 PPABS (368) 18 3 2 PPABS (36S) 18 3 C 14 SCABS V 2 1 010-14 SCABS 15 2 (111-10 SCABS 17 3 011-19 SCABS 17 3 O 5 01043 SCABSIn 18 2 ...d0 1 010-1 $011138. 17 3 n-Methyl hexadecan- 1 10-13 SCABS 10 3 amide. 31 None 010-20 sec. sultate 15 3 32 do 2 do 17 2 33 n-Methyl hexadecan- 2 d0 15 3 amide. 34 Octadecanamide 3 .do 17 2 35 None C12 alky1sulf0nate 15 2 36 Octadecanamide, 3 do 15 2 Hexadecanarnide, 22%; Octadecenamide, 3%.
TABLE V.EFFECT OF VARYING AMIDE TYPE Anionic Surfactant N onionie Surfactant Test N 0. Foam Suppressant Percent Bench Foam Height, mm. Name Percent N ame Percent 37 N-methyl hexadecanamide 2 PPABS (348) 15 6 0 38 N-phenyl octadecanamide 2 PPABS (348)- 15 3 6 Methylene-bis-octadecanamida 3 PPABS (348)- 15 3 0 N ,N-dimethyl octadecanamide 3 PPABS (348)- 18 3 34 N-octadecanoyl morpholide 3 PPABS (348) 18 3 32 4.. N,N-(fi-hydroxyethyl) 3 PPABS (348) 15 2 30 octadecanamide.
TABLE TL-EFFECT OF VARYING NONIONIC Anionic Surfactant Nonionic Surfactant Washing Machine Test Bench Foam No. Foam Suppressant Percent Height, mm.
Name Percent Name Percent Foam Soil Removal,
Percent PPABS (348) 17 Hexadecanamid 1 PPAB S (348) 17 Octadecanamide 1 PPAB S (348) 15 Satisfactory. 36 Octadecanamide, 75%; 2. 5 PPABS (368) 18 2 Very little 42 Hexadecanamide, 22%; Octadecenamide, 3%. Octadecanarnide 2 PPABS (368) 18 2 None C -1g SCABS 17 28 Octadecanamid Cllfls SCABS 17 3 Tetradecanamide PPABS (348) 12 4 do PPABS (348) 12 8 None PPABS (348)-. 5 9 O etadecanamide 0. 5 PPAB S (348) 5 The improved detergent formulations of this invention are suitable for use in dilute aqueous solutions in a variety of washing appliances, such as rotary drum or tumblertype washers, top-loading agitator washers, bottle washers, etc. When so employed, little or no foam is formed, without any adverse effect on the detergency characteristics, in operating at temperatures from about 65 to 140 F., as commonly used in washing practice. This suppression of suds in accordance with the invention permits employing a larger concentration of the active detergent in the preparation of washing solutions, as compared with the concentrations heretofore considered permissible maxima for tumbler-washer operations. A greater wash ing efliciency can therefore be achieved. Furthermore, the tendency to froth upon rinsing .is substantially obviated.
The effectiveness of the low foaming detergent formulations of the present invention can be used in tumblertype washers, as well as in any other washing equipment which utilizes strongly foaming organic detergent materials from the group of sulfates and sulfonates. In fact, these formulations can be employed to reduce foaming in a number of solutions and emulsions, which, upon agitation, produce unduly high suds, causing spillage, pumping difliculties and interfering with a satisfactory filling of containers.
This is a continuation-in-part of application Serial No. 261,501, filed February 27, 1963.
I claim:
1. A detergent composition having good detersive properties and characterized by a low degree of foaming in agitated dilute aqueous solutions thereof consisting essentially of a nonionic surfactant, a normally high foaming anionic detergent component selected from the group consisting of water-soluble salts of organic sulfonic acids and water-soluble salts of sulfuric acid alkyl esters, and to suppress foaming of said detergent component about 2 to 35%, by weight, of said detergent of a foamsuppressing agent of the formula:
wherein R is a saturated alkyl radical of 13 to 21 carbon atoms, and R is selected from the group consisting of hydrogen, a hydrocarbyl radical of 1 to 22 carbon atoms, and N-methyleneamide radicals, the alkyl group in the last-mentioned amide radical having 13 to 21 carbon atoms, the nonionic surfactant being present in an amount of to 75% by weight based on it and anionic detergent component.
2. A composition according to claim 1 wherein the foam-suppression agent is present in an amount of 5 to by weight based on the anionic detergent component.
3. A composition according to claim 2 wherein the anionic detergent component is an alkaryl sulfonate having 9 to carbon atoms in the alkyl group.
4. A composition according to claim 2 wherein the anionic detergent component is alkyl sulfate having 10 to 20 carbon atoms.
5. A detergent composition having good detersive properties and characterized by a low degree of foaming in agitated dilute solutions thereof consisting of (l) a normally high foaming anionic detergent component selected from the group consisting of water-soluble salts of organic sulfonic acids and water-soluble salts of sulfuric acid alkyl esters, (2) a nonionic surfactant, (3) to suppress foaming of said detergent about 2 to 35%, by weight, of said detergent of a foam-suppressing agent having the formula:
wherein R is a saturated alkyl radical of 13 to 21 carbon atoms, and R is selected from the group consisting of hydrogen, a hydrocarbyl radical of 1 to 22 carbon atoms, and Nmethyleneamide radicals, the alkyl group in the last-mentioned amide radical having 13 to 21 carbon atoms, and (4) inorganic detergent salt builders in an amount of 45 to by weight, based on said inorganic detergent builders and detergent component, the amount of nonionic surfactant being present in an amount of 5 to 75%, by weight, based on it and anionic detergent component.
6. A composition according to claim 5 wherein the nonionic surfactant is present in an amount of 10 to 25%.
7. A composition according to claim 5' wherein the anionic detergent component is an alkylaryl sulfonate having 9 to 20 carbon atoms in the alkyl group.
8. A composition according to claim 5 wherein the anionic detergent component is alkyl sulfate having 10 to 20 carbon atoms.
9. A composition according to claim 5 wherein the foam-suppressing agent is present in an amount of 5 to 15 weight percent based on the anionic detergent component.
10. A composition according to claim 9 wherein the foam-suppressing agent is present in an amount of 5 to 15 References Cited by the Examiner UNITED STATES PATENTS 2,588,343 3/1952 Bird et al 252-321 2,588,344 3/1952 Bird et al. 252-321 2,717,881 9/1955 Bird et al. 252321 2,961,410 11/1960 Martin 252 X 2,969,332 1/1961 Lawler et al 252321 X 3,022,250 2/ 1962 Grifo et al. 252---135 3,133,024 5/1964 Feierstein et al 252-135 LEON D. ROSDOL, Primary Examiner.
JULIUS GREENWALD, Examiner.
J. T. FEDIGAN, Assistant Examiner.

Claims (1)

1. A DETERGENT COMPOSITION HAVING GOOD DETERSIVE PROPERTIES AND CHARACTERIZED BY A LOW DEGREE OF FOAMING IN AGITATED DILUTE AQUEOUS SOLUTIONS THEREOF CONSISTING ESSENTIALLY OF A NOINOIC SURFACTANT, A NORMALLY HIGH FOAMING ANIONIC DETERGENT COMPONENT SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLE SALTS OF ORGANIC SULFONIC ACIDS AND WATER-SOLUBLE SALTS OF SULFURIC ACID ALKYL ESTERS, AND TO SUPPRESS FOAMING OF SAID DETERGENT COMPONENT ABOUT 2 TO 35%, BY WEIGHT, OF SAID DETERGENT OF A FOAMSUPPRESSING AGENT OF THE FORMULA:
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Cited By (19)

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US3953381A (en) * 1972-11-09 1976-04-27 Rhone-Progil Composition containing diamide and halocarbon for treatment of surfaces
US4123378A (en) * 1975-09-16 1978-10-31 Ciba-Geigy Ag Stain removing agents and process for cleaning and optionally dyeing textile material
US4497715A (en) * 1982-08-03 1985-02-05 Colgate-Palmolive Company N-Alkylisostearamides as antistatic agents
US4851138A (en) * 1986-09-02 1989-07-25 Akzo, N.V. Fabric softening composition and detergent-composition comprising the same
WO1992006150A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent compositions containing polyhydroxy fatty acid amide and alkyl benzene sulfonate
WO1992006162A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent containing alkyl sulfate and polyhydroxy fatty acid amide surfactants
US5174927A (en) * 1990-09-28 1992-12-29 The Procter & Gamble Company Process for preparing brightener-containing liquid detergent compositions with polyhydroxy fatty acid amines
US5194639A (en) * 1990-09-28 1993-03-16 The Procter & Gamble Company Preparation of polyhydroxy fatty acid amides in the presence of solvents
US5288431A (en) * 1992-06-15 1994-02-22 The Procter & Gamble Company Liquid laundry detergent compositions with silicone antifoam agent
US5332528A (en) * 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
US5338486A (en) * 1990-09-28 1994-08-16 The Procter & Gamble Company High catalyst process for glucamide detergents
US5338487A (en) * 1990-09-28 1994-08-16 The Procter & Gamble Company Catalyzed process for glucamide detergents
US5354425A (en) * 1993-12-13 1994-10-11 The Procter & Gamble Company Tissue paper treated with polyhydroxy fatty acid amide softener systems that are biodegradable
TR27215A (en) * 1990-09-28 1994-12-09 Procter & Gamble Detergent compositions containing polyhydroxy fatty acid amide and alkyl benzene sulfonate.
US5454982A (en) * 1990-09-28 1995-10-03 The Procter & Gamble Company Detergent composition containing polyhydroxy fatty acid amide and alkyl ester sulfonate surfactants
US5625098A (en) * 1991-07-26 1997-04-29 The Procter & Gamble Company Process for preparing N-alkyl polyhydroxyalkyl amines in aqueous/hydroxy solvents
US5700771A (en) * 1990-09-28 1997-12-23 The Procter & Gamble Company Polyhydroxy fatty acid amide surfactants in percarbonate bleach-containing compositions
US5723673A (en) * 1995-06-07 1998-03-03 The Procter & Gamble Company Process for preparing amides of N-alkyl polyhydroxyalkyls
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Publication number Priority date Publication date Assignee Title
US3953381A (en) * 1972-11-09 1976-04-27 Rhone-Progil Composition containing diamide and halocarbon for treatment of surfaces
US4123378A (en) * 1975-09-16 1978-10-31 Ciba-Geigy Ag Stain removing agents and process for cleaning and optionally dyeing textile material
US4497715A (en) * 1982-08-03 1985-02-05 Colgate-Palmolive Company N-Alkylisostearamides as antistatic agents
US4851138A (en) * 1986-09-02 1989-07-25 Akzo, N.V. Fabric softening composition and detergent-composition comprising the same
US5338486A (en) * 1990-09-28 1994-08-16 The Procter & Gamble Company High catalyst process for glucamide detergents
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US5174927A (en) * 1990-09-28 1992-12-29 The Procter & Gamble Company Process for preparing brightener-containing liquid detergent compositions with polyhydroxy fatty acid amines
US5194639A (en) * 1990-09-28 1993-03-16 The Procter & Gamble Company Preparation of polyhydroxy fatty acid amides in the presence of solvents
US5700771A (en) * 1990-09-28 1997-12-23 The Procter & Gamble Company Polyhydroxy fatty acid amide surfactants in percarbonate bleach-containing compositions
US5332528A (en) * 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
WO1992006150A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent compositions containing polyhydroxy fatty acid amide and alkyl benzene sulfonate
US5338487A (en) * 1990-09-28 1994-08-16 The Procter & Gamble Company Catalyzed process for glucamide detergents
US5454982A (en) * 1990-09-28 1995-10-03 The Procter & Gamble Company Detergent composition containing polyhydroxy fatty acid amide and alkyl ester sulfonate surfactants
TR27215A (en) * 1990-09-28 1994-12-09 Procter & Gamble Detergent compositions containing polyhydroxy fatty acid amide and alkyl benzene sulfonate.
WO1992006162A1 (en) * 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent containing alkyl sulfate and polyhydroxy fatty acid amide surfactants
US5625098A (en) * 1991-07-26 1997-04-29 The Procter & Gamble Company Process for preparing N-alkyl polyhydroxyalkyl amines in aqueous/hydroxy solvents
US5288431A (en) * 1992-06-15 1994-02-22 The Procter & Gamble Company Liquid laundry detergent compositions with silicone antifoam agent
US5354425A (en) * 1993-12-13 1994-10-11 The Procter & Gamble Company Tissue paper treated with polyhydroxy fatty acid amide softener systems that are biodegradable
US5723673A (en) * 1995-06-07 1998-03-03 The Procter & Gamble Company Process for preparing amides of N-alkyl polyhydroxyalkyls
US5777165A (en) * 1995-06-07 1998-07-07 The Procter & Gamble Company Process for preparing amides of N-alkyl polyhydroxyalkyl amines

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