US2746931A - Synthetic detergent compositions - Google Patents

Synthetic detergent compositions Download PDF

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US2746931A
US2746931A US124514A US12451449A US2746931A US 2746931 A US2746931 A US 2746931A US 124514 A US124514 A US 124514A US 12451449 A US12451449 A US 12451449A US 2746931 A US2746931 A US 2746931A
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additives
alcohols
detergent
carbon atoms
water
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US124514A
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Peter T Vitale
Liftin Muriel Eileen
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Colgate Palmolive Co
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Colgate Palmolive Co
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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
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/201Monohydric alcohols linear
    • C11D3/2013Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
    • 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
    • C11D1/38Cationic compounds
    • C11D1/65Mixtures of anionic with cationic compounds
    • C11D1/655Mixtures of sulfonated products with alkylolamides of carboxylic acids
    • 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
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2044Dihydric alcohols linear
    • 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
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • 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
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28Sulfonation products derived from fatty acids or their derivatives, e.g. esters, 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
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/521Carboxylic amides (R1-CO-NR2R3), where R1, R2 and R3 are alkyl or alkenyl groups
    • 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
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group

Definitions

  • the present invention relates to new synthetic detergent compositions and, more particularly, to compositions of the type of the alkyl aromatic sulfonate detergents having improved foaming and deterging characteristics, as hereinafter described and claimed.
  • additives have been incorporated in a wide range of concentrations to modify the properties of synthetic detergent compositions in a desired manner. These additives individually may affect one or more of the following properties or mechanisms involved in the action of the detergent composition including foaming, foam stability, dispersion, suspension, interfacial tension, modification of micellar structure, etc. In view of the varied nature of the many synthetic detergents, additives in general exhibit a certain degree of specificity of action.
  • the detergent composition should exhibit excellent foaming properties, particularly for consumer appeal and certain home and industrial uses.
  • Additives which improve one or more properties of a detergent mixture without adverse affect on other properties are desirable whereas the use of additives which exhibit adverse effects, or even both desirable and adverse effects, would appear to be contraindicated.
  • the present invention relates to a detergent composition
  • a detergent composition comprising from about 10 to 50% of water-soluble higher alkyl mononuclear aryl sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher aliphatic alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula specified herein,
  • alkyl mononuclear aromatic sulfonate detergents referred to are well known in the art. More particularly, the aromatic nucleus may be derived from benzene, toluene, xylene, phenol, cresols, phenol ethers, etc. It has also been found that the alkyl group may vary similarly. Thus, for example, the alkyl group may consist of such radicals as dodecyl, hexyl, octyl, nonyl, decyl, keryl, mixed alkyls derived from fatty materials,
  • Typical examples of this class are the sulfonated and alkylated benzene type compounds wherein the alkyl group contains at least about 8 and preferably about 10 to about 16 carbon atoms.
  • the benzene ring may possess other substituents including lower alkyl and hydroxy groups.
  • detergents are commonly used in the form of their water soluble salts.
  • the alkali metal (e. g. sodium, potassium) and ammonium salts are preferred though other salts such as the amine, alkylolamine and alkaline earth metal (e. g. calcium, magnesium) salts may be used if desired.
  • Their concentration in the detergent compositions of the present invention is generally at least 10 and preferably at least about 20% by weight of total solids. With built compositions however, it is preferred to use an active ingredient content of about 20 to about 50% concentration.
  • the aliphatic alcohols used as additives in the present invention are the monohydric and dihydric alcohols of about 12 to 18 carbon atoms.
  • the monohydric alcohols may be primary or secondary; and saturated or unsaturated in character.
  • the saturated straight chain primary alcohols of about 14 to about 18 and more particularly 16 carbon atoms.
  • suitable fatty alcohols are lauryl, myristyl, cetyl, stearyl, palmityl, oleyl alcohols and mixtures thereof, etc. It is not necessary to use the pure substances themselves as the commercial mixtures of these fatty alcohols are also operable and are included within the scope of this invention.
  • the polyhydric alcohols are preferably the diols having a straight chain of about 14-18 carbon atoms and containing adjacent and essentially terminal hydroxyl groups.
  • These aliphatic glycols may have straight or branched chains, and may be saturated in structure.
  • Such diols having branched chains may be suitably employed provided that they are only mildly branched, such that there remains a long straight chain hydrophobic portion in the molecule. It is preferred to use the alkane diols having adjacent hydroxyl groups at a terminal of the linear chain generally.
  • glycols falling within the broad classification are hexadecane 1,2 diol, tetradecane 1,2 diol, octadecane 1,2 diol, dodecane 1,2 diol, hexadecane 2,3 diol, and mixtures thereof, etc. Commercial mixtures of these substances may also be employed with satisfactory results.
  • the monohydric alcohols may be recovered from many fats, oils and waxes of animal, vegetable, or marine origin. The most plentiful means for their production, however, are their synthetic prepa ration from fatty acids, esters, or aldehydes by reduction; or their recovery from oxidized petroleum stocks, etc.
  • the polyhydric alcohols may generally be obtained from cracked paraifin waxes, by oxidation of corresponding long chain olefins, etc.
  • the amides to be used in conjunction with the higher fatty alcohols are preferably the surface-active higher amides having the formula:
  • R-GON wherein R-CO- is an aliphatic acyl radical, preferably of a higher fatty acid, having from about 10 to 20, and preferably about 12 to 16 carbon atoms, and X and Y may each be selected from the group consisting of hydrogen and alkylol radicals having from about 1 to about 5 carbon atoms each, and preferably about two carbon atoms.
  • the acyl radical be about 14 carbon atoms.
  • the monoalkylolamides it is preferred that the acyl radical have about 10 to 16 carbons, whereas with the dialkylolamides, acyl radicals of slightly longer chain length of about 12 to 20 carbon atoms are preferred generally.
  • amides which come within the scope of the invention are myristamide, lauramide, stearamide, myristylethanolamide, palmitylethanolamide, lauric di-ethanolamide, and amide type mixtures prepared from mixtures of higher fatty acids derived from various fats, oil and waxes of animal, vegetable or marine origin.
  • additives may be incorporated either together or separately with the active ingredient at any point during the manufacturing process at which subsequent operations willnot adversely modify the properties of the detergent composition.
  • this addition may be accomplished by adding the alcohols and amides to the active ingredient either in liquid form, or by mixing those materials which are solid under normal conditions in comminuted form. The best results are not achieved by mechanically intermixing the comminuted solid components.
  • a variety of procedures, which have proven to be convenient, economical and productive of the best results are:
  • the higher alcohols and amides may be dissolved in a suitable solvent, e. g. ethanol, and added to a slurry of the active ingredient.
  • a suitable solvent e. g. ethanol
  • a cream emulsion of the higher alcohols and amides in water with a minor proportion of the active ingredient may be prepared and incorporated in the manner set forth above.
  • compositions may be made up in the form of solutions, pastes, or as a dry or partially hydrated solid product, preferably in a finely divided condition.
  • the amount of these added long chain alcohols and amides is generally minor in proportion to the weight of the total detergent composition and sufficient to produce a marked effect on its foaming and detergency properties.
  • the amount of each additive varies within rather definite proportions of the order of about 1 to about 10 by weight since it has been determined that within these somewhat critical limits the desirable efiects appear to be attained to a maximum degree. The best results are attained by the use of concentrations within the range of 1-5% of each of the organic additives, particularly for built compositions.
  • the novel and improved detergent compositions referred to herein generally exhibit increased stability of the foam produced in washing operations, in comparison to the foaming effects produced by the use of either the alcohols or amides alone in these detergent compositions.
  • the fact that the mixed additives in the particular relationship set forth produce foams and suds which are more stable, do not readily break down by evaporation, have in general a longer drainage time and contain more liquid are significant and desirable properties for a detergent composition.
  • the total washingpower of any composition is necessarily the result of the amount of soil removal and soil suspension or redeposition.
  • Additives in general may increase both soil removal and redeposition, or may only increase one such factor and inhibit the other. It has been found however that the mixed additives in the compositions referred to herein have the desirable properties of increasing soil removal markedly with no apparent increase and even some inhibition in soil redeposition.
  • the unitary effect on detergency resulting from a concurrent activation of one factor and non-activation of another is achieved by the mutual cooperation of the fatty alcohols and amides since the improvement may be synergistic in character.
  • a pour foam test designed for comparative study of the relative foam stability of liquids and an appropriate apparatus for carrying out the test is set forth in UnitedStates Patent No. 2,315,983 to Ross and Miles.
  • the foam height in millimeters of solutions tested in accordance with the Ross and Miles patent is read at various time intervals and is an indication of the foam stability.
  • the pour foam test is repeated in distilled water using a detergent composition comprising essentially 40% salts of higher alkyl benzene sulfonates, 12.5% 'trisodium phosphate, 12.5% sodium silicate and the remainder sodium sulfate with palmitylethanolamide and hexadecane 1,2 diol, as the organic additives:
  • the improvement in detergency using the mixed organic additives according to the present invention is a significant feature of this invention. Washing tests indicate that the mixed organic additives have the desirable property of increasing the soil removal of the alkyl aryl sulfonate detergent systems markedly without an adverse effect on soil redeposition. Thus, at 0.5% concentration of the detergent composition in hard water of 300 P. P.
  • Table IV sets forth the results of a standard soil removal test at 120 F. in hard water on cotton fabrics by a higher alkyl aryl sulfonate composition having a high trisodium phosphate, sodium silicate and sulphate formulation.
  • soiled cotton swatches are measured by a Hunter reflectometer before and after washing.
  • the units in the table are the reflectance readings of actual whiteness. The higher the reading the better is the washing power.
  • Comparable results using the mixed additives may be attained in soft water also.
  • the improvements effected by the mixed additives are all the more unusual since at other washing concentrations (e. g. 0.15%) decreased detergency may result from the use of the mixed additives in alkyl aryl sulfonate compositions.
  • Table V sets forth the results of standard soil removal tests on woolen fabrics. In these tests, wool swatches are soiled and washed as uniformly as possible at F. with various detergent compositions in 0.5 concentration in soft water of about 50 P. P. M. hardness.
  • the light reflectance of the soiled woolen samples before and after washing as measured by a Hunter reflectometer is an indication of the amount of soil removed, expressed in Hunter units X 10
  • the standard composition used in these tests comprises about 40% sodium salts of higher alkyl aryl sulfonates wherein the alkyl group averages 9-14 carbon atoms, 40% sodium tri-polyphosphate and 20% sodium sulfate. Wherever organic additives are indicated in Table V, they replace a corresponding amount of sodium sulfate.
  • adjuvant materials may be employed in synthetic detergent compositions. These builders 0r additives may be inorganic or organic in structure, and may be admixed with the active ingredient in any suitable manner. Such adjuvant materials may include any of the substances employed by the art in admixture with sulfonated organic detergents generally, provided the use of any such materials does not neutralize or remove the effectiveness of the mixed higher alcohols and higher amides. It has been found that these added materials may vary greatly both in structure and in concentration Without impairing the improved results of the compositions referred to herein.
  • alkali metal phosphates e. g. hexametaphosphate, tetrapyrophosphate
  • alkali metal sulfates carbonates, etc.
  • Organic materials such as carboxymethylcellulose, :esters (e.. g. ethylene glycol monostearate, methyl palmitate), and the like may also be used under suitable conditions.
  • the polyphosphates are preferably the water soluble inorganic tri-polyphosphates of the formula:
  • MsPaOro M representing an alkali metal or ammonium group.
  • the actions of the tri-polyphosphate and the mixed organic additives in these detergent compositions are not only not antagonistic, but mutually contribute to a balanced detergency system such that a unitary result of vastly improved detergency is achieved thereby.
  • the effect of the mixed organic additives is primarily one of activation of the soil removal power of aromatic sulfonate detergent compositions without any apparent adverse effect, or even a moderate inhibition of the amount of soil redeposition. It has been determined, however, that the tri-polyphosphates appear to exert beneficial results in an opposite direction in these detergency systems. The tri-polyphosphates exhibit their greatest effect on soil suspension or prevention of soil redeposition, and only to a minor extent on the soil removal factor.
  • washing frmulaeper cent composition soil removal and soil redeposition values are determined in hard water in a standard manner involving the use of natural soil on cotton textile items commonly used in the household.
  • the results of these tests using composition I as a standard for comparative purposes are set forth in Table VI.
  • the numbers in the table represent the percent change in soil removal and redeposition effected by compositions II and III from the standard. A plus value indicates the desirable effects of an increase in soil removal and decrease in the amount of redeposited soil; a minus value indicates a decrease in soil removal and increased redeposition of soil.
  • composition II containing the mixed organic additives with tri-polyphosphate is evident from the data.
  • Composition III containing tetrasodiumpyrophosphate gives some improvement in soil removal but has an adverse effect on soil redeposition; whereas composition II exhibits a marked improvement in soil removal and an equivalent inhibition in soil redeposition.
  • the tri-polyphosphates may be used in any desired proportion. To some extent the degree of improvement appears to be proportional to its content in the composition. In general, the greater the percentage of tri-polyphosphate, the better the result where the active ingredient has been maintained constant. It has been found that best results are attainable when the ratio of tri-polyphosphate to the aromatic active ingredient is at least about 1:1. For maximum efliciency of these compositions, the active ingredient should be present in an amount at least about 20% by weight of the total composition.
  • a proportion of active ingredient from about 20% to up to about 50% with a similar proportion of the tri-polyphosphate and a minor amount of the higher alcohols and amides produces sufiicient detergent properties for even heavily-soiled laundry; and such composition is economical to prepare and convenient for use in the home or commercially.
  • the tri-polyphosphates may be incorporated with the active ingredient in any suitable manner. It is possible to mechanically intermix these constituents in the form of small solid particles. However, it is preferred to apply the techniques set forth above for the introduction of the higher alcohols and amides. Thus, the tri-polyphosphate may be added to a slurry of the active ingredient before, during or after incorporation of the organic additives. The resulting mixture may be dried in any convenient manner, e. g.- roll or spray dried. Excessively high temperatures during drying should be avoided however to prevent substantial decomposition of the polyphosphates.
  • compositions containing the mixed organic additives with and without the tri-polyphosphates productive of the improved results achieved by the present invention are additional examples of compositions containing the mixed organic additives with and without the tri-polyphosphates productive of the improved results achieved by the present invention:
  • the diols may well be much more desirable than the monohydric alcohols in the relationship set forth.
  • the amount of monohydric alcohols should be kept within reasonable limits as it must be remembered that they, together with the amides, are adjuncts for the active ingredient salt.
  • the amount of monohydric alcohols would preferably be not more than about in compositions containing about 20 to about 50% active ingredient. In compositions containing about 50% active ingredient, 510% monohydric alcohols may be used with better results than obtained by the use of the same concentration of the alcohols in compositions containing about 20% active ingredient.
  • a detergent composition comprising from about to 50% by weight of water-soluble higher alkyl mononuclear aryl sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher aliphatic alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula:
  • RCO is an aliphatic acyl radical of about 10 to 20 carbon atoms
  • X and Y are each selected from the group consisting of hydrogen and alkylol radicals having up to 5 carbon atoms, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts.
  • a detergent composition comprising about 10 to 50% by weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher fatty alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula:
  • RCO- is a higher fatty acyl radical of about 12 to 16 carbon atoms
  • X and Y are each selected from the group consisting of hydrogen and alkylol radicals of up to 5 carbon atoms, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts.
  • a detergent composition comprising about 10 to 5 0% by weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to 10% of each by weight of a saturated monohydric fatty alcohol of 12 to 18 carbons and a higher fatty acyl primary amide having 10 to 14 carbon atoms in the acyl group, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts.
  • a detergent composition comprising about 10 to 50% by weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to 10% of each by weight of a saturated monohydric fatty alcohol of 12 to 18 carbons and a higher fatty acyl monoalkylolamide having 10 to 16 carbon atoms in the acyl group and up to 5 carbons in the alkylol group, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts.
  • a detergent composition comprising from about 10 to 50% by weight of water-soluble higher alkyl mononuclear aryl sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher aliphatic alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula:
  • RCO- is an aliphatic acyl radical of about 10 to 20 carbon atoms
  • X and Y are each selected from the group consisting of hydrogen and alkylol radicals having up to 5 carbon atoms, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts with about 20% to about 50% by weight water-soluble inorganic tripolyphosphate builder salt.
  • a detergent composition comprising about 10 to 50% by weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher fatty alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula:
  • R-CO- is a higher fatty acyl radical of about 12 to 16 carbon atoms
  • X and Y are each selected from the group consisting of hydrogen and alkylol radicals of up to 5 carbon atoms, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts with about 20% to about 50% by weight sodium tripolyphosphate salt.
  • a detergent composition comprising about 10 to 50% by Weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by Weight of a higher aliphatic glycol of about 12 to 18 carbon atoms and a higher amide compound having the formula:

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Description

SYNTHETTC DETERGENT COMPOSITIONS Peter T. Vitale and Muriel Eileen Liftin, Brooklyn, N. Y., assignors to Colgate-Palmolive Company, Jersey City, N. J., a corporation of Delaware No Drawing. Application October 29, 1949, Serial No. 124,514
9 Claims. (Cl. 252-137) The present invention relates to new synthetic detergent compositions and, more particularly, to compositions of the type of the alkyl aromatic sulfonate detergents having improved foaming and deterging characteristics, as hereinafter described and claimed.
Various additives have been incorporated in a wide range of concentrations to modify the properties of synthetic detergent compositions in a desired manner. These additives individually may affect one or more of the following properties or mechanisms involved in the action of the detergent composition including foaming, foam stability, dispersion, suspension, interfacial tension, modification of micellar structure, etc. In view of the varied nature of the many synthetic detergents, additives in general exhibit a certain degree of specificity of action.
While the exact relationship, if any, between detergency and foam is not known, it is preferred that the detergent composition should exhibit excellent foaming properties, particularly for consumer appeal and certain home and industrial uses. Additives which improve one or more properties of a detergent mixture without adverse affect on other properties are desirable whereas the use of additives which exhibit adverse effects, or even both desirable and adverse effects, would appear to be contraindicated.
It has now been discovered, that the simultaneous presence of higher aliphatic alcohols and of the higher aliphatic amide type compounds in minor proportions in synthetic detergent compositions of the alkyl aryl sulfonate type give improved foaming and deterging properties to such compositions. These improvements are unique since these additives by themselves have neither foaming nor deterging properties. Moreover, these improvements are generally of a synergistic nature. More particularly, the present invention relates to a detergent composition comprising from about 10 to 50% of water-soluble higher alkyl mononuclear aryl sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher aliphatic alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula specified herein,
and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts.
It is significant that the improvement in either the foaming or deterging properties of compositions of the present invention is generally accompanied simultaneously with a significant increase in the other property, since then the two major factors (foam and detergency) in the production of a successful synthetic detergent are activated concurrently.
The higher alkyl mononuclear aromatic sulfonate detergents referred to are well known in the art. More particularly, the aromatic nucleus may be derived from benzene, toluene, xylene, phenol, cresols, phenol ethers, etc. It has also been found that the alkyl group may vary similarly. Thus, for example, the alkyl group may consist of such radicals as dodecyl, hexyl, octyl, nonyl, decyl, keryl, mixed alkyls derived from fatty materials,
by Weight cracked parafiin wax olefins, and polymers of lower mono olefins, etc. While the number of sulfonic acid groups present on the nucleus may vary, it is usual to have only one such group present in order to preserve as much as possible a balance between hydrophobic portions of the molecule.
Typical examples of this class are the sulfonated and alkylated benzene type compounds wherein the alkyl group contains at least about 8 and preferably about 10 to about 16 carbon atoms. The benzene ring may possess other substituents including lower alkyl and hydroxy groups.
These detergents are commonly used in the form of their water soluble salts. Of these, the alkali metal (e. g. sodium, potassium) and ammonium salts are preferred though other salts such as the amine, alkylolamine and alkaline earth metal (e. g. calcium, magnesium) salts may be used if desired. Their concentration in the detergent compositions of the present invention is generally at least 10 and preferably at least about 20% by weight of total solids. With built compositions however, it is preferred to use an active ingredient content of about 20 to about 50% concentration.
The aliphatic alcohols used as additives in the present invention are the monohydric and dihydric alcohols of about 12 to 18 carbon atoms. The monohydric alcohols may be primary or secondary; and saturated or unsaturated in character. Of the monohydric alcohols, it is preferred to use the saturated straight chain primary alcohols of about 14 to about 18 and more particularly 16 carbon atoms. Examples of suitable fatty alcohols are lauryl, myristyl, cetyl, stearyl, palmityl, oleyl alcohols and mixtures thereof, etc. It is not necessary to use the pure substances themselves as the commercial mixtures of these fatty alcohols are also operable and are included within the scope of this invention.
The polyhydric alcohols are preferably the diols having a straight chain of about 14-18 carbon atoms and containing adjacent and essentially terminal hydroxyl groups. These aliphatic glycols may have straight or branched chains, and may be saturated in structure. Such diols having branched chains may be suitably employed provided that they are only mildly branched, such that there remains a long straight chain hydrophobic portion in the molecule. It is preferred to use the alkane diols having adjacent hydroxyl groups at a terminal of the linear chain generally. Examples of suitable glycols falling within the broad classification are hexadecane 1,2 diol, tetradecane 1,2 diol, octadecane 1,2 diol, dodecane 1,2 diol, hexadecane 2,3 diol, and mixtures thereof, etc. Commercial mixtures of these substances may also be employed with satisfactory results.
These long chain aliphatic alcohols may be obtained in any suitable manner. The monohydric alcohols may be recovered from many fats, oils and waxes of animal, vegetable, or marine origin. The most plentiful means for their production, however, are their synthetic prepa ration from fatty acids, esters, or aldehydes by reduction; or their recovery from oxidized petroleum stocks, etc. The polyhydric alcohols may generally be obtained from cracked paraifin waxes, by oxidation of corresponding long chain olefins, etc.
The amides to be used in conjunction with the higher fatty alcohols are preferably the surface-active higher amides having the formula:
R-GON wherein R-CO- is an aliphatic acyl radical, preferably of a higher fatty acid, having from about 10 to 20, and preferably about 12 to 16 carbon atoms, and X and Y may each be selected from the group consisting of hydrogen and alkylol radicals having from about 1 to about 5 carbon atoms each, and preferably about two carbon atoms. With the non-alkylol containing amides, it is preferred that the acyl radical be about 14 carbon atoms. With the monoalkylolamides, it is preferred that the acyl radical have about 10 to 16 carbons, whereas with the dialkylolamides, acyl radicals of slightly longer chain length of about 12 to 20 carbon atoms are preferred generally. Specific examples of amides which come Within the scope of the invention are myristamide, lauramide, stearamide, myristylethanolamide, palmitylethanolamide, lauric di-ethanolamide, and amide type mixtures prepared from mixtures of higher fatty acids derived from various fats, oil and waxes of animal, vegetable or marine origin.
These additives may be incorporated either together or separately with the active ingredient at any point during the manufacturing process at which subsequent operations willnot adversely modify the properties of the detergent composition. In general, this addition may be accomplished by adding the alcohols and amides to the active ingredient either in liquid form, or by mixing those materials which are solid under normal conditions in comminuted form. The best results are not achieved by mechanically intermixing the comminuted solid components. A variety of procedures, which have proven to be convenient, economical and productive of the best results are:
(1) The addition of the higher alcohols and amides in a molten state to a hot aqueous slurry of the active ingredient of about to 50% concentration with vigorous stirring to form a smooth uniform and homogeneous paste.
(2) The higher alcohols and amides may be dissolved in a suitable solvent, e. g. ethanol, and added to a slurry of the active ingredient.
(3) A cream emulsion of the higher alcohols and amides in water with a minor proportion of the active ingredient may be prepared and incorporated in the manner set forth above.
Thereafter, these compositions may be made up in the form of solutions, pastes, or as a dry or partially hydrated solid product, preferably in a finely divided condition.
The amount of these added long chain alcohols and amides is generally minor in proportion to the weight of the total detergent composition and sufficient to produce a marked effect on its foaming and detergency properties. Generally, the amount of each additive varies within rather definite proportions of the order of about 1 to about 10 by weight since it has been determined that within these somewhat critical limits the desirable efiects appear to be attained to a maximum degree. The best results are attained by the use of concentrations within the range of 1-5% of each of the organic additives, particularly for built compositions.
From the viewpoint of foaming generally, the novel and improved detergent compositions referred to herein generally exhibit increased stability of the foam produced in washing operations, in comparison to the foaming effects produced by the use of either the alcohols or amides alone in these detergent compositions. The fact that the mixed additives in the particular relationship set forth produce foams and suds which are more stable, do not readily break down by evaporation, have in general a longer drainage time and contain more liquid are significant and desirable properties for a detergent composition.
Moreover, it has been found that in generai the mixed additives tend to increase the tolerance of these detergent compositions in the assimilation or holding in suspension of a maximum amount of dirt, grease, etc. with decreased foam loss than is found from the use of these additives individually.
With respect to detergency, it may be noted that the total washingpower of any composition is necessarily the result of the amount of soil removal and soil suspension or redeposition. Additives in general may increase both soil removal and redeposition, or may only increase one such factor and inhibit the other. It has been found however that the mixed additives in the compositions referred to herein have the desirable properties of increasing soil removal markedly with no apparent increase and even some inhibition in soil redeposition. The unitary effect on detergency resulting from a concurrent activation of one factor and non-activation of another is achieved by the mutual cooperation of the fatty alcohols and amides since the improvement may be synergistic in character.
These results are evident from a consideration of the following data and examples described hereinafter which are merely illustrative of the present invention, and it will be understood that the invention is not limited thereto.
The effect on the foaming characteristics can be studied quantitatively for a given composition. A pour foam test designed for comparative study of the relative foam stability of liquids and an appropriate apparatus for carrying out the test is set forth in UnitedStates Patent No. 2,315,983 to Ross and Miles. The foam height in millimeters of solutions tested in accordance with the Ross and Miles patent is read at various time intervals and is an indication of the foam stability.
Using a 0.25% concentration of a detergent composition (35% salts of higher alkyl benzene sulfonates, tetrasodium pyrophosphate, 3% sodium silicate, 12% sodium sulfate) and varying the organic additive content only, tests at 110 F. in water of 300 parts per million (p. p. m.) hardness give the following results:
These organic additives individually have an adverse effect on foam. Thus, it may be noted from Table 1 that with the single additives, foam breakdown occurred at 10 minutes, whereas the mixed additives exhibited very good foam stability for 10 and 15 minute periods. In soft water, the improvement attained by the mixed additives is also significant using the above composition and best results are similarly attained using at least a 1:1 ratio of alcohol to amide.
The pour foam test is repeated in distilled water using a detergent composition comprising essentially 40% salts of higher alkyl benzene sulfonates, 12.5% 'trisodium phosphate, 12.5% sodium silicate and the remainder sodium sulfate with palmitylethanolamide and hexadecane 1,2 diol, as the organic additives:
TABLE II Organic Additives g i 4% Palmitylethanolamide 215 1 135490 2-? 2% Hexadeeane 1,2 diol l 210 0 200 200 2% Hexadecaue 1,2 diol 2% Palinitylethanolarnide 220 220 220 I 2'20 min. min. min.
1% Mix 220 220 220 Mix 240 240 230 3% Mix 215 210 210 4% Mix... 220 215 215 2:1 MIX OF CETYL ALCOHOL AND MYRISTAIVIIDE 2% hIiX... 245 245 245 3% Mix... 240 220 220 1:1 h/[IX OF HEXADEOANE 1,2 DIOL AND PALlVIIIYLETH- ANOLAMIDE 1% Mix... 240 240 240 2% Mix 235 235 230 3% Mix 230 230 225 4% lVIix 230 215 1 90-2l0 Oolumn was not completely filled with foam between these two heights.
Similarly, improved results are obtained generally in soft water also. Thus, the above composition containing a 1:2 mix of cetyl alcohol and palmitylethanolamide gives excellent foam stability (205-215 mm. at 15 minutes) in soft water. The composition having a 2:1 mix of cetyl alcohol and myristamide gives a breakdown at 15 minutes in soft water (100-210 mm.). The foam height, however, is still superior to the same composition using cetyl alcohol as the sole organic additive.
The significance of these various data is more striking when the general adverse effect of the alchols on the foam properties of the alkyl aryl sulfonate detergents is reviewed briefly. With the basic composition used in the tests for Table III and the alcohols as the sole organic additives, marked foam breakdown generally occurs at the 10-15 minute intervals in soft water. The foam height with the monohydric alcohols is generally less than 100 mm. at 15 minutes. These effects may be noted specifically with stearyl alcohol, cetyl alcohol, lauryl alcohol, Lorol (mixed alcohols derived from coconut oil), mixed cetyl-stearyl alcohols, mixed cetyl-Lorol alcohols, mixed cetyl-oleyl, etc. The diols as the sole organic additives, however, exhibit relatively good stability, particularly in soft water.
As previously indicated, the improvement in detergency using the mixed organic additives according to the present invention is a significant feature of this invention. Washing tests indicate that the mixed organic additives have the desirable property of increasing the soil removal of the alkyl aryl sulfonate detergent systems markedly without an adverse effect on soil redeposition. Thus, at 0.5% concentration of the detergent composition in hard water of 300 P. P. M., it is found that the addition of 1% cetyl alcohol and 2% palmitylethanolamide in a higher alkyl benzene sulfonate detergent compsition having a high tri-polyphosphate and low sodium sulphate formulation increases soil removal on standard cotton fabrics about 12%, Whereas the amount of soil redeposition appeared to be about constant or within the margin of experimental error.
This improvement in detergency may be of a synergistic order as evidenced by the data in Tables IV and V.
Table IV sets forth the results of a standard soil removal test at 120 F. in hard water on cotton fabrics by a higher alkyl aryl sulfonate composition having a high trisodium phosphate, sodium silicate and sulphate formulation. In this test, soiled cotton swatches are measured by a Hunter reflectometer before and after washing. The units in the table are the reflectance readings of actual whiteness. The higher the reading the better is the washing power.
Comparable results using the mixed additives may be attained in soft water also. The improvements effected by the mixed additives are all the more unusual since at other washing concentrations (e. g. 0.15%) decreased detergency may result from the use of the mixed additives in alkyl aryl sulfonate compositions.
It is also significant that a marked and synergistic improvement in detergency may be effected in the washing of textile items other than cotton fabrics. Thus, Table V sets forth the results of standard soil removal tests on woolen fabrics. In these tests, wool swatches are soiled and washed as uniformly as possible at F. with various detergent compositions in 0.5 concentration in soft water of about 50 P. P. M. hardness. The light reflectance of the soiled woolen samples before and after washing as measured by a Hunter reflectometer is an indication of the amount of soil removed, expressed in Hunter units X 10 The standard composition used in these tests comprises about 40% sodium salts of higher alkyl aryl sulfonates wherein the alkyl group averages 9-14 carbon atoms, 40% sodium tri-polyphosphate and 20% sodium sulfate. Wherever organic additives are indicated in Table V, they replace a corresponding amount of sodium sulfate.
TABLE V Units of Soil Organic Additive o ed The improved detergency resulting from the use of the mixed organic additives in the relationship set forth is self-evident from the data.
Various adjuvant materials may be employed in synthetic detergent compositions. These builders 0r additives may be inorganic or organic in structure, and may be admixed with the active ingredient in any suitable manner. Such adjuvant materials may include any of the substances employed by the art in admixture with sulfonated organic detergents generally, provided the use of any such materials does not neutralize or remove the effectiveness of the mixed higher alcohols and higher amides. It has been found that these added materials may vary greatly both in structure and in concentration Without impairing the improved results of the compositions referred to herein.
Thus, such conventional inorganic builders or additives as the silicates, various alkali metal phosphates (e. g. hexametaphosphate, tetrapyrophosphate), the alkali metal sulfates, carbonates, etc., may be employed in these compositions. Organic materials such as carboxymethylcellulose, :esters (e.. g. ethylene glycol monostearate, methyl palmitate), and the like may also be used under suitable conditions.
Of the indicated vast variety of known builders and additives which may be employed in detergent compositions, it has now been found that the water soluble polyphosphates in conjunction with the mixed organic additives have remarkable effects on the alkyl aryl sulfonate detergent compositions. The polyphosphates are preferably the water soluble inorganic tri-polyphosphates of the formula:
MsPaOro M representing an alkali metal or ammonium group.
The actions of the tri-polyphosphate and the mixed organic additives in these detergent compositions are not only not antagonistic, but mutually contribute to a balanced detergency system such that a unitary result of vastly improved detergency is achieved thereby.
As previously indicated, the effect of the mixed organic additives is primarily one of activation of the soil removal power of aromatic sulfonate detergent compositions without any apparent adverse effect, or even a moderate inhibition of the amount of soil redeposition. It has been determined, however, that the tri-polyphosphates appear to exert beneficial results in an opposite direction in these detergency systems. The tri-polyphosphates exhibit their greatest effect on soil suspension or prevention of soil redeposition, and only to a minor extent on the soil removal factor. Since the total washing efiiciency is due to a combination of both soil removal and soil suspension, it is apparent that the mixed additives of the organic fatty alcohols and amides and the inorganic water soluble tripolyphosphates mutually contribute to produce a somewhat balanced effect since the two factors of improved soil removal and lessened soil redeposition are both activated concurrently to a marked degree.
These unexpected results are not achieved to the same degree when other phosphate compounds, such as tetrasodiumpyrophosphate (N214P207) or trisodiurnphosphate (Na3PO4) are substituted for the tri-polyphosphate. It is not known at this time why the indicated washing mixtures with the tri-polyphosphate should yield a markedly superior cleansing performance compared to mixtures with other phosphates in the detergent systems referred to herein.
These improved results may be illustrated by practical washing tests using the following compositions containing the sodium salts of higher alkyl benzene monosulfonate as the active ingredient:
Washing frmulaeper cent composition In these tests, soil removal and soil redeposition values are determined in hard water in a standard manner involving the use of natural soil on cotton textile items commonly used in the household. The results of these tests using composition I as a standard for comparative purposes are set forth in Table VI. The numbers in the table represent the percent change in soil removal and redeposition effected by compositions II and III from the standard. A plus value indicates the desirable effects of an increase in soil removal and decrease in the amount of redeposited soil; a minus value indicates a decrease in soil removal and increased redeposition of soil.
Table Vl.-Average values of tests Percent change The superiority of composition II containing the mixed organic additives with tri-polyphosphate is evident from the data. Composition III containing tetrasodiumpyrophosphate gives some improvement in soil removal but has an adverse effect on soil redeposition; whereas composition II exhibits a marked improvement in soil removal and an equivalent inhibition in soil redeposition. These unexpected and balanced effects on total washing power by a mixture of the two specified organic and the polyphosphate additives varies to some degree of course with changes in the detergent composition and conditions of testing, e. g. use of woolen samples.
The tri-polyphosphates may be used in any desired proportion. To some extent the degree of improvement appears to be proportional to its content in the composition. In general, the greater the percentage of tri-polyphosphate, the better the result where the active ingredient has been maintained constant. It has been found that best results are attainable when the ratio of tri-polyphosphate to the aromatic active ingredient is at least about 1:1. For maximum efliciency of these compositions, the active ingredient should be present in an amount at least about 20% by weight of the total composition. A proportion of active ingredient from about 20% to up to about 50% with a similar proportion of the tri-polyphosphate and a minor amount of the higher alcohols and amides produces sufiicient detergent properties for even heavily-soiled laundry; and such composition is economical to prepare and convenient for use in the home or commercially.
The tri-polyphosphates may be incorporated with the active ingredient in any suitable manner. It is possible to mechanically intermix these constituents in the form of small solid particles. However, it is preferred to apply the techniques set forth above for the introduction of the higher alcohols and amides. Thus, the tri-polyphosphate may be added to a slurry of the active ingredient before, during or after incorporation of the organic additives. The resulting mixture may be dried in any convenient manner, e. g.- roll or spray dried. Excessively high temperatures during drying should be avoided however to prevent substantial decomposition of the polyphosphates.
The following formulations are additional examples of compositions containing the mixed organic additives with and without the tri-polyphosphates productive of the improved results achieved by the present invention:
EXAMPLE III Certain general conclusions are apparent from the several hundred tests which have been conducted to determine the effects of these mixed organic additives in comparison to their individual use. The most appropriate mixture of organic additives, their proportion to each other, and their concentration in each detergent composition may suitably be determined by routine controls, taking into consideration whether a specific alkyl aryl sulfonate composition with the mixed organic additives with or without the tri-polyphosphates is designed for general home or commercial use in hard or soft water areas; or for specialized uses such as machine washing, washing of cottons, wool fabrics or flooring, etc. For example, in compositions designed for hard water areas, it would be preferably generally to use a mixture of the higher monohydric alcohols and amides. In soft water, the diols may well be much more desirable than the monohydric alcohols in the relationship set forth. In built compositions, the amount of monohydric alcohols should be kept within reasonable limits as it must be remembered that they, together with the amides, are adjuncts for the active ingredient salt. Thus, Where foam stability of a high order is desired, the amount of monohydric alcohols would preferably be not more than about in compositions containing about 20 to about 50% active ingredient. In compositions containing about 50% active ingredient, 510% monohydric alcohols may be used with better results than obtained by the use of the same concentration of the alcohols in compositions containing about 20% active ingredient. In general, where detergency alone is of prime importance less care need be taken in the selection of the optimum concentration of additives since the im proved results in detergency do not vary to the same degree as the improved results in the foam properties attained by the alkyl aryl sulfonate compositions of the present invention.
The term consisting of 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 and characteristics possessed by the composition set forth but to permit the presence of other materials in such amounts as not substantially to affect said properties and characteristics adversely.
Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefor without departing from the principles and true spirit of the invention.
Having described the invention, what is desired to be secured by Letters Patent is:
1. A detergent composition comprising from about to 50% by weight of water-soluble higher alkyl mononuclear aryl sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher aliphatic alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula:
wherein RCO is an aliphatic acyl radical of about 10 to 20 carbon atoms, and X and Y are each selected from the group consisting of hydrogen and alkylol radicals having up to 5 carbon atoms, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts.
2. A detergent composition comprising about 10 to 50% by weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher fatty alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula:
wherein RCO- is a higher fatty acyl radical of about 12 to 16 carbon atoms, and X and Y are each selected from the group consisting of hydrogen and alkylol radicals of up to 5 carbon atoms, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts.
3. A detergent composition comprising about 10 to 5 0% by weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to 10% of each by weight of a saturated monohydric fatty alcohol of 12 to 18 carbons and a higher fatty acyl primary amide having 10 to 14 carbon atoms in the acyl group, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts.
4. A detergent composition comprising about 10 to 50% by weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to 10% of each by weight of a saturated monohydric fatty alcohol of 12 to 18 carbons and a higher fatty acyl monoalkylolamide having 10 to 16 carbon atoms in the acyl group and up to 5 carbons in the alkylol group, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts.
5. A detergent composition comprising from about 10 to 50% by weight of water-soluble higher alkyl mononuclear aryl sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher aliphatic alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula:
wherein RCO- is an aliphatic acyl radical of about 10 to 20 carbon atoms, and X and Y are each selected from the group consisting of hydrogen and alkylol radicals having up to 5 carbon atoms, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts with about 20% to about 50% by weight water-soluble inorganic tripolyphosphate builder salt.
6. A detergent composition comprising about 10 to 50% by weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by weight of a higher fatty alcohol of about 12 to 18 carbon atoms and a higher amide compound having the formula:
wherein R-CO- is a higher fatty acyl radical of about 12 to 16 carbon atoms, and X and Y are each selected from the group consisting of hydrogen and alkylol radicals of up to 5 carbon atoms, and the balance being primarily a mixture of water-soluble inorganic sulfate and phosphate salts with about 20% to about 50% by weight sodium tripolyphosphate salt.
7. A detergent composition comprising about 10 to 50% by Weight of water-soluble higher alkyl benzene sulfonate detergent, in minor proportion thereto and from about 1 to about 10% of each by Weight of a higher aliphatic glycol of about 12 to 18 carbon atoms and a higher amide compound having the formula:
of up to 5 carbon atoms, and the balance being primarily water-soluble inorganic builder salts.
8. A detergent composition in accordance with claim 3 wherein said amide is myristamide and said alcohol is cetyl alcohol.
9. A detergent composition in accordance withclaim 4 wherein said monoallcylolamide is palmitoylmonoethanolamide and said alcohol is cetyl alcohoL.
References Cited in the file of this patent UNITED STATES PATENTS 2,166,315 Martin July 18, 1939 2,366,027 Henke Dec. 26, 1944 2,383,737 Richardson Aug. 28, 1945 2,383,738 Richardson Aug. 28, 1945 2,383,740 Tucker Aug. 28, 1945 2,396,278 Lind -2 Mar. 12, 1946 2,437,253 Henderson Mar. 9, 1948 2,486,922 Strain Nov. 1, 1949 2,490,459 Liiienfeld Dec. 6, 1949 2,519,062 Miskel Aug. 15, 1950

Claims (1)

1. A DETERGENT COMPOSITION COMPRISING FROM ABOUT 10 TO 50% BY WEIGHT OF WATER-SOLUBLE HIGHER ALKYL MONONUCLEAR ARYL SULFONATE DETERGENT, IN MINOR PROPORTION THERETO AND FROM ABOUT 1 TO ABOUT 10% OF EACH BY WEIGHT OF A HIGHER ALIPHATIC ALCOHOL OF ABOUT 12 TO 18 CARBON ATOMS AND A HIGHER AMIDE COMPOUND HAVING THE FORMULA:
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US2870091A (en) * 1955-09-01 1959-01-20 Stepan Chemical Co Detergent composition
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US3101324A (en) * 1960-12-12 1963-08-20 Colgate Palmolive Co Liquid detergent composition
US3188291A (en) * 1959-12-23 1965-06-08 Purex Corp Ltd Detergent compositions and granules and method of making them
US3239468A (en) * 1961-05-26 1966-03-08 Colgate Palmolive Co Hard surface cleaning compositions
US3318817A (en) * 1965-07-16 1967-05-09 Procter & Gamble Process for preparing detergent tablets
JPS6357698A (en) * 1986-08-29 1988-03-12 ライオン株式会社 Surfactant composition suppressed in skin irritation

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US2874127A (en) * 1956-06-29 1959-02-17 California Research Corp Sulfonate detergent compositions of improved foam characteristics
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