US3852211A - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
US3852211A
US3852211A US00279127A US27912772A US3852211A US 3852211 A US3852211 A US 3852211A US 00279127 A US00279127 A US 00279127A US 27912772 A US27912772 A US 27912772A US 3852211 A US3852211 A US 3852211A
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soap
sodium
tallow
ethylene oxide
composition
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T Ohren
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to US00279127A priority Critical patent/US3852211A/en
Priority to SE7310878A priority patent/SE414050B/xx
Priority to CA178,350A priority patent/CA1011057A/en
Priority to JP48089638A priority patent/JPS5748600B2/ja
Priority to GB3771173A priority patent/GB1401726A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/047—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on cationic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/18—Sulfonic acids or sulfuric acid esters; Salts thereof derived from amino alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/342—Phosphonates; Phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/521—Carboxylic amides (R1-CO-NR2R3), where R1, R2 and R3 are alkyl or alkenyl groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/886—Ampholytes containing P
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/92—Sulfobetaines ; Sulfitobetaines

Definitions

  • the soap and curd dispersant are UNITED STATES PATENTS formulated into the granule and the clay attached to 2,531,427 11/1950 Hauser 260/448 the surface of the granule.
  • the resulting compositions 2,594,257 ,4/1952 exhibit enhanced solubility and provide through-the 2,594,258 4/1952 Durgin 252/140 wash fabric softening 2,746,887 5/1956 ONeil 117/139.5 3,407,144 l0/l968 Bath 252/110 x 17 Claims, No Drawings l DETERGENT COMPOSITIONS BACKGROUND OF THE INVENTION
  • Laundry soaps i.e., the water-soluble salts of fatty acids, provide the user with good fabric cleansing coupled with product mildness.
  • soaps deposit on many types of fabrics in the form of a curd and thereby provide desirable softening benefits.
  • soaps deposit on many types of fabrics in the form of a curd and thereby provide desirable softening benefits.
  • soap curd has been found to interfere with the flame retardant finishes commonly applied to childrens chothing. That is to say, flame retardant fabrics coated with a heavy soap curd exhibit decreased levels of flame retardancy which, on removal of the soap curd, are restored to its original level.
  • One method for preventing curd buildup on fabrics laundered with soap is to include a curd dispersant in the laundering bath. While this method achieves the desired result, the laundered fabrics no longer have the desirable softening benefits imparted by soap. More importantly, granular laundering compositions which contain both soap and significant amounts of curd dispersant are difficult to dissolve in aqueous laundering baths. When such products are added to water, the soap tends to undergo a phase transition and agglomerate as a gelatinous material which then deposits in an unsightly manner onthe fabrics being laundered.
  • smectite-type clay material can be attached to the surface of soap-based detergent granules containing certain curd dispersants to substantially enhance the solubility of the granules. Furthermore, once the granules have dissolved, the clay is dispersed throughout the laundry liquor and deposits on the fabric surfaces to provide softening. Thus, the problem of excess curd buildup on fabrics is solved without losing the desirable softening benefits of soapbased compositions.
  • Clays have been utilized in many different types of detergent systems for widely diverse purposes.
  • Clays for example, have been disclosed for use as builders "(Schwartz and Perry, Surface Active Agents, Interscience Publishers, lnc., 1949, p. 233 and Schwartz, Perry and Berch, Surface Active Agents and Detergents, Vol. II, Interscience Publishers, lnc., 1958, pp. 297-300); as water-softeners (British Pat. No. 461,221); as anti-caking agents (US. Pat. Nos. 2,625,513 and 2,770,600); as suspending agents (US. Pat. Nos. 2,594,257, 2,594,258 and 2,920,045); and as fillers (US Pat. No. 2,708,185).
  • clay materials can be deposited on fabrics to impart softening and antistatic properties thereto. Such clay deposition is generally realized by contacting the fabrics to be so treated with aqueous clay suspensions (See, for example, 118. Pat. No. 3,033,699 and 3,594,212).
  • aqueous clay suspensions See, for example, 118. Pat. No. 3,033,699 and 3,594,212.
  • clay minerals of the type used in the presentinvention can beattached to the surface of soap-based detergent granules, especially those containing curd dispersants, to enhance the solubility of the granules in water while concurrently providing fabric softening.
  • compositions which canbe employed to yield simultaneous fabric laundering and fabric softening without interfering with flame retardancy are provided.
  • the present invention encompasses fabric laundering compositions comprising: ('A) a granular particle which comprises: (i) from about 30%to about 80% by weight of said particle of a soap compound, and; (ii) from about 1% to about 30% by weight of said granular particle of a curd-dispersing agent; and (B) an impalpable smectite-type clay having an ion exchange capacity of at least about 50 meq/l00'g. 'of clay, attached to the surface of said granular particle.
  • the compositions have a weight ratio of granular particles to smectite clay in the range of from about 20:1'to about 3:1.
  • the Granular Particle component of the instant laundering composition comprises two essential ingredients (1) a soap compound and (2)'a curd-dispersing agent;
  • the granular particles of the instant invention comprise from about 30% to about 80%, preferably from about 40% to about by weight of theparticles of a soap compound.
  • Useful soap compounds include the ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkanolammonium salts of higher fatty acidscontaining from about 8 to about 24 carbon atoms, preferably from about l to about 20 carbon atoms.
  • Suitable fatty acids can be obtained from natural sources such as, for instance, plant or-animalesters (e.g., palm oil, coconut oil, babassu oil,soybean oil, castor oil, tallow, whale and fish oils, grease,-lard, and mixtures thereof).
  • the fatty acids also can be synthetically produced (e.'g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer- Tropsch process).
  • Resin acids are suitable such as rosin and those resin acids in tall oil.
  • Naphthenic acids are 'low soap, potassium coconut soap and mixtures thereof.
  • the granular particles in addition to the soap component contain from about 1% to about 30%, preferably from about 2% to about 20%, by weight of theparticle of acurd-dispersing agent.
  • curd dispersing agents either prevent the formation of large particles of insoluble lime soaps or prevent such soaps from flocculating so that they are flushed away with the washing or rinsing liquid and do not adhere to fabrics or to surfaces of washing vessels.
  • the general method consists of preparing a series of mixtures containing varying proportions of sodium oleate and the curd dispersing agent being tested. These mixtures contain approximately total soap-pluscurd dispersant in distilled water. Five milliliters of each mixture are then added to 45 milliliters of hard water (usually 200 ppm hardness as CaO). This is called the first'dilution, and it usually results in a turbid but well-dispersed sol. Five milliliters of the first dilution are then added to 45 milliliters of hard water, forming thesecond dilution. This is a severe test since there is now more than enough lime present to precipitate all the soap. Furthermore, the total soap-plus-curd dispersant concentrationis of the, order of 0.1%. The
  • results are expressed as the percentage of dispersant in the soap-curddispersant mixture which is just sufficient to prevent flocculation on the second dilution; The more effective the curd dispersing agent, the lower is the percentage value.
  • a surfactant providing a percentage value greater than 39%in the above-described lime soap peptizing procedure.
  • curd-dispersing agents include certain anionic, semipolar nonionic, ampholytic and zwitterionic materials as well as certain amides and amines. Classes of these curd-dispersing agents are more fully described as follows.
  • Anionicorganic detergents which are alkali metal,
  • esters of a-sulfonated fatty acids in which the esters contain about 12 to about 25 carbon atoms.
  • R is an alkyl or alkenyl moiety of about 10 to about 20 carbon atoms (forming withthe two-carbon atoms a fatty acid group); R is alkyl of l to about 10 carbon atoms; and M is a salt-forming moiety.
  • the salt-formingmoiety Min the hereinbeforedescribed structural formula is awater-solubilizing cation and can be,for example, an alkali metal cation (e.'g., sodium, potassium, lithium), ammonium or substituted ammonium cation.
  • alkali metal cation e.'g., sodium, potassium, lithium
  • substituted ammonium cations include methyl-, dimethyl-,trime thyl-ammonium' and triethanolammonium cations and quaternary ammonium cations such as tetramethyl ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like.
  • this class of compounds include the sodium and potassium salts of esters where R is selected from methyl, ethyhpropyl, butyl, hexyl and octyl groups and the fatty acidgroup (R plus the two carbon atoms in the structure above) is selected from la'uri'c, myristic, palmitic, stearic, palmitoleic, oleic, linoleic acids andmixtures thereof.
  • A'preferred ester material herein is the sodium salt of the methyl ester of a-sulfo nated tallow fatty acid, the term tallow indicating a carbon chain distribution approximately as follows:,C 2.5%, C 28%, 'C 23%, palmitoleic 2%, oleic 41.5%, and linoleic 3% (the first three fattyacids listed are saturated).
  • Suitable salts of a-sulfonate'd fatty esters utilizable herein include the ammonium and tetramethylammonium salts of the hexyl, octyl, ethyl, and butyl esters of a-sulfonated tridecanoic acid; the ,potas-' sium and sodium salts of the ethyl, butyl, hexyl, octyl,' and decyl esters of a-sulfonated pentadecanoic acid;
  • R is alkyl of about 9 to about 23 carbon atoms; R is alkyl of l to about 8 carbon atoms; and M is a saltforming moiety as hereinbefore described.
  • B-acyloxy-alkane-l-sulfonates or alternatively, 2-acyloxy-alkane-l-sulfonates, utilizable herein to provide superior curd dispersion
  • the sodium salt of 2-acetoxy-tridecane-l-sulfonic acid the potassium salt of 2-propionyloxy-tetradecane-1- sulfonic acid
  • the sodium salt of 2-acetoxy-hexadeeane-lsulfonic acid the dimethylammonium salt of 2- heptanoyloxy-tridecane-l-sulfonic acid
  • B-acyloxy-alkane-l-sulfonate salts herein are the alkali metal salts of B-acetoxy-alkane-l-sulfonic acids corresponding to the above formula wherein R is an alkyl moiety of about 12 to about 16 carbon atoms, these salts being preferred from the standpoint of their excellent curd-dispersing properties and ready availability.
  • Anionic organic detergents which are alkyl ether sulfates.
  • RO( C H O), .SO M wherein R is an alkyl or alkenyl moeity of about to about carbon atoms, x is 1 to 30, and M is a saltforming cation as defined hereinbefore.
  • the alkyl ether sulfates useful in the present invention as curd dispersants are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms.
  • R has 14 to 18 carbon atoms.
  • the alcohols can be derived from fats, e. g. coconut oil or tallow, or can be synthetic; Lauryl alcohol and straight chain alcohols derived from tallow are preferred'herein. Such alcohols are reacted with'l to 30, and especially 3 or 6, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 or 6 moles of ethylene oxide per mole of alcohol, is sulfatedand neutralized.
  • alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulfate; lithium tallow alkyl trialkylene glycol ether sulfate; sodium tallow alkyl hexaoxyethylene sulfate; and ammonium tetradecyl octaoxyethylene sulfate.
  • alkali metal coconutand tallow-alkyl oxyethylene ether sulfates having an average of about 3 to about-1O oxyethylene moieties.
  • the alkyl ether sulfates of the present invention are known compounds and are described in US. Pat. No. 3,322,876 to Walker (July 25, 1967) incorporated herein by reference.
  • Anionic organic detergents which are olefin sulfonates having about 12 to about 24 carbon atoms.
  • olefin sulfonates is used herein to mean compounds which can be produced by the sulfonation of a-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture using conditions such that any sultones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates.
  • the sulfur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid S0 chlorinated hydrocarbon, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 etc., when used in the gaseous form.
  • the a-olefins from which the olefinsulfates are derived are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbon atoms. Preferably, they are straight chain olefins.
  • suitable l-olefins include l-dodecene; l-tetradecene; l-hexadecene; loctadecene; '1 -eicosene and l-tetracosene;
  • the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction' conditions, proportions of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
  • a preferred embodiment herein are those olefin sulfonates which are described completely in US. Pat. No. 3,332,880 issued July 25, 1967, to Kessler etaL, hereby incorporated by reference.
  • Nonionic organic detergents which are semipolar detergent compounds.
  • R is alkyl, alkenyl, or monohydroxyalkyl of about 8 to about 18 carbon atoms having from 0 to about 10 ethylene oxide moieties and from 0 to l glyceryl moiety and R and R are each alkyl or'monohydroxyalkyl groups containing from 1 to about 3 carbon.
  • phosphine oxides examples include dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide, 3,6,9-trioxaoctadecyldimethylphosphine oxide,
  • Nonionic organic detergents which are certain organic sulfoxides.
  • R is an alkyl group of 8 to 16 carbon atoms and X is selected from the groupconsisting of methyl, ethyl and B-hydroxyethyl groups.
  • X is selected from the groupconsisting of methyl, ethyl and B-hydroxyethyl groups.
  • Ampholy'tic synthetic detergents which are derivatives of aliphatic secondary and tertiary amines in which the aliphatic'group can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • These detergents have the formula wherein R is alkyl of about 8 to 18 carbon atoms, R is alkyl of 1 to about 3 carbon atoms or is hydrogen, R is alkylene of l to about 4 carbon atoms, Z is carboxy, sulfonate, sulfate, phosphate or phosphonate and M is a salt-forming cation, as hereinbefore described.
  • R is alkyl of about 8 to 18 carbon atoms
  • R is alkyl of 1 to about 3 carbon atoms or is hydrogen
  • R is alkylene of l to about 4 carbon atoms
  • Z is carboxy, sulfonate, sulfate, phosphate or phosphonate
  • M is a salt-forming cation, as hereinbefore described.
  • Examples of compounds falling within this definition aresodium 3-dodecylaminopropionate; sodium 3- dodecylaminopropane sulfonate; N-alkyltaurines
  • Zwitterionic synthetic detergents which are derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic groups can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • a general formula for these compounds is:
  • R is an alkyl, alkenyl, hydroxyalkyl or alkylbenzyl group containing from about 8 to about 24 carbon atoms and having from 0 to about 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety;
  • Y is selected from the group consisting of nitrogen, phospho rus, and sulfur atoms;
  • R is an alkyl or-monohyclroxy alkyl group containing 1 to about 3 carbon atoms;
  • x is 1 when Y is a sulfur atom and 2 whenY is a nitrogen or phosphorus atom,
  • R is an alkylene or hydroxy alkylene group of from 1 to about 4 carbon atoms and
  • Z is a member selected from the group con s'isting' of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
  • Such amide compounds include those aliphatic amides of the general formula:
  • R is hydrogen, alkyl, or alkylol and R and R" are hydrogen, alkyl, alkylol, or alkylene joined through an oxygen atom, the total number of carbon atomsin R, R and R being from about 9 to about 25.
  • RCO N in which RC is the acyl group of a soap-forming carboxylic acid having from about to about 18 carbon atoms, R and R" are each selected from the group consisting of hydrogen, alkyl, and alkylol substituents, and R is an alkylol substituent, the total number of carbon atoms in R, R" and R' being from 1 to 7.
  • Such amine compounds include N-alkyl monoalkylolamines and N-alkyl dialkylolamines in which the alkyl group has from 10 to 16 carbon atoms and the alkanol group has 2 or 3 carbon atoms; N-alkyl morpholines in which the alkyl group has from 10 to 16 carbon atoms; and N-alkyl tris(hydroxymethyl)aminomethane in which the alkyl group has from 10 to 16 carbon atoms.
  • Such compounds include N-dodecylmonoethanolamine, N-dodecyl-tris(hydroxymethyl)aminomethane, N-dodecyl isopropanolamine, N-tetradecyl monoethanolamine, N-dodecyl diethanolamine, 'N-tetradecyl diethanolamine 'and N-dodecyl morpholine.
  • N-dodecylmonoethanolamine N-dodecyl-tris(hydroxymethyl)aminomethane
  • N-dodecyl isopropanolamine N-tetradecyl monoethanolamine
  • N-dodecyl diethanolamine N-dodecyl diethanolamine
  • 'N-tetradecyl diethanolamine 'and N-dodecyl morpholine Compounds of this type-and their use as curd-dispersing agents are described more fully in Brit'- ish Pat. No.
  • the compounds preferred for use in the granular particles of the instant composition include the sodium salt of the methyl ester of a-sulfonated tallow fatty acid; the sodium salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide groups per mole; sodium B-acetoxyhexadecane-l-sulfonate; so-
  • Highly preferred curd dispersing agents herein are the sodium salt of ethoxylated tallow alkyl sulfate averaging about 3 ethylene oxide groups per mole, the sodium salt of ethoxylated tallow alkyl sulfate averaging about 6 ethylene oxide groups per mole, and tallow acyl monoethanolamide.
  • Optional Granule Components Besides the above-described 'soap and curddispersing components, the granular particles of the instant compositions can contain a wide variety of op tional components generally found in conventional fabric laundering formulations.
  • Such optional components include, for example, conventional anionic or nonionic surfactants which are not particularly useful ascurd dispersants and alkaline builder salts.
  • non-curddispersing surfactants are those having a percentage value in the above-described lime soap peptizing test greater than 39% and include the sodium salts of linear alkyl benzene sulfonic acid wherein the alkyl group average about 10 to 18 carbon atoms in length, sodium tallow alkyl sulfate, the condensation productof coconut fatty alcohol with about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of a secondary fatty alcohol containing about 15 carbon atoms with about 9 moles of ethylene oxide per mole of alcohol.
  • such conventional noncurd-dispersing surfactants generally comprise from about 1% to 30% by weight of the granular particle.
  • Typical alkaline builders include sodium tripolyphos- I phate, sodium citrate, sodium nitrilotriacetate, sodium carbonate and sodium mellitate. When employed, such conventional builders generally comprise from about 1% to 30% by weight of the granular particle.
  • optional granule components include the various soil-suspending agents such as carboxymethylcellulose, corrosion inhibitors, dyes, fillers such as sodium sulfate and silica, optical brighteners, bleac'hes such as sodium perborate, suds boosters, suds depressants, germicides, anti-tarnishing agents, pHadjusting agents such as sodium silicate, enzymes,and the like, well known in the art for use in detergent compositions. Bound water can also be present in said compositions.
  • soil-suspending agents such as carboxymethylcellulose, corrosion inhibitors, dyes, fillers such as sodium sulfate and silica, optical brighteners, bleac'hes such as sodium perborate, suds boosters, suds depressants, germicides, anti-tarnishing agents, pHadjusting agents such as sodium silicate, enzymes,and the like, well known in the art for use in detergent compositions.
  • Bound water can also be present in said compositions.
  • the soap-based granules herein can be prepared in standard fashion, e.g., by blending-the soap, curd dispersant and optional ingredients of the granules in a crutcher, and subsequently blowing the mix in standard spray-drying equipment.
  • Clay Compounds 7 increase thesolubility of the combined soap-curd dispersant granules and provide fabric softening concurrently with fabric cleansing.
  • These smectite clays are present in the detergent compositions at concentrations from about 4% to about 25%, preferably from 5% to by weight, of the total composition.
  • the weight ratio of clay to the soap-based granules is from about :1 to about. 3:1 by weight. 4
  • the clay minerals used to provide the solubility and softening properties of the instant compositions can be described as impalpable, expandable, three-layer clays, i.e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least about 50 meq/ 100 g. of clay.
  • impalpable as used to describe the clays employed herein means that the individual clay particles areof a size that they cannot be perceived tactilely. Such particle sizes are within the range below about 50 microns. In general, the clays herein will have a particle size within the range of from about 5 microns to about microns.
  • the term expandable as used to describe clays relates to the ability of the layered clay structure to be-swollen, .or expanded, on
  • the three-layer expandable clays used herein are those materials classified geologically as smectites.
  • smectite-type clays There are two distinct classes of smectite-type clays. In the first, aluminum oxide is present in the silicate crystal lattice; in the second class of smectites, magnesium oxide is present in the silicate crystal lattice.
  • the general formulas of these smectites are Al (Si O (OI-I) and Mg (Si O (OI-U for the aluminum and magnesium oxide type clay, respectively. It is to be recognized that the range of the water of hydration in the above formulas can vary with the processing to which the clay has been subjected. This is immaterial to the use of the smectite clays'in the present invention in that the expandable characteristics of the-hydrated clays are dictated by the silicatelattice structure.
  • atom substitution by iron and magnesium can occur within the crystal lattice of the smectites, while metal cations suchas Na+, CaH-, as well as I-I+, can be copresent in the water of hydration to provide electrical neutrality. Except as noted hereinafter, such cation substitutions are immaterial to the use of the clays herein since the desirable physical properties of the clays are not substantially altered thereby.
  • the three-layer, expandable alumino-silicates useful herein are further characterized by a di'octahedral crystal lattice, while the expandable three-layer magnesium silicates have atrioctahedral crystal lattice.
  • the clays employed in the compositions of the instant invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ion', magnesium ion, and the like. It is cus-.
  • a typicalexchange reaction involving a smectite-type clay is expressed by the following equation:
  • lllite clays varies widely in the range from about 2 meq/ 100 g. for kaolinites to about 150 meg/I00 g., and greater, for certain clays of the montmorillonite variety. lllite clays have an ion exchangecapacity somewhere in the lower 7 portion of the range, i.e., around 26 meq/ 100 g. for an average illite clay.
  • clays constitute a major component of clay soils and, are, in fact, removed from fabric surfaces by means of the instant compositions.
  • smectites such as nontronite, having anion exchange capacity of approximately 50 meq/ 100 g.
  • saponite which has an ion exchange capacity of around meq/ g.
  • montmorillonite which has anion exchange capacity greater than 70 meq/ 100 g.
  • clay minerals useful herein can be characterized as impalpable, expandable, threelayer smectite-type clays having an ion exchange capacity of at least about 50 meq/ 100 g.
  • the attachment of the expandable, three-layer, dioctadedral alumino-silicates and expandable, three-layer, trioctahedral magnesium silicates to the surface of the granules in the manner of this invention provides a means whereby the water solubility of the granules is greatly improved while additionally providing a homogeneous clay dispersion which provides effective fabric softening.
  • the smectite clays used in the compositions herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite.
  • the clays herein are available under commercial names such as fooler clay (clay found in a relatively thin vein above the main bentonite or montmorillonite veins in the Black Hills) and various'tradenames such as Thixogel No. 1 and Gelwhite GP from Georgia Kaolin Co., Elizabeth, NJ. Volclay BC and Volclay No. 325,
  • smectitetype minerals obtained under the foregoing commercial and tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures of the smectite mineralsare suitable for use herein.
  • any of the impalpable smectite-type clays having a cation exchange capacity of at least about 50 meg/ 100 g. are useful herein, certain clays are preferred.
  • Gelwhite GP and fooler clay are extremely white forms of smectite clays and are therefore preferred when formulating white, granular compositions.
  • Volclay BC which is a smectite-type clay mineral containing at least 3% of iron (expressed as Fe O in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in laundry compositions and is preferred from the standpoint of fabric softening performance.
  • l is a preferred clay herein from the standpoint of both product solubility and through-the-wash fabric softening performance.
  • certain smectite clays such as those marketedunder the name bentonite, are sufficiently contaminated by other silicate minerals that their ion exchange capacity falls below the requisite range, and such clays are of no use in the instant compositions.
  • Appropriate clay minerals for use herein can be selected byvirtue of the fact that smectites exhibit a true 14A X-ray diffraction-pattem. This characteristic pattern, together with exchange capacity measurements performed in the manner noted above, provides a basis for selecting suitable impalpable sernctite-type clay minerals for use in the granular detergent compositions disclosed herein.
  • compositions herein are formulated by simply preparing granules comprising the soap, curd dispersant, and any of the optional ingredients mentioned hereinabove, and then contacting the granules with the smectite-type clay. The clay can then be simply ad mixed with the soap-based granules and blended.
  • the clay is attached to the soap-based granules mainly by electrostatic surface forces between the clay and soap granules.
  • the soap-based granules are coated with a material of the type hereinafter disclosed which promotes adhesion of the clay particles to the surface of the granules.
  • a material of the type hereinafter disclosed which promotes adhesion of the clay particles to the surface of the granules.
  • the substantially dry soap-based granules can be first sprayed with said material in liquid form and then admixed with the clay.
  • the clay and sprayed granules are then thorou'ghlyblended to provide good contact and optimum coating of the granules with the clay.
  • the clay and granules are concur rently admixed and sprayed with the adhesion-' promoting material.
  • the clay and granules materials are preferred herein for attaching the clay to v the soap-based granules.
  • the materials used herein havesufficient hydrophilic character that they are easily dissolved or dispersed in water, but they are preferably not hydroscopic.
  • a variety of liquid and liquifiable organic compounds are useful herein for attaching the clay tothe surface of the soap-based granules.
  • all manner of common ethoxylated nonionic surfactants can beused for this purpose.
  • condensation of an alkylene oxide moiety (hydrophilic in nature) with an organic hydrophobic compound which is usually aliphatic or alkyl aromatic in nature can be used.
  • the length of the hydrophilic or polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield colorless, liquid or liquitiable, water dispensable,
  • nonionic surfactants which are useful adhesion promoters herein.
  • nonionic surfactants which can be used as the adhesion-promoting materials herein include: l.
  • the polyethylene oxide condensates of alkyl phenols. These compounds include the condensation prod ucts of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms, in either a straight chain or branched chain configuratiomwith ethylene oxide, said ethylene oxide being-present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substituent in such compounds can be derived, for example, from polymerized propy-' lene, diisobutylene, octene, or nonene.
  • Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol, dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenoL'dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol, di-isooctyl-phenol condensed with about moles of ethylene oxide per mole of phenol.
  • nonionic surfactants of this type include lgepal CO-610 marketed by the GAP Corporation; and Triton X-45, X-l l4, X-l00 and X-l02, all marketed by the Rohm and Haas Company.
  • ethylene oxide with about 10 moles of ethylene' oxide per mole of myristyl alcohol, the condensation product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the abovedescribed coconut. alcohol.
  • nonionic surfactants of this type include Tergitol l5-S -9 marketed by the Union Carbide Corporation, Neodol 23-6.5 marketed by the Shell Chemical Company, and Kyro EOB marketed by The Procter & Gamble Company.
  • the hydrophobic portion of these compounds has a molecularweight of from about 1500 to 1800.
  • the addition-of polyoxyethylene moieties to this hydrophobic portion tends to increase the water-solubility of the molecule as 'a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product.
  • Examplesof compounds of this type include certain of the commercially available Pluronic surfactants marketed by the Wyandotte Chemicals Corporation.
  • the fatty acids are-another class of materials which can be used to promote the attachment of the clays to the surface of the granules.
  • Fatty acids useful herein are thoseC to C straight chain and branched chain aliphatic carboxylic acids which can be'obtained, for example, by the saponification of triglycerides. Both saturated and unsaturated fatty acids are useful herein. Mixtures of fatty acids obtainable from certain designated fats, e.g., tallow fatty acids, obtainable from tallow; coconut fatty acids, obtainable from coconut oil and; palm fatty acids, obtainable from palmoil, are also useful herein.
  • Exemplary fatty acids which can be employed herein to affix the clay to the soap-based granules include lauric, myristic, palmitic, stearic, elaidic, oleic and eicosanoic acids, and mixtures thereof.
  • the fatty alcohols having C to C hydrocarbon chains are also useful herein as adhesion promoters. These materials can be obtained in a variety of ways well known in the art, e.g., from various triglyceride oils, such as palm oil and coconut oil. Exemplary alcohols useful herein include l.-dodecanol, l-tetradecanol, l-hexadecanol and l-octadecanol. I
  • Preferred materials which can be usedherein to attach the smectite clays to the surfaces of the soap-pluscurd dispersant granules include; coconut alcohol ethoxylate containing 6 ethylene oxide units per molecule; tallow alcohol ethoxylate containing, 1 1 ethylene oxide units .per molecule, i.e., tallow ethylene oxide l1); coconut fatty acid mixtures; tallow fatty acid mixtures, the condensate of one mole of ethylene oxide with l-dodecanol; and the condensate of one mole of l-dodecanol with ethylene oxide hexamer.
  • Especially preferred adhesion promoters herein include coconut fatty acids and tallow ethylene oxide (11). 1
  • the optionally employed adhesionpromoting materials serve the additional function of providing an unexpected-additional increment of solubilityto the compositions. That is to say, while' the soap-plus-curd dispersant granules herein exhibit poor solubility in laundering baths on the range of from about 60F. to F., the surface coating of the adhesion-promoting materials enhances this solubility. while the soap-plus-curd dispersant granules coated with the adhesion-promoting materials are not rendered sufficientlysoluble to. be optimally useful forcool water serve to decrease product dust levels. The decreased product dust levels afforded by the adhesion promoters aids in processing and provides a more acceptable product for the consumer.
  • the adhesion-promoting materials herein are face of the soap-based granules, they 'are'preferably used in an amount sufficient to providesaid granules with at least a monolayer coating of said materials.
  • the adhesion-promoting material can comprise from about 0.5% to about 8%, preferably 1% to about 4%, by weight'of the total composition.
  • higher proportions of the adhesion, promoters can be employed, but this represents an economicv waste in thatsuch increased proportions are not required to affix the clay to the granules and donot further increase product solubility to any substantial degree.
  • clay-to-soap-based granules ratio results in compositions wherein a substantial proportion of the surface of the granules are coated with the clay.
  • adhesion-promoting materials are additionally employed, greater coverage of the granules is more easily achieved.
  • soapbased granules having about l%, and greater, of their surfaces coated with the clay exhibit the desirable solubility properties disclosed herein, it is preferred that the clay coat at least about 40% of the granule surface. Such higher degrees of surface coating are most readily achieved by use of the adhesion-promoting materials disclosed above.
  • compositions of the instant invention are added to aqueous laundering liquor to the extent of from about 0.02% to about 2% by weight, preferably form about 0.1% to about 1% by weight. Addition of such compositions provide a laundering liquor pH of from about 7 to 12.
  • a soap-based laundry granule is prepared having the following composition:
  • the foregoing ingredients are mixed in a crutcher and spray-dried to provide a granular, soap-based composition.
  • Such a composition is a stable laundry detergent formulation providing excellent fabric laundering and as noted below also has desirable solubility and fabric softening characteristics when added to laundering liquor to the extent of about 0.12% by weight.
  • a soap-based laundry granule is prepared having the following composition:
  • the foregoing ingredients are mixed in a crutcher and spray-dried to provide a granular, soap based composition. 7
  • Such a composition is a stable laundery detergent formulation providing excellent fabric laundering and. as noted in greater detail below, also has desirable sol ubility and fabric softening characteristics when added to laundering liquor to the extent of about 0.12% by weight.
  • a soap-based laundry granule is prepared having the following composition:
  • the foregoing ingredients are mixed in a crutcher and spray-dried to provide a granular, soap-based composition.
  • a soap-based laundry granule is prepared having the following composition:
  • Component Balance A mixture of tallow and coconut soaps comprising 80% tallow soap and coconut soap.
  • the foregoing ingredients are mixed in a crutcher and spray dried to provide a granular, soap-based composition.
  • Such a composition is a stable, laundry detergent formulation providing excellent fabric laundering and, as noted. in greater detail below, also has desirable solubility' and fabric softening .characteristics when added to laundering liquor to the extent of about 0.7% by weight.
  • Solubility Test The water solubilitiy of foregoing compositions is assessed, as follows Automatic mini-washers each containing about l-Vz gallons of water (7 gr/gal. hardness) and loaded with 6 blue cotton terry' towels (l4 X 14 inches; ca. 250 grams) areemployed in the tests. Machine settings are wash-wear, i.e., gentle agitation. After the water and terry towels are in the machines, test product is poured uniformly into the machine in an amount equivalent to 1 cup per 17-19 gallons, and agitation is begun. After 15 seconds agitation, the machine is stopped and a product lumping grade is assigned. This grade is a visual assessment of the tendency of the product to coagulate or to' form large particles. Small particles are not considered when assigning a lumping grade. Using this visual procedure, a grade of 1 indicates many large lumps; a grade of 10' indicates no large lumps.
  • a second measurement is then taken which measures the length of time unitl all product is dissolved, up to a maximum time of 4 minutes.
  • One unit is substracted from the grade if the time for dissolution of the product is greater than one minute.
  • Lumping is assessed at temperatures of 80F., 100F. and l20F.
  • a TOTAL SOLUBILITY INDEX is then assigned as follows: Lumping Grade at 80F. X 0.2 Lumping e- 100 XII- .Lum s ad e 120F. X 0.4 TOTAL SOLU'BI LITY IN DEX.
  • fatty acid thesodium salt of ethoxylated tallowalk'yl' sulfate having an average of about 6 ethylene oxide groups per mole; sodium l3-acetoxy-hexadecane-lsulfonate; sodium B-acetoxy tridecane-l-sulfonate; the
  • Sofmess Test The through-the-wash fabric softening performance solubility results are obtained ener in the rinse cycle. Microscopic examination of the swatches indicates that substantial amounts of the clay are deposited on the fabric, but no substantial amount of curd is found on the fabric surface.
  • the sodium salt of the methyl'ester of a-sulfonated tallow fatty acid is the sodium salt of ethoxylated tallow alkyl sulfate having an average of about 6 ethylene oxide groups per mole; sodium B-acetoxy-hexadecanel-sulfonate; sodium B-acetoxy tridecanel -sulfonate; the sodium salt of sulfonated l-hexadecene; dimethyldodecylphosphine oxide; sodium hexadecylmethylaminopropionate; 3(N,Ndimethyl-N- alkylammonio)-propanel -sulfonate and 3(N,N- dimethyl-N-alkylammonio )-2-hydroxypropanel sulfonate wherein in both compounds thealkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl- N-hexade
  • a fabric laundering composition comprising A. granular particles which comprise A i. from about 30% to about by-weight of said granular particles of a soap compound, and ii. from about l,% to about 30% by weight of said granular particles of a soap-curd-dispersing agent; and b. an impalpable smectite clay having an ion exchange capacity of at least about 50 meg/1 00 grams, attached to the surface of said granular particles; said composition having a weight ratio of granular particles to impalpable smectite clay of from about 20:1 to 3:1.
  • composition in accordance with claim 1 A wherein the soap compound is a salt of a higher fatty acid containing from about 8 to about 24 car- SOaM wherein R is alkyl or alkenyl of about 10 to 20 carbon atoms, R is alkyl of l to about 10 carbon atoms and M is a salt-forming cation; ii. compounds of the formula v O OikRz R1 H-omsoavr wherein R is alkyl of about 9 to about 23 carbon atoms, R is alkyl of l toabout 8 carbon atoms and M is a salt-forming cation;
  • olefin sulfonates containing from about 12 to'24 carbon atoms
  • R is alkyl of about 8 to 18 carbon atoms
  • R is selected from the group consisting of alkyl of l to about 3 carbon atoms and hydrogen
  • Z is alkylene of l to about 4 carbon atoms
  • Z is selected from the group consisting of carboxy, sulfonate, sulfate, phosphate and phosphonate
  • M is a salt-forming cation
  • R is selected from the group consisting of alkyl, alkenyl, hydroxyalkyl and alkylbenzene groups, all groups containing from about 8 to about 24 carbon atoms and having from O to about ethylene oxide moieties and from 0 to l glyceryl moiety;
  • Y is selected from the group consisting-of nitrogen, phosphorus, and sulfur atoms;
  • R is an alkyl or monohydroxyl alkyl group containing 1 to about 3 carbon atoms;
  • x is vii.
  • R is hydrogen, alkyl or alkylol and R and R" are each hydrogen, alkyl, alkylol, or alkylene joined through an oxygen atom, the total number of carbon atoms in R, R and R" being from about 9 to about 25;
  • soap-curd-dispersing agent is present in said granular particles to the extent of from about 2% to about byweight of said granular particles;
  • impalpable smectite clay is selected from thegroup consisting of dioctahedral expandable three-layer aluminum-silicates and trioctahedral I expandable three-layer magnesium silicates, and is. presentto the extent of from about 4% to about %.by weight of the total composition.
  • composition in accordance with claim 2 A. wherein the soap is selected from the group consisting of sodium tallow soap, sodium coconut soap, potassium tallow soap, potassium coconut soap and mixtures thereof;
  • soap-curd-dispersing agent is selected from the groupconsisting of the sodium salt of the methyl ester of a-sulfonated tallow fatty acid; the sodium, salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide groups per mole; the sodiumjsalt of ethoxylated tallow alkyl sulfate'havi'ng an average of about 6 ethylene oxide groups per mole; sodium B-acetoxy-hexadecane-lsulfonate;.sodium B-acetoxy tridecanel -sulfonate; the sodium salt of sulfonated l-hexadecane; sodium hexadecylmethylaminopropionate;' 3(N,N- dimethyl-N-alkylammonio )-propane l -sulfonate and d '3(N,N-dimethyl-N-
  • smectite clay is selected from the group consisting .of montmorillonites, volchonskoites, nontronites, hectorites, sauconites and vermiculites.
  • soap-curd'dispersing agent is selected from the group consisting of the sodium salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide groups per mole; the sodium salt of ethoxylated tallow alkyl sulfate having an average of about 6 ethylene oxide groups per mole; and tallow acyl monoethanolamide; and B.
  • smectite clay is a montmorillonite.
  • the soap-curddispersing agent is the sodium salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide groups permole and the smectite clay is a sodium montmorillonite.
  • composition in accordance with claim 6 A wherein the soap is selected from the group consisting .of sodium tallow soap, sodium coconut soap, potassium tallow soap, potassium coconut soap and'mixtures thereof; I I, wherein the soap-curd-dispersing agent is selected from-the group consisting of the sodium salt of the methyl-ester of a-sulfonated tallow'fatty acid; the sodium salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide groups-per mole; the sodium salt of ethoxylated tallow alkyl sulfate having an average of about 6 ethylene oxide groups per mole; sodium fi-acetoxy-hexadecane-1- sulfonate; sodium B-acetoxy tride'canel -sulfonate; the sodium salt of sulfonated l-hexadecene; sodium hexadecylmetl'iylaminopropionate;
  • compositionin accordance with claim 7 A wherein the conventional non-soap-curd-- dispersingsurfact'ant is selected from the group consisting of sodium linear alkyl benzene sulfonate wherein the alkyl group averagesfrom about 10 to 18 carbon atoms in length, sodium tallow alkyl sulfate, and B. wherein the adhesion-promoting material is selected from the group consisting of non-ionic surfactants produced by the condensation of an alkylene oxide moiety with an organic hydrophobic compound, fatty acids containing from about 10 to about 22 carbon atoms and fatty alcohols containing from about l to 22 carbon atoms. 9. A composition in accordance with claim 8 A.
  • soap-curd-dispersing agent is selected from the group consisting of the sodium salt of ethoxylated tallow alkyl sulfate averaging about 3 ethylene oxide groups per mole; the sodium salt of ethoxylated tallow alkyl sulfate averaging about 6 ethylene oxide groups per mole; and tallow acyl monoethanolamide; B. wherein the smectite clay is a montmorillonite; C. wherein the conventional non-soap-curddispersing surfactant is sodium linear alkyl benzene sulfonate wherein the alkyl group averages about 12 carbon atoms in length; and D.
  • adhesion-promoting material is selected from the group consisting of coconut alcohol ethoxylate containing 6 ethylene oxide units per molecule; tallow alcohol ethoxyla te containing 1 l ethylene oxide units per molecule; coconut fatty acid mixtures; tallow fatty acid mixtures, the condensate of one mole of ethylene oxide with ldodecanol; and the condensate of one mole of ldodecanol with ethylene oxide hexamer, said adhesion-promoting material being present to the extent of from about 1% to about 4% by weight of the total composition. 10.
  • a composition in accordance with claim 9 wherein the adhesion-promoting material is selected from the group consisting of tallow alcohol ethoxylate containing ll ethylene oxide units per molecule and coconut fatty acid mixtures.
  • the adhesion-promoting material is selected from the group consisting of tallow alcohol ethoxylate containing ll ethylene oxide units per molecule and coconut fatty acid mixtures.
  • the alkaline builder salt is sodium tripolyphosphate.
  • a composition in accordance with claim 12 which, in addition to the granular particles and impalpable smectite clay, contains an adhesion-promoting material comprising from about 0.5% to about 8% by weight of the total composition.

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Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948790A (en) * 1974-01-31 1976-04-06 The Procter & Gamble Company Detergent compositions containing short chain quaternary ammonium clays
US3962132A (en) * 1973-10-31 1976-06-08 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for improving the wettability of natural or synthetic zeolites
US3966629A (en) * 1973-08-24 1976-06-29 The Procter & Gamble Company Textile softening detergent compositions
US3985669A (en) * 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
US4019998A (en) * 1974-09-27 1977-04-26 The Procter & Gamble Company Process for preparing a pyrophosphate-silicate detergent product
US4096081A (en) * 1976-02-06 1978-06-20 The Procter & Gamble Company Detergent compositions containing aluminosilicate agglomerates
US4292035A (en) * 1978-11-13 1981-09-29 The Procter & Gamble Company Fabric softening compositions
US4298480A (en) * 1978-12-11 1981-11-03 Colgate Palmolive Co. Detergent softener compositions
US4326971A (en) * 1978-12-11 1982-04-27 Colgate Palmolive Company Detergent softener compositions
US4329237A (en) * 1979-11-21 1982-05-11 Colgate-Palmolive Company Detergent softener compositions
US4343713A (en) * 1980-10-29 1982-08-10 The Procter & Gamble Company Particulate composition
FR2525232A1 (fr) * 1982-04-15 1983-10-21 Colgate Palmolive Co Detergent adoucissant pour textiles et son procede de fabrication
US4411803A (en) * 1980-10-27 1983-10-25 Colgate Palmolive Company Detergent softener compositions
US4416811A (en) * 1979-11-21 1983-11-22 Colgate-Palmolive Company Detergent softener compositions
US4419250A (en) * 1982-04-08 1983-12-06 Colgate-Palmolive Company Agglomerated bentonite particles for incorporation in heavy duty particulate laundry softening detergent compositions.
US4421657A (en) * 1982-04-08 1983-12-20 Colgate-Palmolive Company Heavy duty laundry softening detergent composition and method for manufacture thereof
US4450085A (en) * 1981-05-01 1984-05-22 Colgate Palmolive Company Detergent softener compositions
US4472287A (en) * 1982-12-13 1984-09-18 Colgate-Palmolive Company Particulate fabric softening composition, fabric softening detergent useful for hand washing laundry and process for manufacture and use thereof
US4482471A (en) * 1982-04-08 1984-11-13 Colgate-Palmolive Company Siliconate-coated sodium perborate
US4482477A (en) * 1982-04-08 1984-11-13 Colgate-Palmolive Company Particulate detergent containing siliconate, composition and method for manufacture thereof
US4482630A (en) * 1982-04-08 1984-11-13 Colgate-Palmolive Company Siliconate-coated enzyme
US4488972A (en) * 1982-04-08 1984-12-18 Colgate-Palmolive Company Bentonite agglomerates
US4526702A (en) * 1982-08-25 1985-07-02 Colgate Palmolive Co. Process for manufacturing bentonite-containing particulate fabric softening detergent composition
US4569773A (en) * 1982-12-13 1986-02-11 Colgate Palmolive Co. Particulate fabric softening detergent composition
US4582615A (en) * 1984-11-26 1986-04-15 Colgate Palmolive Co. Bentonite-sulfate fabric softening particulate agglomerate, processes for manufacture and use thereof, and detergent compositions containing it
US4605509A (en) * 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
US4746445A (en) * 1982-04-08 1988-05-24 Colgate-Palmolive Company Process for manufacturing bentonite agglomerates
US4767546A (en) * 1982-04-08 1988-08-30 Colgate-Palmolive Co. Fabric softening bentonite agglomerates for use in laundry detergents
US4851137A (en) * 1982-04-08 1989-07-25 Colgate-Palmolive Co. Process for manufacturing bentonite agglomerates
US4919838A (en) * 1988-09-30 1990-04-24 Hubert M. Tibbetts Bar shampoo and skin soap
EP0283976A3 (de) * 1987-03-26 1990-06-13 Henkel Kommanditgesellschaft auf Aktien Phosphatfreies, textilweichmachendes Waschmittel
US4999125A (en) * 1989-03-31 1991-03-12 Ecc International Limited Granules of a detergent component coated with an organophilic clay
WO1993001267A1 (en) * 1991-07-08 1993-01-21 The Procter & Gamble Company Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening system
US5318714A (en) * 1988-03-14 1994-06-07 Novo Nordisk A/S Stabilized particulate composition
US5470509A (en) * 1993-07-15 1995-11-28 The Procter & Gamble Company Low pH granular detergent composition having improved biodegradability and cleaning performance
US20050043201A1 (en) * 2003-08-18 2005-02-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent composition
CN111032840A (zh) * 2017-09-06 2020-04-17 花王株式会社 纤维制品用处理剂组合物
WO2024263571A3 (en) * 2023-06-23 2025-01-30 Arxada, LLC Surfactant potentiators for ethoxylated surfactants

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60130290U (ja) * 1984-02-09 1985-08-31 愛知車輛株式会社 自走式高所作業車の転倒防止装置
GB9723810D0 (en) * 1997-11-12 1998-01-07 Mcbride Robert Ltd Fabric softening co-granules

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB461221A (en) * 1936-04-17 1937-02-12 Robert Henry Marriott Compositions suitable for use in the washing of textile materials or for other washing purposes
US2531427A (en) * 1946-05-03 1950-11-28 Ernst A Hauser Modified gel-forming clay and process of producing same
US2594257A (en) * 1949-05-12 1952-04-22 Monsanto Chemicals Detergent composition
US2594258A (en) * 1949-05-12 1952-04-22 Monsanto Chemicals Detergent composition
US2746887A (en) * 1953-06-17 1956-05-22 Polymouth Cordage Company Lubricated fiber strand
US3407144A (en) * 1963-12-11 1968-10-22 Procter & Gamble Detergent composition
US3414520A (en) * 1964-04-27 1968-12-03 Lever Brothers Ltd Detergent composition
US3583923A (en) * 1970-05-26 1971-06-08 Grace W R & Co Cleaning composition
US3625905A (en) * 1967-11-22 1971-12-07 Purex Corp Ltd Detergent composition having softening properties

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB461221A (en) * 1936-04-17 1937-02-12 Robert Henry Marriott Compositions suitable for use in the washing of textile materials or for other washing purposes
US2531427A (en) * 1946-05-03 1950-11-28 Ernst A Hauser Modified gel-forming clay and process of producing same
US2594257A (en) * 1949-05-12 1952-04-22 Monsanto Chemicals Detergent composition
US2594258A (en) * 1949-05-12 1952-04-22 Monsanto Chemicals Detergent composition
US2746887A (en) * 1953-06-17 1956-05-22 Polymouth Cordage Company Lubricated fiber strand
US3407144A (en) * 1963-12-11 1968-10-22 Procter & Gamble Detergent composition
US3414520A (en) * 1964-04-27 1968-12-03 Lever Brothers Ltd Detergent composition
US3625905A (en) * 1967-11-22 1971-12-07 Purex Corp Ltd Detergent composition having softening properties
US3583923A (en) * 1970-05-26 1971-06-08 Grace W R & Co Cleaning composition

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4605509A (en) * 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
US3966629A (en) * 1973-08-24 1976-06-29 The Procter & Gamble Company Textile softening detergent compositions
US3962132A (en) * 1973-10-31 1976-06-08 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for improving the wettability of natural or synthetic zeolites
US3948790A (en) * 1974-01-31 1976-04-06 The Procter & Gamble Company Detergent compositions containing short chain quaternary ammonium clays
US3985669A (en) * 1974-06-17 1976-10-12 The Procter & Gamble Company Detergent compositions
US4019998A (en) * 1974-09-27 1977-04-26 The Procter & Gamble Company Process for preparing a pyrophosphate-silicate detergent product
US4096081A (en) * 1976-02-06 1978-06-20 The Procter & Gamble Company Detergent compositions containing aluminosilicate agglomerates
US4292035A (en) * 1978-11-13 1981-09-29 The Procter & Gamble Company Fabric softening compositions
US4326971A (en) * 1978-12-11 1982-04-27 Colgate Palmolive Company Detergent softener compositions
US4298480A (en) * 1978-12-11 1981-11-03 Colgate Palmolive Co. Detergent softener compositions
US4329237A (en) * 1979-11-21 1982-05-11 Colgate-Palmolive Company Detergent softener compositions
US4416811A (en) * 1979-11-21 1983-11-22 Colgate-Palmolive Company Detergent softener compositions
US4411803A (en) * 1980-10-27 1983-10-25 Colgate Palmolive Company Detergent softener compositions
US4343713A (en) * 1980-10-29 1982-08-10 The Procter & Gamble Company Particulate composition
US4450085A (en) * 1981-05-01 1984-05-22 Colgate Palmolive Company Detergent softener compositions
US4482630A (en) * 1982-04-08 1984-11-13 Colgate-Palmolive Company Siliconate-coated enzyme
US4851137A (en) * 1982-04-08 1989-07-25 Colgate-Palmolive Co. Process for manufacturing bentonite agglomerates
US4482471A (en) * 1982-04-08 1984-11-13 Colgate-Palmolive Company Siliconate-coated sodium perborate
US4482477A (en) * 1982-04-08 1984-11-13 Colgate-Palmolive Company Particulate detergent containing siliconate, composition and method for manufacture thereof
US4419250A (en) * 1982-04-08 1983-12-06 Colgate-Palmolive Company Agglomerated bentonite particles for incorporation in heavy duty particulate laundry softening detergent compositions.
US4488972A (en) * 1982-04-08 1984-12-18 Colgate-Palmolive Company Bentonite agglomerates
US4421657A (en) * 1982-04-08 1983-12-20 Colgate-Palmolive Company Heavy duty laundry softening detergent composition and method for manufacture thereof
US4767546A (en) * 1982-04-08 1988-08-30 Colgate-Palmolive Co. Fabric softening bentonite agglomerates for use in laundry detergents
US4746445A (en) * 1982-04-08 1988-05-24 Colgate-Palmolive Company Process for manufacturing bentonite agglomerates
FR2525232A1 (fr) * 1982-04-15 1983-10-21 Colgate Palmolive Co Detergent adoucissant pour textiles et son procede de fabrication
US4526702A (en) * 1982-08-25 1985-07-02 Colgate Palmolive Co. Process for manufacturing bentonite-containing particulate fabric softening detergent composition
US4569773A (en) * 1982-12-13 1986-02-11 Colgate Palmolive Co. Particulate fabric softening detergent composition
US4472287A (en) * 1982-12-13 1984-09-18 Colgate-Palmolive Company Particulate fabric softening composition, fabric softening detergent useful for hand washing laundry and process for manufacture and use thereof
US4582615A (en) * 1984-11-26 1986-04-15 Colgate Palmolive Co. Bentonite-sulfate fabric softening particulate agglomerate, processes for manufacture and use thereof, and detergent compositions containing it
EP0283976A3 (de) * 1987-03-26 1990-06-13 Henkel Kommanditgesellschaft auf Aktien Phosphatfreies, textilweichmachendes Waschmittel
US5318714A (en) * 1988-03-14 1994-06-07 Novo Nordisk A/S Stabilized particulate composition
US4919838A (en) * 1988-09-30 1990-04-24 Hubert M. Tibbetts Bar shampoo and skin soap
US4999125A (en) * 1989-03-31 1991-03-12 Ecc International Limited Granules of a detergent component coated with an organophilic clay
WO1993001267A1 (en) * 1991-07-08 1993-01-21 The Procter & Gamble Company Detergent compositions containing polyhydroxy fatty acid amide surfactants and a clay softening system
US5470509A (en) * 1993-07-15 1995-11-28 The Procter & Gamble Company Low pH granular detergent composition having improved biodegradability and cleaning performance
US20050043201A1 (en) * 2003-08-18 2005-02-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent composition
WO2005017086A1 (en) * 2003-08-18 2005-02-24 Unilever Plc Detergent composition
CN100422302C (zh) * 2003-08-18 2008-10-01 荷兰联合利华有限公司 洗涤剂组合物
CN111032840A (zh) * 2017-09-06 2020-04-17 花王株式会社 纤维制品用处理剂组合物
US11332698B2 (en) * 2017-09-06 2022-05-17 Kao Corporation Treatment agent composition for textile products
WO2024263571A3 (en) * 2023-06-23 2025-01-30 Arxada, LLC Surfactant potentiators for ethoxylated surfactants

Also Published As

Publication number Publication date
CA1011057A (en) 1977-05-31
JPS49132104A (OSRAM) 1974-12-18
JPS5748600B2 (OSRAM) 1982-10-16
GB1401726A (en) 1975-07-30
SE414050B (sv) 1980-07-07

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