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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
• • 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
  • C11D1/62—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions

Definitions

• the instant invention relates to qranular built laundry detergent compositions which provide simultaneous laundering, softening and anti-static benefits on textiles during conventional fabric laundering operations.
• Such compositions employ a combination of synthetic detergent compounds, organic or inorganic detergent builders, particular smectite clay compounds having particular cation exchange characteristics and cationic anti-static agents.
• Clays have been utilized in many different types of detergent systems for widely diverse purposes.
• Clays for example, have been disclosed for utilization as builders (Schwartz and Perry, Surface Active Agents, lnterscience Publishers, Inc., 1949, pp. 232 and 299); 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 properties thereto.
• Such clay deposition is usually realized by contacting fabrics to be so treated with aqueous clay suspensions (see, for example, US. Pat. Nos. 3,033,699 and 3,594,221).
• the copending application of Storm and Nirschl, Ser. No. 271,943, filed July 14, 1972, and Ohren, Ser. No. 279,127, filed Aug. 9, 1972, relate to the use of clays as softeners in laundry compositions.
• clays as fabric softeners is described in the cited art, such clay softeners are not entirely suitable for this purpose since they do not possess antistatic properties.
• Commercially acceptable softeners provide anti-static benefits, and such benefits have come to be expected by the user of such products. Indeed, fabrics coated with clays, while exhibiting a soft hand, tend to develop higher levels of static charge than the uncoated fabrics.
• compositions containing clay-plusquaternary ammonium compounds are not suitable for laundering fabrics while concurrently imparting softness and anti-static benefits thereto.
• compositions which can be employed to concurrently launder, soften, and impart anti-static benefits to fab rics.
• the present invention encompasses granular built laundry detergent compositions comprising: (a) from about 2 to about 30 percent by weight of a non-soap synthetic detergent compound selected from the group consisting of anionic synthetic detergents, nonionic synthetic detergents, ampholytic synthetic detergents, zwitterionic synthetic detergents and mixtures thereof; (b) from about 10 to about 60 percent by weight of an organic or inorganic detergent builder salt; (c) from about 1 to about 50.
• a non-soap synthetic detergent compound selected from the group consisting of anionic synthetic detergents, nonionic synthetic detergents, ampholytic synthetic detergents, zwitterionic synthetic detergents and mixtures thereof.
• n can be 1 to 3 in the compounds herein.
• the weight ratio of smectite-type clay to quaternary ammonium compound in the compositions herein is from about 40:1 to about 1:1, and is preferably about 5:1.
• the quaternary ammonium compound is present in releasable combination with the compositions herein.
• releasable combination is meant that, on admixture with water, the soluble components of the composition granules dissolve and the clay and quaternary compound are independently suspended in the aqueous medium.
• compositions herein preferably provide a solution pH of from about 7 to about 12 when dissolved in water at a concentration of about 0.12 percent by weight.
• the invention encompasses methods for concurrently cleansing, softening and providing antistatic effects on fibers and fabrics comprising laundering said fibers or fabrics in an aqueous laundry bath containing an effective amount (e.g., from about 0.02 to about 2 percent by weight) of a laundry detergent composition as described above.
• compositions and processes of this invention employ four essential ingredients: the water-soluble detergency compound; the detergency builder; the clay softener; and the quaternary ammonium anti-static agent.
• the detergency compound functions in standard fashion to remove soil from fabrics being laundered.
• the detergency builder functions both to enhance the cleansing action of the detergency compound and to uniformly disperse the clay softener.
• the smectite-type clay functions to soften the laundered fabrics.
• the quaternary ammonium compound provides anti-static effects on the fabrics and adds an increment of softening benefits to the fabrics.
• the quaternary ammonium anti-static agents are employed in the instant compositions at a concentration of from about 0.5 to about 15 percent, preferably from about 0.5 to about percent by weight, and are therefore present in the laundering liquors at levels from about 5 ppm to about 150 ppm.
• the quaternary anti-stats are used at a clay-to-quaternary weight ratio of from about 40:1 to about 1:1, preferably about 5:1.
• the anti-static agents of this invention are quaternary ammonium salts of the formula wherein each R group is a hydrocarbyl (i.e., alkyl or alkenyl) group containing from about ID to about 22 car bon atoms and each R group is a short-chain hydrocarbyl group containing from 1 to about 4 carbon atoms.
• X in the above compounds can be any saltforming anion, e.g., halide, hydroxide, sulfate, carbonate, phosphate, etc.
• the charge on the anion is designated as n, where n is 1-3.
• the number of cationic ammonium groups, n will equal the charge, n, on the anion to provide electrical neutrality.
• the quaternary ammonium anti-static agents herein are characterized by their limited solubility in water. That is to say, such quaternary salts are essentially insoluble in water, existing therein in what appears to be the mesomorphic liquid crystalline state.
• the insolubility of the quaternary salts used herein is a critical aspect of this invention inasmuch as water-soluble quaternary salts become chemically affixed to the surface of the clay or react with the preferred anionic surfactants.
• the quaternary anti-static agent is affixed to the surface of the clay, or has reacted with the anionic surfactant, it does not provide the desired antistatic effects on fabics.
• Quaternary ammonium compounds are not generally considered to be useful in combination with anionic surfactants since the opposite charges on these two types of compounds cause them to react and precipitate from solution. Yet, the anionics are a preferred class of surfactants for laundering fabrics. Surprisingly, it has now been found that the desirable anti-static effects of the insoluble quaternary ammonium com pounds used herein are not negated when employed in combination with anionic surfactants. Apparently. the insoluble nature of the di-long chain quaternary compounds renders them somewhat compatible with anionics; whatever the reason, the quaternary ammonium anti-stats herein perform their anti-static function when used in combination with clays and anionic surfactants.
• the quaternary ammonium anti-static agents used in this invention can be prepared in various ways wellknown in the art. Many such materials are commercially available.
• the quaternaries are often made front alkyl halide mixtures corresponding to the mixed alkyl chain lengths in fatty acids.
• the ditallow quaternaries are made from alkyl halides having mixed C -C chain lengths. Such mixed di-long chain quaternaries are useful herein and are preferred from a cost standpoint.
• any anionic group can be the counter-ion in the quaternary compounds used herein.
• the anionic groups in the quaternary compounds can be exchanged, one for another, using standard anion exchange resins.
• quaternary ammonium salts having any desired anion are readily available. While the nature of such anions has no effect on the compositions and processes of this invention, chloride ion is the preferred counter-ion from a cost standpoint.
• substantially water-insoluble quaternary ammonium antistatic agents suitable for use in the compositions and processes of the instant invention. All of the quaternary ammonium compounds listed can be formulated in rcleasable combination with the detergent compositions herein, but the compilation of suitable quaternary compounds hereinafter is only by way of example and is not intended to be limiting of such compounds.
• Ditallowdimethylammonium chloride is an especially preferred quaternary anti-static agent for use herein by virtue of its low cost, low solubility and high-anti-static activity; other useful di-long chain quaternary compounds are dicetyldimethylammonium chloride; bis-docosyldimethylammonium chloride; didecyldimethylammonium chloride; ditallowdimethylammonium bromide; dioleoyldimethylammonium hydroxide; ditallowdiethylammonium chloride; ditallowdipropylammonium bromide; ditallowdibutylammonium fluoride, cetyldecylmethylethylammonium chloride, bis- [ditallowdimethylammonium lsulfate; tris- [ditallowdimethylammonium]-phosphate; and the like.
• Synthetic Detergent From about 2 to about 30 percent by weight, preferably from about 5 to about 20 percent by weight, of the instant compositions comprise a non-soap synthetic detergent selected from the group consisting of anionic synthetic detergents, nonionic synthetic detergents, ampholytic synthetic detergents, and zwitterionic synthetic detergents. Examples of synthetic detergents of these types are described as follows:
• Anionic Detergents include watcr-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a moiety selected from the group consisting of sulfonic acid and sulfuric acid ester moieties.
• alkyl is the alkyl portion of higher acyl moieties.
• this group of synthetic detergents which form a part of the preferred built detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 20 carbon atoms in straight chain or branched-chain configuration, e.g., those of the type described in U.S. Pat. Nos.
• Anionic phosphate surfactants are also useful in the present invention. These are surface active materials having substantial detergent capability in which the anionic solubilizing group connecting hydrophobic moieties is an oxy acid of phosphorus.
• the more common solubilizing groups are -SO,,H and SO H.
• Alkyl phosphate esters such as (RO) PO H and R0- PO H in which R represents an alkyl chain containing from about 8 to about carbon atoms are useful herein.
• phosphate esters can be modified by including in the molecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units.
• Formulae for these modified phosphate anionic detergents are formula 0 n OCR CH CH SO M where R is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group); R is alkyl of 1 to about 8 carbon atoms; and M is a water-soluble cation.
• the water-soluble cation, M, in the hereinbefore described structural formula 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-, and trimethylammonium 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.
• beta-acyloxy-alkancl sulfonates or alternatively 2-acyloxy-alkanel sulfonates, useful herein include the sodium salt of 2 acetoxy-tridecane-l-sulfonic acid; the potassium salt of 2-propi0nyloxy-tetradecane-l-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxypentadccane-1- sulfonic acid; the sodium salt of 2-acetoxy-hexadecancl-sulfonic acid; the potassium salt of 2octanoyloxytetradecane-l-sulfonic acid; the sodium salt of 2- acetoxy-heptadecane-l-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-l-sulfonic acid; the potassium salt of 2-acetoxy-
• beta-acyloxy-alkane-l-sulfonate salts herein are the alkali metal salts of beta-acetoxy-alkanel-sulfonic acids corresponding to the above formula wherein R is an alkyl of about 12 to about 16 carbon atoms, these salts being preferred from the standpoints of their excellent cleaning properties and ready availability.
• alkylated a-sulfocarboxylates containing about 10 to about 23 carbon atoms, and having the formula R II OR wherein R is C to C alkyl, M is a water-soluble cation as hereinbefore disclosed, preferably sodium ion, and R is short-chain alkyl, e.g., methyl, ethyl, propyl, and butyl.
• R is C to C alkyl
• M is a water-soluble cation as hereinbefore disclosed, preferably sodium ion
• R is short-chain alkyl, e.g., methyl, ethyl, propyl, and butyl.
• alkylated a-sulfocarboxylates preferred for use herein include:
• lithium methyl-a-sulfolaurate as well as mixtures thereof.
• a preferred class of anionic organic detergents are the B-alkyloxy alkane sulfonates. These compounds have the following formula:
• R H l 2 I R p g, .Jo rr where R is a straight chain alkyl group having from 6 to 20 carbon atoms, R is a lower alkyl group having from I (preferred) to 3 carbon atoms, and M is a watersoluble cation as hereinbefore described.
• Balkyloxy alkane sulfonates or alternatively 2-alkyloxy-alkane-l-sulfonates, having low hardness (calcium ion) sensitivity useful herein to provide superior cleaning levels under household washing conditions include:
• alkyl ether sulfates Other synthetic anionic detergents useful herein are alkyl ether sulfates. These materials have the formula RO(C H.,O),SO M wherein R is alkyl or alkenyl of about 10 to about carbon atoms, x is 1 to 30, and M is a watersoluble cation as defined hereinbefore.
• the alkyl ether sulfates useful in the present invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms. Preferably, 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 6, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 6 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
• alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulfate; lithium tallow alkyl triethylene glycol ether sulfate; and sodium tallow alkyl hexaoxyethylene sulfate.
• alkali metal coconutand tallow-alkyl oxyethylene ether sulfates having an average of about 1 to about 10 oxyethylene moieties.
• the alkyl ether sulfates of the present invention are known compounds and are described in US Pat. No. 3,332,876, to Walker (July 25, 1967), incorporated herein by reference.
• anionic non-soap synthetic detergents which come within the terms of the present detergents, which come within the terms of the present invention, are the compounds which contain two anionic functional groups. These are referred to as dianionic detergents.
• Suitable di-anionic detergents are the disulfonates, disulfates, or mixtures thereof which may be represented by the following formulae:
• R is an acyclic aliphatic hydrocarbyl group hav ing 15 to 20 carbon atoms and M is a water-solubilizing cation, for example, the C to C20 disodium 1,2- alkyldisulfates, C to C dipotassium-l,2-alkyldisulfonates or disulfates, disodium l,9-hexadecyl disulfates, C to C disodium-l ,2-alkyldisulfonates, disodiuum 1,9-stearyldisulfates and 6,lO-octadecyldisulfates.
• M is a water-solubilizing cation
• the aliphatic portion of the disulfates or disulfonates is generally substantially linear, thereby imparting desirable biodegradable properties to the detergent compound.
• the water-solubilizing cations include the customary cations known in the detergent art, i.e., the alkali metals, and the ammonium cations, as well as other metals in group [1A, IIB, lllA, IVA and NE of the Periodic Table except for boron.
• the preferred watersolubilizing cations are sodium or potassium.
• Still another anionic synthetic detergents include the class designated as succinamates.
• This class includes such surface active agents as disodium N-octadecylsulfosuccinamate; tetrasodium N-( l ,2-dicarboxyethyl)-N- octadecylsulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.
• 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 in conditions such that any sultones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates.
• the sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid S0 chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 etc., when used in the gaseous form.
• inert diluents for example by liquid S0 chlorinated hydrocarbons, 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 olefin sulfonates 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; l-eicosene and l-tetracosene.
• the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.
• preferred compounds include sodium linear alkyl benzene sulfonate wherein the alkyl chain averages from about to 18, more preferably about 12, carbon atoms in length, sodium tallow alkyl sulfate; 2-acetoxytridecane-l-sulfonic acid; sodium methyl-asulfopalmitate; sodium B-methoxyoctadecylsulfonate; sodium coconut alkyl ethylene glycol ether sulfonate; the sodium salt of the sulfuric acid ester of the reaction product of one mole of tallow alcohol and three moles of ethylene oxide; and mixtures thereof.
• nonionic surfactants are compounds produced by the condensation of an alkylene oxide (hydrophilic in nature) with an organic hydrophobic compound which is usually aliphatic or alkyl aromatic in nature.
• the length of the hydrophilic of polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
• Another type of nonionic surfactants are the so-called polar nonionics derived from amine oxides, phosphine oxides or sulfoxides. Examples of suitable nonionic surfactants include:
• the polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the 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 may be derived, for example, from polymerized propylene, 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 moles of ethylene oxide per mole of phenol, di-isooctylphenol condensed with about 15 moles of ethylene oxide per mole of phenol.
• Commercially available nonionic surfactants of this type include lgepal CO-6l0 marketed by the GAP Corporation; and Triton X-45, X-l l4, X-100 and X- 102, all marketed by the Rohm and Haas Company.
• the condensation products of aliphatic alcohols with ethylene oxide may either be straight or branched and generally contains from about 8 to about 22 carbon atoms.
• ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of tridecanol, myristyl alcohol condensed 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 23-65 marketed by the Shell Chemical Company and Kyro EOB marketed by the Procter & Gamble Company.
• the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
• the hydrophobic portion of these compounds has a molecular weight of from about 1,500 to 1,800 and of course exhibits water insolubility.
• the addition of polyoxycthylene 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.
• Examples of compounds of this type include certain of the commercially available Pluronic surfactants marketed by the Wyandotte Chemicals Corporation.
• the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine consist of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of from about 2,500 to about 3,000.
• This base is condensed with ethylene oxide to the extent that the condensation product contains from about 40 to about percent by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
• Examples of this type of nonionic surfactant include certain of the commercially available Tetronic compounds marketed by the Wyandotte Chemicals Corporation.
• Surfactants having the formula RR RN O (amine oxide surfactants) wherein R is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R' which is an alkyl group containing from about 10 to about 18 carbon atoms and no ether linkages, and each R and R is selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms,
• amine oxide surfactants include: dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(Z-hydroxyethyl)dodecylamine oxide, bis- (2-hydroxyethyl)-3-dodecoxy-l-hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-(2- hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.
• Surfactants having the formula RR R P O phosphine oxide surfactants
• R is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R which is an alkyl group containing from about 10 to about 18 carbon atoms and no ether linkages, and each R and R is selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms.
• phosphine oxide detergents include: dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide, dipropyldodecylphosphine oxide, bis-(hydroxymethyl)- dodecylphosphine oxide, bis-(2-hydroxyethyl)dodecylphosphine oxide, (2-hydroxypropyl)methyltetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-(2-hydroxy-dodecyl)phosphine oxide and the
• sulfoxide surfactants include octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxy- 4-dodecoxybutyl methyl sulfoxide, octadecyl 2- hydroxyethyl sulfoxide, and dodecylethyl sulfoxide.
• nonionic surfactants include the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide per mole of nonyl phenol, the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide per mole of coconut fatty alcohol, the condensation product of tallow fatty alcohol with about 1 1 moles of ethylene oxide per mole of tallow fatty alcohol and the condensation product of a secondary fatty alcohol containing about carbon atoms with about 9 moles of ethylene oxide per mole of fatty alcohol.
• Ampholytic Synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be staight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g.,
• Zwitterionic Synthetic Detergents containing from about 3 to 18 carbon atoms and at least one aliphatic substituent containing an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfato, phosphato, or phosphono.
• anionic water-solubilizing group e.g., carboxy, sulfonate, sulfato, phosphato, or phosphono.
• R is alkyl, alkenyl or a hydroxyalkyl containing from about 8 to about 18 carbon atoms and containing if desired up to about 10 ethylene oxide moieties and/or a glyceryl moiety
• Y is nitrogen, phosphorus or sulfur
• R is alkyl or monohydroxyalkyl containing 1 to 3 carbon atoms
• x is 1 when Y is S, 2 when Y vis N or P
• R is alkylene or hydroxyalkylene containing from 1 to about 5 carbon atoms
• Z is a carboxy, sulfonate, sulfate, phosphate or phosphonate group.
• Zwitterionic surfactants include 3-(N,N-dimethyl-N-hexadecylammonio )-propanel sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2- hydroxypropane-l-sulfonate; 2-(N,N-dimethyl-N- dodecy'lammonio)ace tate; 3-(N,N-dimethyl-N- dodecylammonio)propionate; 2-(N,N-dimethyl-N- octadecylammonio)ethane-l-sulfate; 3-(P,P-dimethyl- P-dodecylphosphonio)propane-lsulfonate; 2(S- methyl-S-tert-hexadecylsulfonio)ethane-1-sulfonate; 3-(S-methyl-S-dode
• Preferred compounds of this class from a commercial standpoint are 3-(N,N-dimethyl-N- hexadecylammonio)-2-hydroxypropanel -sulfonate; 3-(N,N-dimethyl-N-alkylammonio)-2- hydroxypropane-l-sulfonate; the alkyl group being derived from tallow fatty alcohol; 3-(N,N-dimethyl-N- hexadecylammonio )propanel -sulfonate; 3-( N ,N- dimethyl-N-tetradecylammonio)propanel -sulfonate; 3-(N,N-dimethyl-N-alkylammonio-Z-hydroxypropanel-sulfonate, the alkyl group being derived from the middle cut of coconut fatty alcohol; 3-(N,N- dimethyldodecylammonio )-2-hydroxypropanesulfonate; 4-(N,N-di
• R is an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group containing from 10 to 20 carbon atoms
• M is a bivalent radical selected from the group consisting of aminocarbonyl, carbonylamino, carbonyloxy, aminocarbonylamino, the corresponding thio groupings and substituted amino derivatives
• R and R are alkylene groups containing from 1 to 12 carbon atoms
• R is alkyl or hydroxyalkyl containing from 1 to carbon atoms
• R is selected from the group consisting of R groups R,,-MR and R COOMe wherein R R R R and R are as defined above and Me is a monovalent salt-forming cation.
• Compounds of the type include N,- N-bis(oleylamidopropyl)-N-methyl-N-carboxymethylammonium betaine; N,N-bis(stearamidopropyl-N- methyl-N-carboxymethylammonium betaine; N- (stearamidopropyl)-N-dimethyl-N-carboxymethylammonium betaine; N,N-bis(oleylamidopopy1)-N-(2- hydroxyethyl)-N-carboxylmethylammonium betaine; and N-Nbis-(stearamidopropyl)-N-(2-hydroxyethyl)- N-carboxymethylammonium betaine.
• Zwitterionic surfactants of this type are preparing in accordance with methods described in US. Pat. No. 3,265,719 and DAS 1,018,421.
• R9 cu (CI-I CH so wherein R is an alkyl group, R is a hydrogen atom or an alkyl group, the total number of carbon atoms in R and R being from 8 to 16 and o i 2 R 11 12 13 wherein R is an alkarylmethylene group containing from about 8 to 24 carbon atoms in the alkyl chain; R is selected from the group consisting of R groups and alkyl and hydroxyalkyl groups containing from 1 to 7 carbon atoms; R is alkyl or hydroxylakyl containing from 1 to 7 carbon atoms; R is alkylene or hydroxyalkylene containing from 1 to 7 carbon atoms and Z is selected from the group consisting of sulfonate. carboxy and sulfate.
• Examples of zwitterionic surfactants of this type include 3-(N-d0decylbenzyl-N,N- dimethylammonio)propane-l -sulfonate; 4-( N- dodecylbenzyl-N,N-dimethylammonio)butanel sulfonate; 3-(N-hexadecylbenzyl-N,N- dimethylammonio)propane-l-sulfonate; 3-(N- dodecylbenzyl-N,N-dimethylammonio)propionate; 4- (N-hexadecylbenzyl-N,N-dimethylammonio)butyrate; 3-(N-tetradecylbenzyl-N,N-dimethylammonio)propane-l-sulfate; 3-(N-dodecylbenzylN,N- dimethylammonio)-2-hydroxypropane-l-sulfonate
• R is an alkylphenyl cycloalkylphenyl or alkenylphenyl group containing from 8 to 20 carbon atoms, in the alkyl, cycloalkyl or alkenyl moiety;
• R and R are each aliphatic groups containing from 1 to 5 carbon atoms;
• R and R are each hydrogen atoms, hydroxyl groups or aliphatic groups containing from 1 to 3 carbon atoms and
• R is an alkylene group containing from 2 to 4 carbon atoms.
• Examples of zwitterionic surfactants of this type include 3-(N-dodecylphenyl-N,N- dimethylammonio)propane-l-sulfonate; 4-(N- hexadecylphenyl-N,N-dimethyl )butanel -sulfonate; 3-(N-tetradecylphenyl-N,N-dimethylammonio)-3,3- dimethylpropane-l-sulfonate and 3-(N-dodecylphenyl- N ,N-dimethylammonio )-3 -hydroxypropane- 1 sulfonate.
• Compounds of this type are described more fully in British Pat. Nos. 970,883 and 1,046,252, incorporated herein by reference.
• preferred compounds include 3-(N,N- dimethyl-N-alkylammonio)-propane-1-sulfonate and 3(N,N-dimethyLN-alkylammonio)-2hydroxypropanel-sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl- N-hexadecylammonio)-propane-l-sulfonate; 3(N,N- dimethyl-N-hexadecylammonio)-2-hydroxypropane-lsulfonate; 3-(N-dodecylbenzyl-N,N-
• dodecylbenzyl-N,N-dimethylammonio)propionate 6- (N-dodecylbenzyLN ,N-dim ethylammonio )hexanoate; and (N,N-dimethyl-N-hexadecylammonio)acetate.
• the detergent compositions of the instant invention contain, as an essential component, an alkaline, polyvalent anionic detergent builder salt.
• these water-soluble alkaline builder salts serve to maintain the pH of the laundry solution in the range of from about 7 to about 12, preferably from about 8 to about ll.
• these builder salts enhance the fabric cleaning performance of the overall compositions while at the same time serve to suspend particulate soil release from the surface of the fabrics and prevent its redeposition on the fabric surfaces.
• the detergency builder salts serve to suspend clay soils of the kaolinite and illite types and prevent their redeposition on fabrics, they do not appear to interfere with the deposition on fabric surfaces of the smectite-type clay softeners used herein.
• these polyanionic builder salts have been found to cause the smectite-type clays present in the granular detergent formulations of the invention to be readily and homogeneously dispersed throughout the aqueous landering medium with a minimum of agitation. The homogeneity of the clay dispersion is necessary for the clay to function effectively as a fabric softener, while the ready dispersability allows granular detegent compositions to be formulated.
• Suitable detergent builder salts useful herein can be of the poly-valent inorganic and poly-valent organic types, or mixtures thereof.
• suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, polyphosphates, tripolyphosphates, bicarbonates, silicates and sulfates.
• Specific examples of such salts include the sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, orthophosphates and hexametaphosphates.
• organic alkaline detergency builder salts are: (l) water-soluble amino polyacetates, e.g., sodium and potassium ethylenediamine tetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g., so dium and potassium phytates; (3) water-soluble polyphosphonates, including, sodium, potassium and lithium salts of ethane-l-hydroxy-l,l-diphosphonic acid; sodium, potassium and lithium salts of methylenediphosphonic acid and the like.
• Additional organic builder salts useful herein include the polycarboxylate materials described in U.S. Pat. No. 2,264,103, including the water-soluble alkali metal salts of mellitic acid.
• the water-soluble salts of polycarboxylate polymers and copolymers such as are described in U.S. Pat. No. 3,308,067, incorporated herein by reference, are also suitable herein.
• alkali metal salts of the foregoing inorganic and organic poly-valent anionic builder salts are preferred for use herein from an economic standpoint, the ammonium, alkanolammonium, e.g., triethanol ammonium, diethanol ammonium, and the like, water-soluble salts of any of the foregoing builder anions are useful herein.
• Mixtures of organic and/or inorganic builders can be used herein.
• One such mixture of builders is disclosed in Canadian Pat. No. 755,038, e.g., a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane-l-hydroxy-l,l-diphosphonate.
• sodium tripolyphosphate sodium nitrilotriacetate, sodium mellitate, sodium citrate and sodium carbonate are preferred herein for this builder use.
• Sodium tripolyphosphate is especially preferred herein as a builder both by virtue of its detergency builder activity and its ability to homogeneously and quickly disperse the smectite clays throughout the aqueous laundry media without interfering with clay deposition on the fabric surface.
• Sodium tripolyphosphate is also especially effective for suspending illite and kaolinite clay soils and retarding their redeposition on the fabric surface.
• the detergent builders are used at concentrations of from about 10 percent to about 60 percent, preferably 20 percent to 50 percent, by weight of the detergent compositions of this invention.
• the fourth essential component of the present compositions consists of particular smectite clay materials to provide fabric softening concurrently with fabric cleansing. These smectite clays are present in the detergent compositions at levels from about 1 percent to about 50 percent, preferably from 5 percent to l5 percent by weight, of the total compositions.
• the clays used herein are impalpable," i.e., have a particle size which cannot be perceived tactilely.
• lmpalpable clays have particle sizes below about 50 microns; the clays used herein have a particle size range of from about 5 microns to about 50 microns.
• the clay minerals used to provide the softening properties of the instant compositions can be described as expandable, three-layer clays, i.e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least 50 meg/ g. of clay.
• expandable as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water.
• the three-layer expandable clays used herein are those materials classitied 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, magne sium oxide is present in the silicate crystal lattice.
• the general formulas of these smectites are Al (Si O (OH) and Mg (Si O (OH) 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 silicate lattice structure.
• the three-layer, expandable alumino-silicates useful herein are futher characterized by a dioctahedral crystal lattice, while the expandable three-layer magnesium silicates have a trioctahedral crystal lattice.
• the clays employed in the compositons of the instant invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ion, magnesium ion, and the like. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed.
• a sodium clay is one in which the absorbed cation is predominantly sodium.
• Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions.
• a typical exchange reaction involving a smectite-type clay is expressed by the following equation:
• smectite clay Na
• NH OHZ smectite clay HN NaOH Since in the foregoing equilibrium reaction, one equivalent weight of ammonium ion replaces an equivalent weight of sodium, it is customary to measure cation exchange capacity (sometimes termed base exchange capacity) in terms of milliequivalents per 100 g. of clay (meg/100 g.).
• the cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration or by a methylene blue procedure, all as fully set forth in Grimshaw, The Chemistry and Physics of Clays, pp. 264-265, Interscience (1971).
• the cation exchange capacity of a clay mineral relates to such factors as the expandable properties of the clay, the charge of the clay, which, in turn, in determined at least in part by the lattice structure, and the like.
• the ion exchange capacity of clays varies widely in the range from about 2 meg/100 g. for kaolinites to about 150 meg/100 g., and greater, for certain clays of the montmorillonite variety.
• Illite clays have an ion exchange capacity somewhere in the lower portion of the range, i.e., around 26 meg/100 g. for an average illite clay.
• illite and kaolinite clays are not useful in the instant compositions. Indeed, such illite and kaolinite clays constitute a major component of clay soils and, as noted above, are removed from fabric surfaces by means of the instant compositions.
• smectites such as nontronite, having an ion exchange capacity of approximately 50 meg/ 100 g.
• saponite which has an ion exchange capacity of around 70 meg/100 g.
• montmorillonite which has an ion exchange capacity greater than 70 meg/100 g.
• clay minerals useful herein can be characterized as expandable, three-layer smectite-type clays having an ion exchange capacity of at least about 50 meg/100 g.
• smectite clays used in the compositions herein are all commerically available.
• Such clays include, for example, montmorillonite, volchonskoite, nontronite,
• smectite-type minerals obtained under the foregoing tradenames can comprise mixtures of the various discreet mineral entities. Such mixtures of the smectite minerals are suitable for use herein.
• smectite-type clays having a cation exchange capacity of at least about 50 meg/ g. are useful herein, certain clays are preferred.
• Gelwhite GP is an extremely white form of smectite clay and is therefore preferred when formulating white granular detergent compositions.
• Volclay BC which a smectite-type clay mineral containing at least 3 percent 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 product performance.
• certain smectite clays marketed under 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 by virtue of the fact that smectites exhibit a true 14A x-ray diffraction pattern. This characteristic pattern, taken in combination with exchange capacity measurements performed in the manner noted above, provides a basis for selecting particular smectite-type minerals for use in the granular detergent compositions disclosed herein.
• the detergent compositions disclosed herein can contain other materials commonly used in such compositions.
• various soil-suspending agents such as carboxymethylcellulose, corrosion inhibitors, dyes, fillers such as sodium sulfate and silica, optical brighteners, suds boosters, suds depressants, germicides, anti-tarnishing agents, pl-I adjusting agents such as sodium silicate, enzymes, and the like, well-known in the art for use in detergent compositions, can also be employed herein.
• Bound water can also be present in said detergent compositions.
• the clay-containing detergent compositions of this invention are in granular form.
• the compositions can be conveniently prepared in standard fashion by admixing the detergent compound, clay and optional ingredients in a crutcher and spray-drying the mixture to form granules.
• the quaternary ammonium anti-static agent can be sprayed on the granules from a melt. It is a critical aspect of this invention to avoid affixing the quaternary compound to the surface of the clay by an ion exchange mechanism; accordingly, it is preferable to avoid spraying the detergent granules with an aqueous solution or suspension of the quaternary compound.
• the ion-exchange problem is avoided by employing a melt of the quaternary compound to spray the granules.
• the compositions are then added to water to provide a laundering liquor containing the instant compositions to the extent of from about 0.02 percent to about 2 percent by weight.
• Soiled fabrics are added to the laundering liquor and cleansed in the usual manner.
• the effective amount of the detergent compositions to be used will depend to an extent on the weight of clothes being laundered and their degree of soiling.
• Aqueous laundering baths containing said compositions provide adequate cleaning, softening and anti-static benefits with soiled fabrics, especially cotton and cotton/polyester blends.
• the suspended clay material in the laundering liquor also serves to adsorb fugitive dyes in solution, thereby reducing or inhibiting dye transfer.
• the granular built detergent compositions and processes of the instant invention are illustrated by the following examples.
• the following test is used to assess through-the-wash anti-static efficacy of the test products.
• a bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35 polyester/cotton blend; 17% nylon; 18% Dacron”) is washed for minutes in a miniature agitator containing two gallons of aqueous washing liquor containing the test laundry compositions (as set forth, below).
• the laundering temperature is 100F; water hardness 7 gr/gal. artificial hardness.
• the bundle comprises 5% by weight of the washing liquor.
• the bundle is spun dry and rinsed for two minutes in two gallons of water at 100F and 7 gr/gal. hardness.
• the fabrics are then dried in a commercial dryer for 50 minutes.
• the static charge on each fabric is then measured by a standard electrostatic technique.
• the sum of the absolute values of the charges on all fabrics in the bundle, divided by the sum of the area (yards of the total fabric surface (2 sides of the fabric) is then computed.
• This so-called static value in volts/yd, correlates with gross observations of the effects of static charges on fabric surfaces, i.e., electrical shocks, fabric clinging, etc.
• no static cling is exhibited by fabrics having a static value of less than about 1.5 v./yd substantial static cling is noted in fabrics having a static value above about 4.5 v./yd.
• Composition A Component Weight Percent Anionic surfactant 16.6 Sodium tripolyphosphate 43.3 Sodium silicate 5.8 Sodium sulfate 10.0 Gelwhite GP 9 8 Ditallowdimethylammonium chloride 2 0 Miscellaneous minors** Moisture 1.22:1 ratio of sodium tallow alkyl sulfatezsodium C linear alkyl benzene sulfonate "Including brightencrs. carboxymethylcellulose, coconut alcohol ethoxylate and perfume Composition A is prepared by admixing all components except the ditallowdimethylammonium chloride in a crutcher and spray-drying to form granules consisting of the surfactant, builder, clay, etc.
• composition B Component Weight Percent Anionic surfactant* 12.8 Sodium tripolyphosphate 37.8 Sodium silicate 4.5 Sodium sulfate 10.8 Volclay BC Ditallow dimethyl ammonium chloride 092 Miscellaneous minors 4.2 Moisture Balance 1.22:1 sodium tallow alkyl sulfatezsodium C, linear alkyl benzene sull'onalc "Including perfume, hrighteners, carhoxymelhylcellulnse and coconut hexaelhoxylate ca. 0.6%
• Composition B (prepared in the same manner as Composition A, above) was employed in the anti-static test set forth hereinabove. In this test, Composition B was used at a solution concentration of 0.131 percent by weight. Fabrics laundered in the aqueous bath containing Composition B were tested for static charge following each of two wash-rinse-drying cycle. After one cycle, fabrics laundered in Composition B had a static value of 1.2; after two cycles the static value was 1.7. As a point of comparison, fabrics laundered in a built, anionic detergent composition without clay or quaternary ammonium salt had a static value of 8.0 after the first cycle and 8.6 after the second cycle. Fabrics laundered in a built, anionic detergent composition containing a clay softener had a higher static value than fabrics laundered in liquors without clay.
• compositions herein provide substantial softening and anti-static benefits. Furthermore, the compositions herein overcome the problem associated with increased static charge buildup on fabrics laundered with detergents containing clay softeners, alone.
• compositions A and B of the instant invention also provide excellent cleaning and detergency when employed in washing solutions at the specified concentrations.
• Substantially similar detergency, softening and antistatic benefits are obtained when the anionic surfactant mixture in Compositions A and B is replaced with an equivalent amount of the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide per mole of nonyl phenol; the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide per mole of coconut fatty alcohol; the condensation product of tallow fatty alcohol with about 11 moles ethylene oxide per mole of tallow fatty 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 fatty alcohol, respectively.
• Substantially similar detergency, softening and antistatic benefits are obtained when the sodium tripolyphosphate builder in Compositions A and B is replaced with an equivalent amount of sodium nitrilotriacetate; sodium mellitate; sodium citrate; and sodium carbonate, respectively.
• Substantially similar detergency, softening and antistatic benefits are obtained when the clay softening agent in Compositions A and B is replaced with an equivalent amount of volchonskoite; nontronite; hectorite; sauconite; and vermiculite, respectively, all such clays having an ion-exchange capacity at least about 50 meg./ 100 g.
• Substantially similar detergency, softening and antistatic benefits are obtained when the quaternary ammonium anti-static agent in Compositions A and B is replaced by ditallowdimethylammonium bromide; ditallowdiethylammonium chloride; dioctadecyldibutylammonium chloride; and ditallowdimethylammonium hydroxide, respectively.
• the compositions provide still other advantages.
• the dye-transfer inhibition noted above is a significant advantage not commonly shared by ordinary laundering and fabric softening compositions.
• the particular class of clays described herein which are deposited on the fabrics provide a soil-release benefit.
• the clays are adsorbed by the fabrics being washed providing an improved soil-release surface.
• the benefit from this treatment is that during subsequent washings, stains and soils are more easily removed from the fabrics as compared to a fabric which has not previously been exposed to a treatment by the clay-containing compositions of this invention.
• all of these benefits are enjoyed without impairing the water-absorbent qualities of the treated fabric. This is in marked contrast with ordinary quanternary ammonium fabric softeners which reduce the water-absorbent property of treated fabrics after sev' eral fabric treatments.
• a granular, built laundry detergent composition comprising:
• a non-soap synthetic detergent compound selected from the group consisting of anionic synthetic detergents, nonionic synthetic detergents, ampholytic synthetic detergents, zwitterionic synthetic detergents and mixtures thereof;
• a substantially water-insoluble quaternary ammonium anti-static agent of the formula [R N R' ],,X", wherein each R is a hydrocarbyl group containing from about 10 to about 22 carbon atoms, each R is a hydrocarbyl group containing from 1 to about 4 carbon atoms, X is an anion and n is an integer from 1 to 3, at a weight ratio of said smectite-type clay to quaternary ammonium antistatic agent of from about 40:1 to about lzl;
• said quaternary ammonium compound being in releasable combination in said composition.
• the builder salt is selected from the group consisting of alkali metal carbonates, alkali metal borates, alkali metal phosphates, alkali metal polyphosphates, alkali metal tripolyphosphatcs, alkali metal bicarbonates, alkali metal sulfates, watersoluble amino polyacetates, water-soluble salts of phytic acid, and water-soluble polyphosponates, and is present at from about 20 percent to about 50 by weight;
• the smectite-type clay softening agent is selected from the group consisting of dioctahedral expandable three-layer alumino-silicates and trioctahedral expandable three-layer magnesium silicates and is present at from about 5 percent to about 15 percent by weight; and
• composition according to claim 1 wherein the smectite clay softening agent is selected from the group consisting of montmorillonites, volchonskoites, nontronites, hectorites, sauconites and vermiculites.
• composition according to claim 1 wherein the anionic surfactant is a water-soluble salt of an organic sulfuric reaction product containing an alkyl group of from about 8 to about 22 carbon atoms and a moiety selected from the group of sulfuric acid ester moieties and sulfuric acid ester moieties.
• a composition according to claim 1 wherein the builder salt is selected from the group consisting of sodium tripolyphosphate, sodium nitrilotriacetate, sodium mellitate, sodium citrate and sodium carbonate.
• composition according to claim 1 wherein the anti-static agent is ditallowdimethylammonium chloride.
• composition according to claim 6 wherein the smectite-type clay softening agent is montmorillonite.
• composition according to claim 6 wherein the smectite-type clay softening agent is Gelwhite GP.
• composition according to claim 6 wherein the smectite-type softening agent is Volclay BC,
• a granular, built laundry detergent composition comprising:
• a process for simultaneous laundering softening, and providing anti-static benefits to fabrics comprising contacting said fabrics with an aqueous medium containing from about 0.02 percent by weight to about 2 percent by weight of a composition in accordance with

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• 1972
  • 1972-11-10 US US305416A patent/US3862058A/en not_active Expired - Lifetime
• 1973
  • 1973-11-02 PH PH14184A patent/PH10878A/en unknown
  • 1973-11-05 CA CA184,962A patent/CA1016707A/en not_active Expired
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