Detergent compositions containing water insoluble starch

Abstract

Laundry detergent compositions comprising an organic surface-active agent and low concentrations of substantially water-insoluble granular starch; said compositions imparting anti-wrinkling, ease of ironing, softness (enhanced bulkiness), and anti-static effects to fabrics washed therein. In a preferred embodiment, the inventive compositions in addition contain a Smectite-type clay capable of further softening (providing lubricity to) fabrics laundered therein.

Description

BACKGROUND OF THE INVENTION

This invention relates to laundry detergent compositions which comprise in addition to conventional organic surface-active components a substantially water-insoluble starch in granular form.

Modern laundry detergent compositions, machinery and adjunct chemical additives, e.g., fabric softeners, washing machines and dryers, are haphazardly aimed at achieving benefits other than the obvious goal of rendering a clean wash. Among the benefits sought to be imposed upon the fabrics carried through an entire cycle from washing to drying are fluffiness, softness, body, reduced electrostatic charge, diminished wrinkling, and ease of ironing. No single product or machine process is presently available which will achieve all of these benefits simultaneously.

For example, present day fabric softeners impart a softness to the fabric (actually this softness is best likened to a tactile sensation of lubricity, which is distinguishable from fabric softness occasioned by enhanced fabric bulkiness) and control of electrostatic charge. Modern day washing machines and dryers by means of elaborate cycles and temperature control are able to markedly improve the extent of fabric wrinkling. Other products such as the well-known laundry starches impart, when applied after the washing cycle, an ease of ironing benefit and impart a body to the fabric, i.e., a sizing effect.

The detergent compositions of this invention, however, impart all of these benefits simultaneously through the wash. That is, the laundry compositions of this invention, by some imperfectly understood physico-chemical interaction at the fiber or yarn level, impart through the wash cycle the above enumerated benefits. These benefits are solely attributable to the presence of starch granules hereinafter defined in combination with organic surface-active agents.

Detergent compositions comprising starch are not new per se. It has long been known that gross quantities of starch by means of its gel-forming character impart desirable physical properties to toilet soap bars. Also, the properties of starch as a binding agent, as an agglomerating agent, as a film-forming agent, and as an inert diluent have been exploited in granulated detergent compositions. Starch and starch derivatives have also been used in gross amounts in synthetic detergent compositions to improve the efficiency of the prilling process, that is, formation of the detergent granule from the aqueous medium in which it was either synthesized or resolubilized. For these prior art purposes there is no criticality as to the integrity, size or freeness (discreteness) of the starch granule. In fact, the starch for such prior art processes is typically modified by degradation or derivatization to enhance its water solubility and film-forming propensities. In any event, prior art detergent compositions comprising some form of starch are characteristically of poor deterging power and impart a harsh stiffness to fabrics.

Accordingly, it is an object of the present invention to provide starch-containing detergent composition which impart anti-wrinkling, ease of ironing, fabric softening (herein, the term "softening" is related to increased bulkiness), anti-static, folding ease and enhanced fabric drapability effects to fabrics laundered therein.

It is an additional object of the present invention to provide detergent compositions capable of simultaneously cleaning and softening fabrics washed therein with a view to obtaining a degree of softening (lubricity), comparable to what results from the use of rinse softeners applied subsequently to conventional washing, i.e., during the rinsing operation.

By utilizing certain materials capable of conferring desirable fabric benefits when present in combination with organic surface-active agents, these above-described objectives can now be attained and laundry detergent compositions formulated which are capable of simultaneously cleaning the fabrics laundered therein and also imparting to these fabrics a series of desirable properties including anti-wrinkling, ease of ironing, fabric softening, anti-static, folding ease and enhanced fabric drapability properties.

SUMMARY OF THE INVENTION

The instant invention provides detergent compositions which are capable of concurrently cleansing and imparting desirable fabric properties to the fabrics laundered therein. Such compositions comprise:

a. from about 4% to about 60% by weight of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergent and mixtures thereof; and

b. from 0.1% to about 6% by weight of granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65.degree.C.

In a preferred embodiment, the inventive compositions contain, in addition to the essential ingredients referred to hereinbefore, from about 1% to about 50% by weight of a smectite-type clay having an ion-exchange capacity of at least about 50 meg/100 grams.

In its method aspects this invention relates to a method for treating fabrics to simultaneously cleanse and impart anti-wrinkling, ease of ironing, softening and anti-static properties. Such a method comprises treating fabrics in an aqueous liquor comprising:

a. from about 10 ppm (parts per million) to about 5000 ppm of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergent and mixtures thereof; and

b. from about 0.1 ppm to about 900 ppm of granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65.degree.C.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to detergent compositions capable of concurrently cleaning and imparting desirable textile properties to fabrics washed therewith.

These compositions comprise: (1) an organic surface-active agent and (2) a particular granular starch; in a preferred embodiment, the instant compositions also contain a smectite-type clay.

Unless indicated to the contrary, the "%" indications stand for "% by weight".

The essential starch component for use in the compositions of the instant invention is substantially water-insoluble, has an average particle diameter from 1.0 to about 45, preferably from about 5 to about 25 micrometers, and has a swelling power of less than about 15 at a temperature at 65.degree.C. The starch component is to be incorporated in an amount from 0.1% to about 6%, preferably from 0.2% to about 4%. Above the upper limit, the previously enumerated benefits derivable from the compositions of this invention are diminished to the extent that an undesirable stiffness to textiles laundered with the instant compositions occurs. This stiffness negative is attributable to high levels of starch, i.e., exceeding about the limits as claimed. The starch granules and fractures must be substantially structurally intact for properly performing their function within the compositions of the invention.

As explained hereinafter, however, without being limited as a result thereof, it is thought that the well-defined and firm shape of the granular starch particles in the laundering liquor is essential to the extent that said characteristics directly contribute to the beneficial fabric properties. Modification of the starch granule in a matter such as gelatinizing, derivatizing, or degrading is to be avoided to the extent it leads to starches which can lose their firm shape and also do not qualify for use in the present invention. Soluble or gelatinizable starches having a swelling power of more than about 15 at 65.degree.C are less suitable as they tend to lose their individual shape and consequently run into the fiber which, in turn, leads to undesirable stiffness of fabrics.

The swelling power is determined according to the method set forth in Cereal Chem., 36, pp. 534-544 (1959) Harry W. Leach, et al. Ten grams of starch is suspended in 180 ml. of distilled water in a tared 250-ml. centrifuge bottle. The suspension is mechanically stirred with a small stainless-steel paddle (0.75-inch wide, 1.5-inches high) at a rate just sufficient to keep the starch completely suspended (i.e., 200 r.p.m.) This low speed avoids shearing the fragile swollen granules and consequent solubilization of the starch. The bottle is lowered into a thermostatted water bath maintained at a temperature of 65.degree.C (.+-.0.1.degree.C.) and held for 30 minutes, slow stirring being continued during this period. The bottle is then removed, wiped dry, and placed on the torsion balance. The stirrer is removed and rinsed into the bottle with sufficient distilled water to bring the total weight of water present to 200.0 g. (including the moisture in the original starch). The bottle is stoppered, mixed by gentle shaking, and then centrifuged for 15 minutes at 2200 r.p.m. (i.e., 700 times gravity). The clear supernate is carefully drawn off by suction to within one-quarter inch of the precipitated paste. An aliquot of this supernate is evaporated to dryness on the steam bath and then dried for 4 hours in the vacuum oven at 120.degree.C. The percentage of solubles extracted from the starch is calculated to dry basis. The remaining aqueous layer above the sedimented starch paste is then siphoned off as quantitaively as possible. The bottle and paste are reweighed on the torsion balance, and the swelling power calculated as the weight of sedimented paste per g. of dry-basis starch.

Starches having a swelling power of more than 15 at 65.degree.C are not suitable for use in the instant composition. Although the final choice of starch which will meet requirements of this invention depends upon the origin of the material and also upon process conditions such as bleaching, degradation, and isolation applied to a given species, suitable starches can for example be obtained from corn, wheat, and rice. Current potato and tapioca starches have a swelling power exceeding 15 at a temperature of 65.degree.C and, therefore, are not suitable for being used in the compositions of this invention. More complete information concerning water-insoluble starches, the processes for their preparation and isolation from a variety of raw materials are well known [see for example, The Starch Industry, Knight, J. W. Pergamon Press, London (1969)].

These critical limitations as to the nature of the starch granule were determined initially by actual experimentation. While applicants will not be held by any theoretical interpretation of these critical limitations, it appears that the starch granules interact with the textile material at the fiber level to impart the above enumerated benefits to the textile fabric as a whole. In this respect it is to be noted that textile materials consist essentially of assemblies of fine flexible fibers arranged in more or less orderly geometrical arrays. Individual fibers within the assembly are usually in a bent or twisted configuration and are in various states of contact with neighboring fibers. When the assembly is deformed the fibers move relative to each other and this relative motion accounts to a large extent for the characteristic flexibility of textile materials. To what extent a given textile material will recover when a deforming force is removed is largely determined by the nature of the interaction of the individual fibers making up the textile material. Textile fibers are viscoelastic and hence will exhibit delayed recovery from strain. However, the large number of interfiber contact points provide frictional restraints which further hinder the recovery process. In most textile structures the area of interfiber contact is probably less than 1% of the total fiber area. The force per contact point is generally estimated to be within the range of 1 to 10 dynes.

It is with this view of textile materials that applicants hypothesis going to explain the efficacy of starch granules in imparting the related effects of anti-wrinkling, ease of ironing, softness (bulkiness) and anti-static benefits can be appreciated. For purposes of conceptualization this hypothesis will hereinafter be referred to as the "ball bearing effect". The conceptualization is useful in interpreting the interaction of the starch granules and the textile matrix under imposed forces of deformation.

By means of microscopic analysis and staining techniques, it has been determined that textile fabrics treated in accordance with the present invention are characterized by having discrete starch granules intimately dispersed, in a substantive fashion, in the interstices of the fiber matrix. It is believed that these starch granules, so interfiberly positioned, act in the manner of ball bearings to reduce interfiber forces during deformation of the textile fabric as a whole. The gross effect is the enhancement of visco-elastic recovery (anti-wrinkling effect) and diminution of the forces operable at interfiber contact points (ease of ironing effect). Under this conceptualization the starch granule diameter limitation is appreciated since most commercially available textile fibers have diameters which fall within the range of about 10 to about 30 micrometers. Therefore, to be effective, the starch granules of the invention must be comparable to the textile fiber diameters.

The above-mentioned benefits of softness (bulkiness) and anti-static effects are similarly related to the presence of the starch granule at points within interstices of individual fiber yarns. Microscopic examination of textile yarns in cross section reveals that textiles treated in accordance with the present invention have greater yarn diameters than similar textile yarns which are distinguishable by the absence of starch granules. Apparently, the starch granules positioned in the interfiber spaces effectively open up the yarn (apparent increase in bulk) resulting in a softer, fluffier textile fabric. The anti-static benefit appears to be related to moisture control occasioned by the copresence of starch granules in the textile fabric during machine drying, but effects conceptualized under the ball bearing hypothesis may also operate to diminish static buildup.

Doubtlessly, the so-called ball bearing effect is not exclusively operable in the obtainment of the above-identified benefits. The sole purpose in discussing such a hypothesis is to provide some common criteria for selection of starch materials encompassed by the detergent compositions of this invention. But by whatever mechanism the starch enables the above-identified benefits to be obtained, it is to be emphasized that the above-discussed hypothesis is in no way to be construed as a limitation upon the present invention.

The starch granules as a dry powder, can be admixed with a previously prepared detergent, or the starch granules as a cold water dispersion can be sprayed onto a previously prepared detergent formulation just prior to packaging. But in every case, the starch admixing step is subsequent to any moist heating step which might alter the native granular integrity of the starch granule.

The essential organic detergent suitable for use use in the compositions of the present invention is selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof. Said component is to be used in an amount from about 4% to about 60%, preferably from about 6% to about 40%.

Examples of suitable detergent compound which can be employed in accordance with the present invention include the following:

ANIONIC DETERGENTS

Water-soluble soaps. Suitable soaps include the sodium, potassium, ammonium and alkanolammonium (e.g., mono-, di-, and triethanolammonium) salts by higher fatty acids (C.sub.10 -C.sub.22). The sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps, are particularly useful.

Anionic synthetic detergents also include water-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. (Included in the term alkyl is the alkyl portion of higher acyl moieties.) Examples of 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 higher alcohols (C.sub.8 -C.sub.18 carbon atoms) produced by reducing 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. 2,220,099 and 2,477,383 (especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 11.8 carbon atoms and commonly abbreviated as C.sub.11.8 LAS); sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium and potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl groups contain from about 8 to about 12 carbon atoms.

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, of course, are --SO.sub.4 H and --SO.sub.3 H. Alkyl phosphate esters such as (R--O).sub.2 PO.sub.2 H and ROPO.sub.3 H.sub.2 in which R represents an alkyl chain containing from about 8 to about 20 carbon atoms are useful herein.

These 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 ##SPC1##

in which R represents an alkyl group containing from about 8 to 20 carbon atoms, or an alkylphenyl group in which the alkyl group contains from about 8 to 20 carbon atoms, and M represents a soluble cation such as hydrogen, sodium, potassium, ammonium or substituted ammonium; and in which n is an integer from 1 to about 40.

Another class of suitable anionic organic detergents useful in this invention includes salts of 2-acyloxyalkane-1-sulfonic acids. These salts have the formula ##SPC2##

where R.sub.1 is alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group); R.sub.2 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. Specific examples of substituted ammonium cations include methyl-, dimethyl-, and trimethyl-ammonium 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.

Specific examples of beta-acyloxy-alkane-1-sulfonates, or alternatively 2-acyloxy-alkane-1-sulfonates, useful herein include the sodium salt of 2-acetoxy-tridecane-1-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-1-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of 2-propionyloxy-docosane-1-sulfonic acid; the isomers thereof.

Preferred beta-acyloxy-alkane-1-sulfonate salts herein are the alkali metal salts of beta-acetoxy-alkane-1-sulfonic acids corresponding to the above formula wherein R.sub.1 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.

Typical examples of the above described beta-acetoxy alkanesulfonates are described in the literature: Belgium Pat. No. 650,323 issued July 9, 1963, discloses the preparation of certain 2-acyloxy alkanesulfonic acids. Similarly, U.S. Pat. Nos. 2,094,451 issued Sept. 18, 1937, to Guenther et al. and 2,086,215 issued July 6, 1937 to DeGroote disclose certain salts of beta-acetoxy alkanesulfonic acids. These references are hereby incorporated by reference.

Another class of anionic detergent compounds herein, both by virtue of superior cleaning properties and low sensitivity to water hardness (Ca++ and Mg++ ions) are the alkylated .alpha.-sulfocarboxylates, containing about 10 to about 23 carbon atoms, and having the formula ##SPC3##

wherein R is C.sub.8 to C.sub.20 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. These compounds are prepared by the esterification of .alpha.-sulfonated carboxylic acids, which are commercially available, using standard techniques. Specific examples of the alkylated .alpha.-sulfocarboxylates for use herein include:

ammonium methyl-.alpha.-sulfoplamitate,

triethanolammonium ethyl-.alpha.-sulfostearate,

sodium methyl-.alpha.-sulfopalmitate,

sodium ethyl-.alpha.-sulfopalmitate,

sodium butyl-60 -sulfostearate,

potassium methyl-.alpha.-sulfolaurate,

lithium methyl-.alpha.-sulfolaurate,

as well as mixtures thereof.

Still another class of anionic organic detergents are the .beta.-alkyloxy alkane sulfonates. The compounds have the following formula: ##SPC4##

where R.sub.1 is a straight chain alkyl group having from 6 to 20 carbon atoms, R.sub.2 is a lower alkyl group having from 1 (preferred) to 3 carbon atoms, and M is a water-soluble cation as hereinbefore described.

Specific examples of .beta.-alkyloxy alkane sulfonates, or alternatively 2-alkyloxy-alkane-1-sulfonates, having low hardness (calcium ion) sensitivity useful herein to provide superior cleaning levels under household washing conditions include:

potassium-.beta.-methoxydecanesulfonate,

sodium 2-methoxytridecanesulfonate,

potassium 2-ethoxytetradecylsulfonate,

sodium 2-isopropoxyhexadecylsulfonate,

lithium 2-t-butoxytetradecylsulfonate,

sodium .beta.-methoxyoctadecylsulfonate, and

ammonium .beta.-n-propoxydodecylsulfonate.

Additional examples of anionic non-soap synthetic detergents which come within the terms of the present invention are the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Other anionic synthetic detergents of this variety are set forth in U.S. Pat. Nos. 2,486,921; 2,486,922; and 2,396,278.

Additional examples of anionic, non-soap, synthetic detergents, which come within the terms of the present invention, are the compounds which contain two anionic functional groups. These are referred to as di-anionic detergents. Suitable di-anionic detergents are the di-sulfonates, disulfates, or mixtures thereof which may be represented by the following formulae:

R(SO.sub.3).sub.2 M.sub.2, R(SO.sub.4).sub.2 M.sub.2, R(SO.sub.3)(SO.sub.4)M.sub.2,

where R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example, the C.sub.15 to C.sub.20 disodium 1,2-alkyldisulfates, C.sub.15 to C.sub.20 dipotassium-1,2-alkyldisulfonates or disulfates, disodium 1,9-hexadecyl disulfates, C.sub.15 to C.sub.20 dipotassium-1,2-alkyldisulfonates or disulfates, disodium 1,9-hexadecyl disulfates, C.sub.15 to C.sub.20 disodium-1,2-alkyldisulfonates, disodium 1,9-stearyldisulfates and 6,10-octadecyldisulfates.

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 IIA, IIB, IIIA, IVA and IVB of the Periodic Table except for boron. The preferred water-solubilizing cations are sodium or potassium. These dianionic detergents are more fully described in British Pat. No. 1,151,392 which claims priority on an application made in the United States of America (Sec. No. 564,556) on July 12, 1966.

Still other anionic synthetic detergents include the class designated as succinamates. This class includes such surface active agents as disodium N-octadecylsulfo-succinamate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl-sulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.

The preferred surface-active agents for use in the compositions of the instant invention include alkyl ether sulfates and "olefin sulfonates".

The preferred alkyl ether sulfates have the formula

RO(C.sub.2 H.sub.4).sub.x SO.sub.3 M

wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, an M is a salt forming cation such as alkali metal (sodium, lithium, potassium) ammonium, amines and substituted ammonium. Examples of these latter include lower C.sub.1-4 alkyl amines, and mono, di and trimethanol and ethanolamines.

Especially preferred are those alkyl ether sulfates wherein R has from about 14 to about 18 carbon atoms and wherein x has an average value of about 1 to about 6. Specific examples of especially preferred species are: sodium coconut alkyl ethylene glycol ether sulfate; sodium tallow alkyl triethylene glycol ether sulfate; sodium tallow alkyl pentaoxyethylene sulfate; ammonium tetradecyl pentaoxyethylene sulfate and ammonium lauryl hexaoxyethylene sulfate.

Especially preferred alkyl ether sulfate components have an average (arithmetic mean) carbon chain length within the range of from about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms; and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide, preferably from about 2 to 3 moles of ethylene oxide.

Such mixtures comprise from about 0.05% to 5% by weight of mixture of C.sub.12-13 compounds, from about 55% to 70% by weight of mixture of C.sub.14-15 compounds, from about 25% to 40% by weight of mixture of C.sub.16-17 compounds and from about 0.1% to 5% by weight of mixture of C.sub.18-19 compounds. In addition, such preferred alkyl ether sulfate mixtures comprise from about 15% to 25% by weight of mixture of compounds having a degree of ethoxylation of 0, from about 50% to 65% by weight of mixture of compounds having a degree of ethoxylation from 1 to 4, from about 12% to 22% by weight of mixture of compounds having a degree of ethoxylation from 5 to 8 and from about 0.5% to 10% by weight of mixture of compounds having a degree of ethoxylation greater than 8.

Examples of alkyl ether sulfate mixtures falling within the above-specified ranges are set forth in Table I.

TABLE 1 ______________________________________ MIXTURE CHARACTERISTIC ALKYL ETHER SULFATE MIXTURE ______________________________________ Average carbon chain I II III IV Length (No. C Atoms) 14.86 14.68 14.86 14.88 12-13 carbon atoms (wt. %) 4% 1% 1% 3% 14-15 carbon atoms (wt.%) 55% 65% 65% 57% 16-17 carbon atoms (wt.%) 36% 33% 33% 38% 18-19 carbon atoms (wt.%) 5% 1% 1% 2% Average degree of ethoxylation (No. Moles EO) 1.98 2.25 2.25 3.0 O moles ethylene oxide (wt.%) 15% 21% 22.9% 18% 1-4 moles ethylene oxide (wt.%) 63% 59% 65% 55% 5-8 moles ethylene oxide (wt.%) 21% 17% 12% 22% 9+ moles ethylene oxide (wt.%) 1% 3% 0.1% 5% Salt K Na Na Na ______________________________________

The preferred olefin sulfonates utilizable herein have from about 12 to about 24 carbon atoms. Said ingredients can be produced by sulfonation of .alpha.-olefins by means of uncomplexed sulfurdioxide followed by neutralization in conditions such that any sultones present are hydrolyzed to the corresponding hydroxy-alkane sulfonates. The .alpha.-olefin starting materials preferably have from 14 to 16 carbon atoms. Said preferred .alpha.-olefin sulfonates are described in great detail in U.S. Pat. specification No. 3,332,880, Adriaan Kessler et al., patented July 25, 1967, enclosed herein by reference.

Said .alpha.-olefin sulfonates can be represented either by individual species or by mixtures containing structurally different sulfonation products. Preferred mixtures are disclosed by Kessler et al.; one such mixture consists essentially of from about 30% to about 70% by weight of a Component A, from about 20% to about 70% by weight of a Component B, and from about 2% to about 15% of a Component (C), wherein

a. said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-1-sulfonic acids containing from about 20 to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;

b. said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 20 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms at least 90% of the hydroxy radical substitutions being in 3, 4, and 5 positions; and

c. said Component C is a mixture comprising from about 30-95% water-soluble salts of alkene disulfonates containing from about 20 to about 24 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 20 to about 24 carbon atoms, said alkene disulfonates containing a sulfonic group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atoms, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

Especially preferred for use in the instant compositions are 3-, 4-, and 5-hydroxy alkyl sulfonates and mixtures thereof. Specific examples of said hydroxy-sulfonates include sodium salts of

sodium 3-hydroxy-n-decyl-1-sulfonate,

sodium 3--hydroxy-n-dodecyl-1-sulfonate,

sodium 3-hydroxy-n-tetradecyl-1-sulfonate,

sodium 3-hydroxy-n-hexadecyl-1-sulfonate,

sodium 3-hydroxy-n-octadecyl-1-sulfonate,

sodium 3-hydroxy-n-eicosyl-1-sulfonate,

sodium 3-hydroxy-n-docosyl-1-sulfonate,

sodium 3-hydroxy-n-tetracosyl-1-sulfonate,

sodium 4-hydroxy-n-decyl-1-sulfonate,

sodium 4-hydroxy-n-dodecyl-1-sulfonate,

sodium 4-hydroxy-n-tetradecyl-1-sulfonate,

sodium 4-hydroxy-n-hexadecyl-1-sulfonate,

sodium 4-hydroxy-n-octadecyl-1-sulfonate,

sodium 4-hydroxy-n-eicosyl-1-sulfonate,

sodium 4-hydroxy-n-docosyl-1-sulfonate,

sodium 4-hydroxy-n-tetracosyl-1-sulfonate,

sodium 5-hydroxy-n-decyl-1-sulfonate,

sodium 5-hydroxy-n-dodecyl-1-sulfonate,

sodium 5-hydroxy-n-tetradecyl-1-sulfonate,

sodium 5-hydroxy-n-hexadecyl-1-sulfonate,

sodium 5-hydroxy-n-octadecyl-1-sulfonate,

sodium 5-hydroxy-n-eicosyl-1-sulfonate,

sodium 5-hydroxy-n-docosyl-1-sulfonate, and

sodium 5-hydroxy-n-tetracosyl-1-sulfonate.

Among these preferred species the 4-hydroxy substituent is preferred, e.g. for use in combination with 3-hydroxy- and 5-hydroxy-compounds. This means that in a binary system of these, the 4-hydroxy is present in excess of 50% by weight of the active detergent ingredient.

NONIONIC SYNTHETIC DETERGENTS

Most commonly, 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 or 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:

1. 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 sgraight 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 15 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 Igepal CO-610 marketed by the GAF Corporation; and Triton X-45, X-114, X-100 and X-102, all marketed by the Rohm and Haas Company.

2. The condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol may either be straight or branched and generally contains from about 8 to about 22 carbon atoms. Examples of such 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 above-described coconut alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol 15-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.

3. The condensation products of ethylene oxide with a hydrophobic bases formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from about 1500 to 1800 and of course exhibits water insolubility. 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. Examples of compounds of this type include certain of the commercially available Pluoronic surfactants marketed by the Wyandotte Chemicals Corporation.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic base of these products consists of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of from about 2500 to about 3000. This bae is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% 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.

5. Surfactants having the formula R.sup.1 R.sup.2 R.sup.3 N.fwdarw.O (amine oxide surfactants) wherein R.sup.1 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.sup.1 which is an alkyl group containing from about 10 to about 18 carbon atoms and no ether linkages, and each R.sup.2 and R.sup.3 is selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms;

Specific examples of amine oxide surfactants include: dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, bis-(2-hydroxyethyl)-3-dodecoxy-1-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.

6. Surfactants having the formula R.sup.1 R.sup.2 R.sup.3 P.fwdarw.O (phosphine oxide surfactants) wherein R.sup.1 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.sup.1 which is an alkyl group containing from about 10 to about 18 carbon atoms and no ether linkages, and each R.sup.2 and R.sup.3 is selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms.

Specific examples of the 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)dodecyclphosphine oxide, (2-hydroxypropyl)methyltetradecylphospine oxide, dimethyloleylphosphine oxide, and dimethyl-(2-hydroxydodecyl)phosphine oxide and the corresponding decyl, hexadecyl, and octadecyl homologs of the above compounds.

7. Surfactants having the formula ##SPC5##

(sulfoxide surfactants) wherein R.sup.1 is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxyl substituents, at least one moiety of R.sup.1 being an alkyl group containing no ether linkages and containing from about 10 to about 18 carbon atoms, and wherein R.sup.2 is an alkyl group containing from 1 to 3 carbon atoms and from zero to two hydroxyl groups. Specific examples of sulfoxide surfactants include octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, 3-hydroxy-tridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl-2-hydroxyethyl sulfoxide, and dodecylethyl sulfoxide.

Of all the above-described types of nonionic surfactants, preferred 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 11 moles of 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.

AMPHOLYTIC SYNTHESIS DETERGENTS

Amholytic 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 straight 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., carboxy, sulfonate, sulfato. Examples of compounds falling within this definition are sodium 3-(dodecylamino)-propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadeconoate, disodium 3-(N-carboxymethyldodecylamino)-propane-1-sulfonate, disodium octadecyl-iminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine. Sodium 3-(dodecylamino)-propane-1-sulfonate is preferred.

ZWITTERIONIC SYNTHETIC DETERGENTS

Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amine, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. In all of these compounds there is at least one aliphatic group, straight chain or branched, 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. Examples of various classes of zwitterionic surfactants operable herein are described as follows:

Compounds corresponding to the general formula ##SPC6##

wherein R.sub.1 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.sub.1 is nitrogen, phosphorus or sulfur, R.sub.2 is alkyl or monohydroxyalkyl containing 1 to 3 carbon atoms; x is 1 when Y.sub.1 is S, 2 when Y.sub.1 is N or P; R.sub.3 is alkylene or hydroxyalkylene containing from 1 to about 5 carbon atoms; and Z is a carboxy, sulfonate, sulfate, phosphate or phosphonate group. Examples of this class of zwitterionic surfactants include 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate; 2-(N,N-dimethyl-N-dodecylammonio)acetate; 3-(N,N-dimethyl-N-dodecylammonio)-propionate; 2-(N,N-dimethyl-N-octadecylammonio)ethane-1-sulfate; 3-(P,P-dimethyl-P-dodecylphosphonio)propane-1-sulfonate; 2-(S-methyl-S-tert-hexadecylsulfonio)ethane-1-sulfonate; 3-(S-methyl-S-dodecylsulfonio)propionate; 4-(S-methyl-S-tetradecylsulfonio)butyrate; 3-(N,N-dimethyl-N-4-dodecenylammonio)propane-1-sulfonate; 3-(N,N-dimethyl-N-2-diethoxyhexadecylammonio)propane-1-phosphate; and 3-(N,N-dimethyl-N-4-glyceryldodecylammonio)propionate.

Preferred compounds of this class from a commercial standpoint are 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate, the alkyl group being derived from tallow fatty alcohol; 3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate; 3-(N,N-dimethhyl-N-tetradecyl-ammonio)propane-1-sulfonate; 3-(N,N-dimethhyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate, the alkyl group being derived from the middle cut of coconut fatty alcohol; 3-(N,N-dimethyldodecylammonio)-2-hydroxypropane-1-sulfonate; 4-(N,N-dimethyl-tetradecylammonio)butane-1-sulfonate; 4-(N,N-dimethyl-N-hexadecylammonio)butane-1-sulfonate; 4-(N,N-dimethyl-hexadecylammonio)butyrate; 6-(N,N-dimethyl-N-octadecylammonio)hexanoate; 3-(N,N-dimethyl-N-eicosylammonio)-3-methylpropane-1-sulfonate; and 6-(N,N-dimethyl-N-hexadecylammonio)hexanoate.

Means for preparing many of the surfactant compounds of this class are described in U.S. Pat. Nos. 2,129,264, 2,774,786, 2,813,898, 2,828,332 and 3,529,521 and German Pat. No. 1,018,421 all incorporated herein by reference.

Compounds having the general formula: ##SPC7##

where R.sub.4 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.sub.5 and R.sub.8 are alkylene groups containing from 1 to 12 carbon atoms; R.sub.6 is alkyl or hydroxyalkyl containing from 1 to 10 carbon atoms; R.sub.7 is selected from the group consisting of R.sub.6 groups R.sub.4 --M--R.sub.5 .sup.-, and --R.sub.8 COOMe wherein R.sub.4, R.sub.5, R.sub.6 and R.sub.8 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(oleylamidopropyl)-N-(2-hydroxyethyl)-N-carboxymethylammonium betaine; and N-N-bis-(stearamidopropyl)-N-(2-hydroxyethyl)-N-carboxymethylammonium betaine. Zwitterionic surfactants of this type are prepared in accordance with methods described in U.S. Pat. No. 3,265,719 and DAS No. 1,018,421.

Compounds having the general formula ##SPC8##

wherein R.sub.9 is an alkyl group, R.sub.10 is a hydrogen atom or an alkyl group, the total number of carbon atoms in R.sub.9 and R.sub.10 being from 8 to 16 and ##SPC9##

represents a quaternary ammonio group in which each group R.sub.11, R.sub.12 and R.sub.13 is an alkyl or hydroxyalkyl group or the groups R.sub.11, R.sub.12 and R.sub.13 are conjoined in a heterocyclic ring and n is 1 or 2. Examples of suitable zwitterionic surfactants of this type include the .gamma. and .delta. hexadecyl pyridino sulphobetaines, the .gamma. and .delta. hexadecyl .gamma.-picolino sulphobetaines, the .gamma. and .delta. tetradecyl pyridino sulphobetaines and the hexadecyl trimethylammonio sulphobetaines. Preparation of such Zwitterionic surfactants is described in South African patent application No. 69/5788.

Compounds having the general formula ##SPC10##

wherein R.sub.14 is an alkarylmethylene group containing from about 8 to 24 carbon atoms in the alkyl chain; R.sub.15 is selected from the group consisting of R.sub.14 groups and alkyl and hydroxyalkyl groups containing from 1 to 7 carbon atoms; R.sub.16 is alkyl or hydroxyalkyl containing from 1 to 7 carbon atoms; R.sub.17 is alkylene or hydroxyalkylene containing from 1 to 7 carbon atoms and Z.sub.1 is selected from the group consisting of sulfonate, carboxy and sulfate. Examples of zwitterionic surfactants of this type include 3-(N-dodecylbenzyl-N,N-dimethylammonio)propane-1-sulfonate; 4-(N-dodecylbenzyl-N,N-dimethylammonio)butane-1-sulfonate; 3-(N-hexadecylbenzyl-N,N-dimethylammonio)propane-1-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate; 4-(N-hexadecylbenzyl-N,N-dimethylammonio)butyrate; 3-(N-tetradecylbenzyl-N,N-dimethylammonio)propane-1-sulfate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-2-hydroxypropane-1-sulfonate; 3-[N,N-di(dodecylbenzyl)-N-methylammonio]propane-1-sulfonate; 4-[N,N-di(hexadecylbenzyl)-N-methylammonio]-butyrate; and 3-[N,N-di(tetradecylbenzyl)-N-methylammonio]-2-hydroxypropane-1-sulfonate.

Zwitterionic surfactants of this type as well as methods for their preparation are described in U.S. Pat. Nos. 2,697,116; 2,697,656 and 2,669,991 and Canadian Pat. No. 883,864, all incorporated herein by reference.

Compounds having the general formula ##SPC11##

wherein R.sub.18 is an alkylphenyl, cycloalkylphenyl or alkenylphenyl group containing from 8 to 20 carbon atoms, in the alkyl, cycloalkyl or alkenyl moiety; R.sub.19 and R.sub.20 are each aliphatic groups containing from 1 to 5 carbon atoms; R.sub.21 and R.sub.22 are each hydrogen atoms, hydroxyl groups or aliphatic groups containing from 1 to 3 carbon atoms and R.sub.23 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-1-sulfonate; 4-(N-hexadecylphenyl-N,N-dimethyl)butane-1-sulfonate; 3-(N-tetradecylphenyl-N,N-dimethylammonio)-3,3-dimethylpropane-1-sulfonate and 3-(N-dodecylphenyl-N,N-dimethylammonio)-3-hydroxypropane-1-sulfonate. Compounds of this type are described more fully in British Pats. Nos. 970,883 and 1,046,252, incorporated herein by reference.

Of all the above-described types of zwitterionic surfactants, preferred compounds include 3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and 3 (N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate; (N-dodecylbenzyl-N,N-dimethylammonio)acetate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; and (N,N-dimethyl-N-hexadecylammonio)acetate.

The clay component for use in the preferred compositions of the instant invention consists of particular smectite clay materials. These smectite clays are present in the detergent compositions at levels from about 1% to about 50%, preferably from 5% to 20% of the total compositions.

A complete disclosure of operable clay and methods for incorporating same into detergent compositions is set forth in the commonly assigned co-pending application of Storm and Nirschl, Ser. No. 271,943, filed July 14, 1972, which is herewith incorporated by reference.

Such clay minerals used to enhance the beneficial 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 meq/100 g. of clay. The term "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 classified geologically as smectites.

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.sub.2 (Si.sub.2 O.sub.5).sub.2 OH).sub.2 and Mg.sub.3 (Si.sub.2 O.sub.5) (OH).sub.2, 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. Furthermore, atom substitution by iron and magnesium can occur within the crystal lattice of the smectites, while metal cations such as Na+, Ca++, as well as H+, can be co-present 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 dioctahedral crystal lattice, while the expandable three-layer magnesium silicates have a trioctahedral crystal lattice.

As noted hereinabove, 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 customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, 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 caly (Na) + NH.sub.4 OH .revreaction. smectite clay (NH.sub.4) + 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 (meq./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, is 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 meq/100 g. for kaolinites to about 150 meq/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 meq/100 g. for an average illite clay.

It has been determined that illite and kaolinite clays, with their relatively low ion exchange capacities, are not useful in the preferred embodiments of 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. However, smectites, such as nontronite, having an ion exchange capacity of approximately 50 meq/100 g., saponite, which has an ion exchange capacity of around 70 meq/100 g., and montmorillonite, which has an ion exchange capacity greater than 70 meq/100 g., have been found to be useful in the instant compositions. Accordingly, clay minerals useful herein can be characterized as expandable, three-layer smectite-type clays having an ion exchange capacity of at least about 50 meq/100 g.

Said clay component, especially in combination with the granular starch component, reinforces the beneficial properties of fabrics laundered therewith, particularly the softening (lubricity) characteristics, by reference to what is obtained from compositions of the instant invention which do not contain said smectite-type clay. Said additional benefits can be ascribed -- without being limited by this theory -- to the physical characteristics and ion-exchange properties of the clay used. That is to say, experiments have shown that non-expandable clays such as the kaolinites and the illites, which are both classes of clays having ion exchange capacities below 50 meq/100 g., do not provide the beneficial aspects of the clays employed in the instant compositions. Furthermore, the unique physical and electrochemical properties of the smectite clays apparently cause their interaction with, and dispersion by, the additional components of the instant compositions.

The smectite clays used in the preferred 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 various tradenames, for example, Thixogel No. 1 and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volclay No. 325, from American Colloid Co., Skokie, Illinois; Black Hills Bentonite BH450, from International Minerals and Chemicals; and Veegum Pro and Veegum F, from R. T. Vanderbilt. It is to be recognized that such 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.

While any of the smectite-type clays having a cation exchange capacity of at least about 50 meq/100 g. are useful herein, certain clays are preferred. For example, Gelwhite GP is an extremely white form of smectite clay and is therefore preferred when formulating white granular detergent compositions. Volclay BC, which is a smectite-type clay mineral containing at least 3% of iron (expressed as Fe.sub.2 O.sub.3) 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. On the other hand, 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.

Detergent builder salts can also advantageously be employed in the compositions of the present invention. Said component can be inorganic or organic in nature and can be selected from a wide variety of known builder salts; said builders are used in an amount from about 10% to about 60%, preferably from about 10% to about 40%. The weight ratio of organic surface-active agent to detergent builder salt is from 20:1 to 1:20, and preferably from 10:1 to 1:10. Suitable alkaline, inorganic builder salts include the alkali metal carbonates, aluminates, phosphates, polyphosphates and silicates. Specific examples of these salts are sodium or potassium tripolyphosphates, aluminates, carbonates, phosphates and hexametaphosphates. Suitable organic builder salts include the alkali metal, ammonium and substituted ammonium polyphosphonates, polyacetates, and polycarboxylates.

The polyphosphonates specifically include the sodium and potassium salts of ethylene diphosphonic acid, sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Other examples include the water-soluble [sodium, potassium, ammonium and substituted ammonium (substituted ammonium, as used herein, includes mono-, di-, and triethanol ammonium cations)] salts of ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,12-triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2-3-tetraphosphonic acid. Examples of these polyphosphonic compounds are disclosed in British Pat. Nos. 1,026,366; 1,035,913; 1,129,687; 1,136,619; and 1,140,980.

The polyacetate builder salts suitable for use herein include the sodium, potassium lithium, ammonium, and substituted ammonium salts of the following acids; ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)-ethylenediaminetriacetic acid, N-(2-hydroxyethyl)-nitrilodiacetic acid, diethylenetriaminepentaacetic acid, 1,2-diaminocyclohexanetetraacetic acid and nitrilotriacetic acid. The trisodium salts of the above acids are generally preferred.

The polycarboxylate builder salts suitable for use herein consist of water soluble salts of polymeric aliphatic polycarboxylic acids as, for example, described in U.S. Pat. No. 3,308,067 to F. L. Diehl, patented Mar. 7, 1967; this patent being hereby incorporated by reference.

Preferred detergent builder salts for use in the compositions of the instant invention include the water-soluble salts of: (1) amino polycarboxylates; (2) ether polycarboxylates; (3) citric acid; and (4) aromatic polycarboxylates derived from benzene. These preferred detergent builder salts are preferably used in an amount from about 10% to about 40%.

The water-soluble amino-polycarboxylate compounds have the structural formula ##SPC12##

wherein R is selected from ##SPC13##

wherein R' is ##SPC14##

and each M is selected from hydrogen and a salt-forming cation.

These materials include the water-soluble aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)nitrilodiacetates. Especially preferred are water-soluble salts of nitrilotriacetic acid.

The water-soluble "ether polycarboxylates" have the formula: ##SPC15##

wherein R.sub.1 is selected from ##SPC16##

and R.sub.2 is selected from ##SPC17##

whereby R.sub.1 and R.sub.2 from a closed ring structure in the event said moieties are selected from ##SPC18##

each M is selected from hdrogen and a salt-forming cation.

Specific examples of this class of carboxylate builders include the water-soluble salts of oxydiacetic acid having the formula ##SPC19##

oxydisuccinic acid having the formula ##SPC20##

carboxy methyl oxysuccinic acid having the formula ##SPC21##

furan tetracarboxylic acid of the formula ##SPC22##

and tetrahydrofuran tetracarboxylic acid having the formula ##SPC23##

The salt-forming cation M can be represented, for example, by alkali metal cations such as potassium, lithium and sodium and also ammonium and ammonium derivatives.

Water-soluble polycarboxylic builder salts derived from citric acid constitute another class of a preferred builder for use herein. Citric acid, also known as 2-hydroxy-propane-1,2,3-tricarboxylic acid, has the formula ##SPC24##

Citric acid while it occurs in free state in nature, large quantities of it are produced, for example, as by-product of sugar departing from sugar beets. For use in the compositions of this invention, it can be desirable to use the acid and partially neutralized species whereby the neutralizing cation is preferably selected from alkali metal ions such as sodium, potassium, lithium and from ammonium and substituted ammonium such as mono-, di-, and trimethylolammonium and also mono-, di-, and triethanolammonium cations.

Water-soluble salts of mellitic acid, benzenepentacarboxylic acid and mixtures thereof constitute another class of preferred polycarboxylate builders for use in the subject compositions.

A particular aspect of the present invention encompasses a method for treating fabrics for concurrently cleansing and imparting beneficial characteristics to fabrics. To that effect, the fabrics are treated in an aqueous liquor comprising as an essential component, from about 10 ppm to about 5000 ppm, preferably from about 100 ppm to about 3000 ppm of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergent and mixtures thereof. Suitable and preferred detergents for use in the instant method are the same as those which do fit the composition aspect of this invention; these species have been described in great detail hereinbefore.

Another essential ingredient for use in the aqueous liquor is represented by granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65.degree.C. Said starch ingredient is used to the extent from about 0.1 ppm to 900 ppm, preferably from about 2 ppm to about 200 ppm. Starch species suitable for being used are identical to those which fit the requirements of the composition aspects of this invention; said species are described in great detail hereinbefore.

In a preferred method aspect, fabrics are treated in an aqueous liquor comprising, in addition to the essential organic surface-active agents and starch referred to hereinbefore, as well from about 50 ppm to about 5000 ppm, preferably from about 50 ppm to 2500 ppm of a smectite-type clay having an ion-exchange capacity of at least about 50 meg./100 g.

The aqueous washing liquor used for carrying out the method of this invention can for example be prepared by adding to a substantially aqueous medium, laundry formulations corresponding to the detergent compositions encompassed in this invention. Similar results are obtained, however, by adding the individual ingredients to the aqueous medium. As an example thereof, one may consider adding to the aqueous medium a granular detergent compositions containing all ingredients except starch which is to be added separately. It is also possible to prepare a detergent composition containing actives and other usual ingredients whereas the starch is added in combination with fillers like sodium sulfate or with builders like sodium carbonate. Another possiblity resides in preparing a combination of the starch together with clay and other suitable additives; said mixture is than added to the aqueous solution containing, for example, the additional essential components.

In the foregoing, the essential ingredients which are comprised in the detergent formulations of this invention are described in great detail. Other optional and frequently, dependable upon the purpose of the composition, desirable components such as smectite-type clays and detergent builder salts have been described in great detail as well. In addition to said ingredients, however, in the finished detergent formulations of this invention, there can be added major amounts of other optional detergent composition ingredients which make the product more effective and more attractive. So, for example, organic and inorganic peroxy bleach compounds can be incorporated in these compositions in an amount from about 5% to about 40%.

The peroxy bleach compound can be represented by all usual inorganic and organic ingredients which are known to be satisfactory for being incorporated for that purpose in detergent compositions. Examples of inorganic peroxy bleach compounds are the alkaline metal salts of perborates, percarbonates, persilicates, persulfates, and perphosphates. As is well known, the perborates can have different degrees of hydration. Although frequently the tetra hydrate form is used, it is for certain purposes desirable to incorporate perborates having a lower degree of hydration water, for example, one mole, two moles, or three moles. Organic peroxy bleach agents may be used as well. The like ingredients can be incorporated as such, i.e., they have been prepared perviously or they may be prepared in situ through the addition of, for example, any peroxy bleach agents suitable for being used in combination with an organic peroxy bleach activator.

Specific examples of the organic peroxy bleach compounds are the water-soluble salts of mono- and di-peroxy acids such as perazelaic acid, monoperoxy phthalic acid, diperoxy terephthalic acid, 4-chlorodiperoxyphthalic acid. Preferred aromatic peracids include the water-soluble salts of diperiosphthalic acid, m-chloroperbenzoic acid and p-nitroperbenzoic acid.

In the event the peroxy bleach compound is to be prepared in situ, then its precursors, i.e. the peroxy bleach agent and peroxygen activators are to be added separately to the detergent composition. The peroxygen bleach can be represented by all oxygen bleaching agents which are commonly used in detergent technology, i.e. organic and inorganic species, as mentioned hereinbefore. The activating agents can be represented by all the oxygen activators known as being suitable for use in detergent technology. Specific examples of the preferred activators include acylated glycoluriles, tetra-acetyl methylene diamine, tetra-acetyl ethylene diamine, triacetyl isocyanurate and benzoylimidazole. Acid anhydride activators which bear at least one double bond between carbon atoms in .alpha.,.alpha..sup.1 to the carbonyl group of the anhydride radical can be used as well. Examples thereof are phthalic and maleic anhydrides. Especially preferred bleach activators are based on aldehydes, ketones, and bisulfite adducts of aldehydes and ketones. Examples of these especially preferred activators include: 1,4-cyclohexanedione; cyclohexanone; 3-oxo-cyclohexylacetic acid; 4-tertbutylcyclohexanone; 5-diethylmethylammonio-2-pentanone nitrate; N-methylmorpholinioacetophenone nitrate; acetone; methyl ethyl ketone; 3-pentanone; methyl-pyruvate; N-methyl-4-oxopiperidine oxide; 1,4-bis(N-methyl-4-oxopiperidiniomethyl) benzene chloride; N-methyltropinonium nitrate; 1-methyl-4-oxo-tetrahydrothiapyranonium nitrate; N-benzyl; N-methyl-4-oxo-piperidinium nitrate; N,N-dimethyl-4-oxo-piperidinium nitrate; di-2-pyridyl ketone; and chloral hydrate.

In the event, the peracid is prepared in situ, then the molar ratio of peroxygen bleach agent to bleach activator shall preferably be in the range from about 5:1 to 1:2, especially from 2:1 to 1:1.2.

Other detergent composition ingredients used herein include suds regulating agents such as suds boosters and suds suppressing agents, tarnish inhibitors, soil suspending agents, buffering agents, additional enzymes, brighteners, fluorescers, perfumes, dyes and mixture. The suds boosters can, e.g. be represented by diethanolamides. Silicones, hydrogenated fatty acid, and hydrophobic alkylene oxide condensates can be used in the like compositions for sudes suppressing purposes or, more generally, for suds regulating purposes. Benzotriazole and ethylenethiourea can be used as tarnish inhibitors. Carboxymethyl cellulose is a well-known soil suspending agent. In addition to the initial proteolytic constituents, different enzymes such as amylase can be added as well. The above additional ingredients, when used in the instant compositions are employed in the usual conventional concentrations.

As indicated earlier there is no criticality as to combining the above-mentioned components in preparation of the detergent compositions of this invention other than the requirement that the starch component ultimately be represented in discrete, unmodified granular form in the environment of the laundering liquor. As mentioned earlier, if the composition is in granular or flaked form the starch granules are merely admixed in dry form or sprayed on from a non-heated aqueous dispersion. In detergent compositions of liquid form the starch granules are likewise merely added in proper proportion. However, for liquid compositions it is desirable to select a starch which does not exhibit a strong gel-forming tendency in the environment of the liquid detergent composition. Also, in such liquid compositions, the presence of conventional dispersing agents are desirable in order to prevent settling of the starch granules within the packaging container.

In order to evaluate the detergent compositions of the present invention it was necessary to perform certain tests upon textile fabrics treated in accordance with the present invention. The manner of these tests is set forth below.

ANTI-STATIC TEST

A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35 polyester/cotton blend; 17% nylon; 18% Dacron) is washed for 10 minutes in a miniature agitator washer containing 2 gallons of aqueous washing liquor containing the test laundry compositions (as set forth below). The laundering temperature is 100.degree.F; water hardness 7 grains/gallon artificial hardness. The bundle comprises 5% by weight of the washing liquor. The bundle is spun dry and rinsed for 2 minutes in 2 gallons of water at 100.degree.F and 7 grains/gallon hardness. The fabrics are then dried in a commercial dryer.

The static charge on each fabric is then measured by a standard electrostatic technique within a Faraday cage. The sum of the absolute values of the charges on all fabrics in the bundle, divided by the sum of the area (yards.sup.2) of the total fabric surface (2sides of the fabric) is then computed. This so-called "static value" (volts/yard.sup.2) correlates with gross observations of the effects of static charges on fabric surfaces, i.e., electrical shocks, sparks, fabric clinging, etc. Depending on the fabric bundle tested, no static clinging is exhibited by fabrics having a static value less than about 1.5 volts/yards.sup.2 ; substantial static clinging is noted in fabrics having a static value above 4.5 volts/yard.sup.2.

ANTI-WRINKLING TEST

A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35 polyester/cotton blends; 17% nylon; 18% Dacron) is washed for 10 minutes in a miniature agitator washer containing 2 gallons of aqueous washing liquor containing the test laundry compositions (as set forth below). The laundering temperature is 100.degree.F; water hardness 7 grains/gallon artificial hardness. The bundle is spun dried and rinsed for 2 minutes in 2 gallons of water at 100.degree.F and 7 grains/gallon hardness. The fabrics are then dried in a commercial dryer.

The extent of wrinkling on a given piece of fabric is then measured by mounting the fabric on a flat, movable surface within a light-tight box. A fine beam of light from a source above the fabric impinges upon the fabric at an angle of 90.degree.. As the mounted fabric is moved through a predetermined distance, a miniature photocell affixed adjacent to the stationary light source responds to scattered light at an angle of 45.degree. to the fabric surface. A plot of the light intensity measured by the photocell versus the length of the fabric path traversed gives a profile (curve) which is in all practical respects a facsimile of the surface of the test fabric. That is, a smooth, unwrinkled fabric gives essentially a straight line of constant light intensity; whereas a wrinkled fabric gives a series of peaks and minima. The ratio of the absolute distance through which the fabric was moved to the length of the plotted curve is quantitatively related to the extent of wrinkling.

EASE OF IRONING TEST

A bundle of mixed fabrics (ca. 53% all-cotton; 12% 65/35 polyester/cotton blends; 17% nylon; 18% Dacron) is washed for 10 minutes in a miniature agitator washer containing 2 gallons of aqueous washing liquor containing the test laundry compositions (as set forth below). The laundering temperature is 100.degree.F; water hardness 7 grains/gallon artificial hardness. The bundle comprises 5% by weight of the washing liquor. The bundle is spun dry and rinsed for 2 minutes in 2 gallons of water at 100.degree.F and 7 grains/gallon hardness. The fabrics are then dried in a commercial dryer.

The ease of ironing of each fabric is then measured by using an instrumented, but otherwise conventional, iron. In essence, the iron by means of sensors fitted in its interior measures the amount of effort required by a naive operator to smooth the surface of the test fabric to a subjectively smooth appearance. The total amount of work required to achieve this appearnace in a function of the force exerted on the iron (measured) and the distance traversed by the iron in the plane of the fabric (measured). These tests are performed against untreated controls by naive operators.

Other tests such as softness (related to bulkiness), ease of folding, fabric drapability, fragrance and general state of cleanliness were assessed subjectively by expert panelists against unmarked controls.

The laundry detergent compositions and process of the instant invention are illustrated by the following examples.

EXAMPLE I

Composition A

EXAMPLE I ______________________________________ Composition A Component % by Weight ______________________________________ Anionic Surfactant* 16.8 Sodium Tripolyphosphate 49.5 Sodium Silicate 6.0 Sodium Sulfate 13.1 Granular Cornstarch 0.3 Miscellaneous Minors & Moisture** Balance ______________________________________ *Linear alkyl sodium sulfonate, averaging 13 carbon atoms. **Including brighteners, coconut alcohol ethoxylate and perfume.

Composition A was prepared by admixing all components except the cornstarch in a crutcher and spray dried to form granules. These granules were then uniformly mixed with the granular cornstarch. Another composition, substantially equivalent to Composition A, was prepared by spraying an aqueous dispersion of the starch granules onto the detergent granules followed by removal of excess moisture to yield a granular cornstarch concentration of 0.3 weight percent.

Composition A was admixed with water at a concentration of 0.12% by weight and used to launder soiled fabrics in standard fashion. The fabrics were cleansed and dried and subjected to the above-mentioned tests. The test fabrics as compared against control fabrics exhibit reduced wrinkling, easier ironing, enhanced softness and reduced static charge.

Substantially equivalent results are obtained when the cornstarch of composition A is replaced at concentration levels of 0.1, 1.5, 2.0, 3.0, and 4.0 wt. % respectively.

EXAMPLE II

Composition B

EXAMPLE II ______________________________________ Composition B Components % by Weight ______________________________________ Anionic Surfactant* 20.0 Sodium Tripolyphosphate 47.0 Sodium Silicate 4.5 Sodium Sulfate 10.8 Rice Granular Starch 1.2 Miscellaneous Minors & Moisture** Balance ______________________________________ *1.22:1 Sodium tallow alkyl sulfate:sodium C.sub.11.8 linear alkylbenzene sulfonate **Including perfume, brighteners, carboxymethyl cellulose and coconut hexaethoxylate, ca. 0.6%.

Composition B (preparation in the same manner as Composition A, above) is employed in the anti-wrinkling, ease of ironing and anti-static tests set forth hereinabove. The test fabrics are laundered in an aqueous bath containing Composition B (0.13 wt. %) and exhibit superior properties with respect to anti-wrinkling, ease of ironing, softness and anti-static in comparison with untreated controls.

Substantially equivalent softening, anti-static results, ease of ironing and anti-wrinkling are obtained when the particular anionic surfactant in Compositions A and B is replaced with an equivalent amount of 2-acetoxytridecane-1-sulfonic acid; sodium methyl-.alpha.-sulfopalmitate; sodium-.beta.-methoxyoctadecyl sulfonate; sodium cocount alkyl ethylene glycoether sulfonate; and the sodium salt of the sulfuric acid ester of the reaction product of 1 mole of tallow fatty alcohol and 3 moles of ethylene oxide, respectively.

Substantially equivalent softening, anti-wrinkling, ease of ironing and anti-static benefits are obtained when the particular anionic surfactant in Compositions A and B is replaced with an equivalent amount of a condensation product of nonylphenol with about 9.5 moles of ethylene oxide per mole of nonylphenol; the condensation product of coconut fatty alcohol with about 6 moles of ethyleneoxide per mole of cocount fatty alcohol; the condensation product of tallow fatty alcohol with about 11 moles of ethyleneoxide 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 ethyleneoxide per mole of fatty alcohol, respectively.

Substantially equivalent softening, anti-wrinkling, ease of ironing, and anti-static benefits are obtained when the particular anionic surfactant in Compositions A and B is replaced with an equivalent amount of 3-N,N-dimethyl-N-alkyl ammonio)propane-1-sulfonate or 3(N,N-dimethyl-N-alkyl ammonio)-2-hydroxy-propane-1-sulfonate wherein in both compounds of the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecyl ammonio)-propane-1-sulfonate; 3(N,N-dimethyl-N-hexadecyl ammonio)-2-hydroxy propane-1-sulfonate; 3(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)acetate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate; 6-(-dodecyl-benzyl-N,N-dimethylammonio)hexanoate; 2-(N,N-dimethyl-N-hexadecylammonio)-acetate; and sodium 3-(dodecylamino)-propane-1-sulfonate, respectively.

Substantially equivalent softening, anti-wrinkling, ease of ironing and anti-static 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 equivalent softening, ease of ironing, anti-wrinkling, and anti-static benefits are obtained the granular cornstrach in Composition A and the granular rice starch in Composition B are replaced successively with tapioca, wheat, sweet potato, grain sorghum, arrow root granular starch, and mixtures thereof at the following concentrations: 0.1, 0.8, 1.2, 2.0, 3.0, and 5.0 respectively.

EXAMPLE III

Composition C

A laundary detergent product is prepared having the following composition:

Components Wt. % ______________________________________ Sodium Soap.sup.(1) 40.0 Potassium Soap.sup.(1) 11.2 TAE.sub.3 S.sup.(2) 10.7 C.sub.11.8 LAS.sup.(3) 8.8 Sodium Silicate 8.9 Sodium Sulfate 11.9 Brightener 0.57 Perfume 0.17 Water 3.4 Granular Cornstarch 1.0 Miscellaneous Balance ______________________________________ .sup.(1) Soap mixture comprising 90% tallow and 10% coconut soaps. .sup.(2) Sodium salt of ethoxylated tallow alkyl sulfate having an averag of about 3 ethylene oxide units per molecule. .sup.(3) Sodium salt of a linear alkyl benzene sulfonate having an averag alkyl chain length of about 12 carbon atoms.

The foregoing ingredients, except the cornstarch, are mixed in a crutcher and spray dried to provide a granular, soap based composition. To this soap based composition is added 1.0 wt. % of cornstarch having an average particle diameter of 20 micrometers.

The foregoing composition is added to an aqueous laundering liquor at 100.degree.F at a concentration of about 0.12 wt. %. The composition rapidly dissolves and the starch granules are uniformly and independently dispersed throughout the laundering liquor. Fabrics laundered in said luqior are concurrently cleansed, and benefited with respect to wrinkling, ease of ironing, softness and anti-static finish as determined by the beformentioned tests against control fabrics laundered exactly as above except in the absence of the starch component.

EXAMPLE IV

Composition D

A laundry detergent product is prepared having the following composition:

Components Wt. % ______________________________________ Sodium Soap.sup.(1) 40.0 Potassium Soap.sup.(1) 11.2 TAE.sub.3 S.sup.(2) 10.7 C.sub.11.8 LAS.sup.(3) 8.8 Sodium Silicate 8.9 Sodium Sulfate 11.9 Brighteners 0.57 Perfume 0.17 Water 3.4 Granular Wheat Starch 2.0 Miscellaneous Balance ______________________________________ .sup.(1) Soap mixtures comprise 90% tallow and 10% coconut soaps. .sup.(2) Sodium salt of ethyoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide units per molecule. .sup.(3) Sodium salt of linear alkyl benzene sulfonate having an average alkyl chain length of about 12 carbon atoms.

The foregoing ingredients, except the wheat starch, are mixed in a crutcher and spray dried to provide a granular, soap based composition. To this composition is added 2.0 wt. % of a granular wheat starch having an average particle diameter of 27 micrometers.

The foregoing composition is a stable laundry detergent formulation having excellent water dispersibility and providing excellent fabric laundering, fabric softening, ease of ironing, anti-wrinkling and anti-static characteristics when added to laundering liquors to the extent of about 0.12% by weight.

EXAMPLE V

Composition E

A laundry detergent product is prepared having the following composition:

Components Wt. % ______________________________________ Sodium Soap.sup.(1) 51.8 Tallow Monoethanolamide 2.5 Sodium Tripolyphosphate 11.5 Sodium Ethylenediaminetetraacetate 0.21 Sodium Silicate 5.50 Carboxymethylcellulose 0.33 Sodium Perborate 15.6 Granular Rice Starch 0.3 Perfume, Brighteners, Moisture & Miscellaneous Balance ______________________________________ .sup.(1) A mixture of tallow and coconut soaps comprising 80% tallow soap and 20% coconut soap.

The foregoing ingredients, except the rice starch, are mixed in a crutcher and spray dried to provide a granular, soap based composition. To this composition is added 0.3 wt. % of rice starch having an average granular diameter of 5 micrometers.

The foregoing composition provides excellent fabric laundering and has desirable solubility, fabric softening, anti-wrinkling, ease of ironing, and anti-static characteristics when used to launder fabrics in an aqueous liquor at concentrations of about 0.7% by weight.

EXAMPLE VI

Composition F

A laundry detergent product is prepared having the following composition:

Components Wt. % ______________________________________ Soap.sup.(1) 53.5 Tallow Monoethanolamide 2.6 Sodium Tripolyphosphate 11.8 Sodium Ethylenediaminetetraacetate 0.22 Sodium Silicate 5.7 Carboxymethylcellulose 0.34 Sodium Perborate 16.0 Granular Sweet Potato Starch 1.0 Perfume, Brighteners, Moisture & Miscellaneous Balance ______________________________________ .sup.(1) A mixture of tallow and coconut soaps comprising 80% tallow soap and 20% coconut soap.

The foregoing ingredients, except the granular sweet potato starch, are mixed in a crutcher and spray dried to provide a granular, soap based composition. To this composition is added 1.0 wt. % of a granular sweet potato starch.

The composition is added to an aqueous laundry bath at 100.degree.F at a concentration of 0.5% by weight. Said laundering bath provides excellent fabric laundering and imparts desirable fabric softening, ease of ironing, anti-wrinkling and anti-static characteristics to nylon, cotton, polyester and polyester/cotton blends laundered therein.

It is to be recognized that various substitutions for the components in the compositions set forth hereinabove can be made without obviating the advantageous properties of said compositions. For example, substantially equivalent results are obtained when, in the above described compositions, the ethoxylated tallow alkylsulfate curd dispersing agent of Compositons C and D and the tallow monoethanolamide curd dispersing agent of Compositions E and F are replaced with an equivalent amount of the sodium salt of ethoxylated tallow alkyl sulfate having an average of about six ethylene oxide groups per molecule; sodium .beta.-acetoxy-hexadecane-1-sulfonate; sodium .beta.-acetoxytridecane-1-sulfonate; the sodium salt of sulfonated 1-hexadecene; dimethyldodecylphosphine oxide; sodium hexadecylaminopropionate; 3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and 3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane- 1-sulfonate wherein both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate; methyl-.beta.-hydroxydodecylsulfoxide; stearic ethanolamide; or N-dodecylmonoethanolamine, respectively.

Substantially equivalent results are obtained when in the above described compositions the sodium tripolyphosphate builder of Compositions E and F is replaced with an equivalent amount of sodium citrate, sodium carbonate, sodium mellitate, or sodium nitrilotriacetate, respectively.

Substantially equivalent softening, anti-wrinkling, ease of ironing and anti-static benefits are obtained when the granular starch composition in Compositions C, D, E and F is replaced with an equivalent amount of grain sorghum, tapioca, and waxy sorghum, respectively, all such granular starches having a granular diameter ranging from about 1.0 to about 45.0 micrometers.

EXAMPLE VII

A through the wash-cycle fabric softener additive having the following composition is prepared:

Components Parts ______________________________________ Sodium bicarbonate 19.5 Granular starch (swelling power 5 at 65.degree.C, average particle diameter 20 micrometer) 0.5 Sodium montmorillonite 20 ______________________________________

This additive is used for treating textiles in combination with a detergent base granule having the following composition.

______________________________________ Components Parts ______________________________________ Sodium linear dodecyl benzene sulfonate 6 Sodium silicate solids (ratio SiO.sub.2 /Na = 2.0) 12 Sodium carbonate 12 Sodium sulfate 28 Minors 2 ______________________________________

The softener additive is either combined with the detergent base granule prior to dissolving said mixture in the washing liquor or is added separately to the washing liquor. In both cases the product concentration, based on the sum of both, is 0.12% by weight, representing 0.05% by weight of softener additive and 0.07% by weight of detergent base granule.

Fabrics treated with the laundering liquor of this invention exhibit superior fabric properties relative to what is obtained from a similar method containing equivalent concentration of a detergent composition known in the art.

EXAMPLE VIII

A laundry detergent product is prepared having the following composition:

Components Parts ______________________________________ Sodium tallow alkyl trioxy ethylene sulfate 20 Starch (swelling power 7, average particle diameter 20 micrometers) 2 Clay (GELWHITE GP) 22 Sodium oxydisuccinate 20 Sodium perborate 20 Sodium sulfate 10 Minor ingredients and moisture 6 ______________________________________

The above composition provides excellent cleaning and outstanding fabric properties to textiles laundered therein.

Substantially identical results are obtained when sodium tallow alkyl trioxyethylene sulfate is replaced with an equivalent quantity of sodium cocount alkyl ethylene glycol ether sulfate; sodium tallow alkyl glycol ether sulfate; sodium tallow alkyl pentaoxyethylene sulfate; ammonium tetradecylpentaoxy ethylene sulfate; ammonium lauryl hexaoxyethylene sulfate; sodium tallow alkyl hexaoxyethylene sulfate; and also by the Alkyl Ether Sulfate Mixtures Nos. I, II, III, and IV from Table I.

Substantially similar results are also obtained in the event the sodium tallow alkyl trioxyethylene sulfate is substituted by an equivalent amount of a surface-active mixture, said mixture consisting essentially of about 50% of a Component A, about 40% of a Component B, and about 10% of a Component C, wherein

a. said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-1-sulfonic acids containing from about 20 to about 24 carbon atoms, said mixture of positional isomers including about 20% of an alpha-beta unsaturated isomer, about 50% of a beta-gamma unsaturated isomer, about 20% of gamma-delta unsaturated isomer, and about 10% of a delta-epsilon unsaturated isomer;

b. said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 20 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms at least 90% of the hydroxy radical substitutions being in 3, 4, and 5 positions; and

c. said Component C is a mixture comprising from about 70% water-soluble salts of alkene disulfonates containing from about 20 to about 24 carbon atoms, and from about 30% water-soluble salts of hydroxy disulfonates containing from about 20 to about 24 carbon atoms, said alkene disulfonates containing a sulfonic group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atoms, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

Substantially similar results are also obtained when the sodium tallow alkyl trioxyethoxy sulfate is replaced with an equivalent amount of a mixture of the sodium salts of 3-, 4-, and 5-hydroxy alkyl sulfonates, whereby in a binary system of these, the 4-hydroxy is present in excess of 50% by reference to the sum of the 3-, or 5-hydroxy with the 4-hydroxy alkyl sulfonates.

It is especially significant that each of the benefits described above in no way impairs or interferes with the general overall cleaning effectiveness of the detergent composition. The fact that these benefits are obtained during the relatively brief span of a washing cycle, for example, about 6 to about 12 minutes, is especially note-worthy.

Claims

What is claimed is:

1. A laundry detergent composition comprising:

a. from about 4% to about 60% by weight of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof; and

b. from 0.1% to about 6% by weight of granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65.degree.C.

2. A detergent composition in accordance with claim 1 wherein the component (a) surface-active agent is present to the extent of from about 6% to about 40% by weight.

3. A detergent composition in accordance with claim 2 wherein the component (b) granular starch is present to the extent of from about 0.2% to about 4% by weight.

4. A detergent composition in accordance with claim 3 wherein the component (a) organic surface-active agent is selected from the group consisting of:

i. alkyl ether sulfates having the formula

RO(C.sub.2 H.sub.4 O).sub.x SO.sub.3 M

wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30 and M is a salt forming cation; and

ii. olefin sulfonates having from about 12 to about 24 carbon atoms.

5. A detergent composition in accordance with claim 4 which contains also a detergent builder salt to the extent of from about 10% to about 60% by weight; the weight ratio of said builder to the organic surface-active agent being in the range from about 20:1 to 1:20.

6. A laundry detergent composition comprising

a. from about 4% to about 60% by weight of an organic surface-active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof;

b. from 0.1% to about 6% by weight of a granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65.degree.C; and

c. from about 1% to about 50% by weight of a smectite-type clay having an ion-exchange capacity of at least about 50 meg/100 g.

7. A detergent composition in accordance with claim 6 wherein the component (a) surface-active agent is present to the extent of from about 6% to about 40% by weight.

8. A detergent composition in accordance with claim 7 wherein the component (b) granular starch is present to the extent of from about 0.2% to about 4% by weight.

9. A detergent composition in accordance with claim 8 wherein the component (a) organic surface-active agent is selected from the group consisting of:

i. alkyl ether sulfates having the formula

RO(C.sub.2 H.sub.4 O).sub.x SO.sub.3 M

wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30 and M is a salt forming cation; and

ii. olefin sulfonates having from about 12 to about 24 carbon atoms.

10. A detergent composition in accordance with claim 9 which contains also a detergent builder salt to the extent of from about 10% to about 60% by weight; the weight ratio of said builder to the organic surface-active agent being in the range of from about 20:1 to 1:20.

11. A method for treating fabrics to simultaneously cleanse and impart anti-wrinkling, ease of ironing, softening and anti-static properties, said method comprising treating fabrics in an aqueous liquor comprising:

a. from about 10 ppm to about 5000 ppm of an organic surface active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof; and

b. from about 0.1 ppm to about 900 ppm of a granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65.degree.C.

12. A method in accordance with claim 11 wherein the component (a) organic surface active agent is present to the extent of from about 100 ppm to about 3,000 ppm; and the component (b) starch is used to the extent of from about 2 ppm to about 200 ppm.

13. A method for treating fabrics to simultaneously cleanse and impart anti-wrinkling, ease of ironing, softening and anti-static properties, said method comprising treating fabrics in an aqueous liquor comprising:

a. from about 100 ppm to about 5000 ppm of an organic surface active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic detergents and mixtures thereof;

b. from about 0.1 ppm to about 900 ppm of granular substantially water-insoluble starch having an average particle diameter from 1.0 to about 45 micrometers and a swelling power of less than about 15 at a temperature of 65.degree.C; and

c. from about 50 ppm to about 2,500 ppm of a smectite-type clay having an ion exchange capacity of at least about 50 meg/100 g.

14. A method in accordance with claim 13 wherein the component (a) organic surface-active agent is present to the extent of from about 100 ppm to 3,000 ppm; the component (b) starch is used to the extent of from about 2 ppm to about 200 ppm; and the component (c) smectite-type clay is used to the extent of about 50 ppm to about 2,500 ppm.