FIELD OF THE INVENTION

The present invention is generally directed to a granular detergent composition having improved solubility in cold temperature laundeπng solutions More particularh the invention is directed to a detergent composition containing high levels of a sulfated surfactant selected from the group consisting of alkyl sulfates (also referenced herein as "AS"), alkyl ethoxy sulfates (also referenced herein as "AES"), and secondary alkyl sulfates (also referenced herein as "SAS") and mixtures thereof, and a hydrotrope selected from the group consisting of sulfyl succinates, xylene sulfonates, cumene sulfonates and mixtures thereof, together which improve solubilitv in cold temperature washing solutions (e g 5°C to 30°C) and high water hardness conditions (e g 7 grains/gallon) For purposes of producing a high densitv, compact detergent composition, the detergent of the invention is in the form of detergent agglomerates rather than sprav dned granules

BACKGROUND OF THE INVENTION Typically, conventional detergent compositions contain mixtures of vanous surfactants in order to remove a wide vanety of soils and stains from surfaces For example, vanous anionic surfactants, especially the alkyl benzene sulfonates, are useful for removing paniculate soils and vanous nonionic surfactants, such as the alkyl ethoxylates and alkylphenol ethoxylates, are useful for removing greasy soils

While the art is replete with a wide vanety of surfactants for those skilled in the art of detergent formulation, most of the available surfactants are specialty chemicals which are not suitable for routine use in low cost items such as home laundeπng compositions The fact remains that many home-use laundry detergents still compπse one or more of the conventional alkyl benzene sulfonates or pnmary alkyl sulfate surfactants Another class of surfactants which has found use in vanous compositions where emulsification is desired compnses the secondary alkyl sulfates The conventional secondary alkyl sulfate surfactants are available as generally pasty, random mixtures of sulfated linear and/or partially branched alkanes For example, Rossall et al, U S Patent No 4.235,752, disclose a detergent surfactant which is a Ci o-i8 secondary alkyl sulfate containing 50% of 2/3 sulfate isomers and 40% of vanous other effective isomers The surfactant mateπals disclosed by Rossall et al is for use pπmaπly in dishwashing operations Such matenals have not come into widespread use in laundry detergents since they do not offer any advantages over alkvl benzene sulfonates, especially with respect to water solubility which facilitates production of high-surfactant granular detergents Accordingly, Rossall et al do not provide a high density laundry detergent having improved solubility in either cold temperature wash solutions or high hardness water conditions

The limited solubility of alky l sulfate surfactants including both primary and secondary alkyl sulfates is especially pre\alent in modern granular laundry detergents which are typically used in cold temperature (e.g. 5°C to 30°C) washing solutions and are formulated in "condensed" or "compact" form for low dosage usage. For the consumer, the smaller package size attendant with compact detergent products provides for easy storage and handling. For the manufacturer, unit storage costs, shipping costs and packaging costs are lowered

The manufacture of acceptable compact or condensed granular detergents has its difficulties. In a typical compact detergent formulation, the so<alled "inert" ingredients such as sodium sulfate are substantially eliminated However, such ingredients do play a role in enhancing solubility of conventional detergents. As a consequence, compact detergents often suffer from solubility problems, especially in cold temperature laundeπng solutions. Moreover, conventional compact or low density detergent granules are usually prepared by spray drying processes which result in extremely porous detergent particles that are quite amenable to being dissolved in aqueous washing solutions. By contrast, compact detergents are typically compnsed of less porous, high density detergent particles which are less soluble, e.g. agglomerates Thus, since the compact form of granular detergents typically comprise particles or granules which contain high levels of detersive ingredients with little or no room for solubilizing agents, and since such particles are intentionally manufactured at high bulk densities, the net result can be a substantial problem with regard to in- use solubility. In the art of detergency, the use of hydrotropes have generally been associated with liquid detergent compositions to increase the solubility of vanous detergent ingredients in the composition For example, Gutierrez et al, U.S. Patent No 4,528, 144 (Lever), is directed to a liquid detergent compositions containing terpene sulfonate hydrotropes and vanous other detergent ingredients in a similar fashion, Lamberti et al, U.S. Patent No 4.623.483 (Lever), is also directed to a liquid detergent composition comprising a hydrotrope and other conventional detergent ingredients Both of the Lamberti et al and Gutierrez patents only suggest liquid compositions and are silent with respect to granular or agglomerated versions of the detergent disclosed therein Thus, these patents do not speak to the solubility problem associated with cold temperature laundering solutions, a problem particularly prevalent when using detergents which are not spray-dried. Accordingly, despite the disclosures in the art, there remains a need for a detergent composition which has improved solubility, especially in cold temperature washing solutions This need is especially prevalent in the art of compact or high density detergents currently being used by consumers. There is also a need for such a detergent composition which also has improved solubility under high water hardness conditions. Also, there is a need for such a detergent composition which exhibits improved biodegradability

SUMMARY OF THE INVENTION The present invention meets the needs identified above by prov iding a detergent composition in the form of agglomerates which exhibit improved solubility or dissolution of the anionic surfactants in cold temperature washing solutions as well as under high water hardness conditions The detergent composition compnses a surfactant system having a high level of a sulfated surfactant selected from the group of alkyl sulfates, alkyl ethoxy sulfates secondary alkyl sulfates and mixtures thereof, in combination with a hydrotrope selected from the group consisting of sulfyl succinates, xylene sulfonates, cu ene sulfonates and mixtures thereof Other adjunct detergent ingredients may also be included in the detergent agglomerates which form the detergent composition For example, high active (high surfactant levels) particles may be optionally included to enhance cleaning For purposes of enhancing biodegradabi ty, the detergent composition does not contain any phosphates

As used herein, the phrase "improved solubility" means that the solubility of the anionic surfactants of the detergent composition is enhanced by at least 5% in the laundenng solution when employed in the manner of this invention, as compared to the solubility of the same anionic surfactants per se, under the same test conditions (i e water temperature and pH. stirring speed and Ume, particle size, water hardness, and the like) As used herein, the term "agglomerates" refers to particles formed by agglomerating particles which typically have a smaller mean particle size than the formed agglomerates All percentages, ratios and proportions used herein are by weight, unless otherwise specified All documents including patents and publications cited herein are incorporated herein by reference

In accordance with one aspect of the invention, a detergent composition in the form of agglomerates is provided herein The detergent composition compnses from about 1% to 50% by weight of a detersive surfactant system The surfactant system itself compnses by weight of the surfactant system, at least about 30% of a sulfated surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof The detergent composition includes from about 1% to about 50% of a hydrotrope selected from the group consisting of sulfyl succinates. xylene sulfonates, cumene sulfonates and mixtures thereof Also, the detergent composition includes at least about 1% by weight of a detergency builder to enhance cleaning The surfactant system, hydrotrope, and builder are agglomerated to form detergent agglomerates which are substantially free of phosphates The anionic surfactants in the detergent composition have improved solubility in an aqueous laundeπng solution Thus, the solubility of the sulfated surfactant (AS. AES and/or SAS) is enhanced by at least 5%, preferably 10 to 50%, over those same surfactants alone under the same test conditions in aqueous washing solutions at cold temperatures, I e 5°C to 30°C In accordance with another aspect of the invention, a method for laundeπng soiled fabπcs is provided The method compnses the step of contacting soiled fabπcs with an effective amount of a

detergent composition as descπbed herein in an aqueous laundeπng solution An effective amount is typically on the order of 1000 to 1500 ppm

Accordingly, it is an object of the present invention to provide a granular detergent composition which has improved solubility, especially in cold temperature washing solutions It is also an object of the invention to provide such a detergent composition which has improved biodegradability These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed descnption of the prefened embodiment and the appended claims

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The invention is directed to a granular detergent composition having improved solubility in cold temperature laundeπng solutions A multitude of consumers around the world launder soiled clothes in conventional washing machines unique to their particular geographic location Typically, these conventional washing machines launder the soiled clothes in water supplied at relatively cold temperatures, for example in range of 5°C to 30°C, and at high hardness concentrations, e g 7 grains/gallon (nch with Ca and Mg ions) Most of the modem day consumers also use compact or condensed laundry detergents to accomplish their laundeπng needs Under the aforementioned conditions, solubility of cunent detergents in aqueous laundeπng solutions has been a problem This problem is especially exacerbated when the detergent composition has high levels of alkyl sulfates, alkyl ethoxy sulfate and/or secondary alkyl sulfates which are not particularly amenable to dissolution in cold aqueous laundeπng solutions Such surfactants are particularly useful in modem laundry detergents since they minimize or eliminate the need for linear alkylbenzene sulfate surfactants which generally have poor biodegradability

It has been found that the solubility of a high-content alkyl sulfate. alkyl ethoxy sulfate and/or secondary alkyl sulfate ("sulfated" surfactant system) detergent composition can be increased by incorporating a hydrotrope selected from the group consisting of sulfyl succinates, xylene sulfonates, cumene sulfonates and mixtures thereof To that end. the preferred detergent composition of the invention compnses from about 1% to about 50%, preferably from about 15% to about 40%, by weight of a hydrotrope The surfactant system of the detergent composition compnses at least 30%, preferably from about 35% to about 90%, of a sulfated surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof Preferably, the detergent composition is in the form of agglomerates and has an overall density of 650 g/1 or higher It has been found that such a detergent composition containing agglomerates having the aforementioned surfactant system and hydrotrope surpπsingly has significantly improved solubility in cold temperature (5°C to 30°C) washing solutions as well as under high water hardness conditions

Preferably, the detergent composition of the invention also compnses at least about 1%. preferably from about 10% to about 40%, of a detergency builder The detergent composition mav

also include one or more of adjunct detergent ingredients Nonhmiting examples of the detergencv builder and such adjunct ingredients are descπbed in detail hereinafter Preferablv the detergent composition herein is formulated and processed to achie e a density of at least 650 g/1 for purposes of producing a "compact" detergent product For purposes of enhancing biodegradability, the detergent agglomerates which form the detergent composition of the invention preferably do not contain phosphates Further, it is important for the detergent composition to be in the form of "agglomerates" as opposed to spray dned granules This is particularly important since most sulfated surfactants cannot be readily subjected to spray drying processes without causing or creating extremeK adverse plumes from the spray drying towers

The "improved solubility" achieved by the detergent com osition is concerned with enhanced solubility of the anionic surfactants contained in the sun „tant system, I e AS, AES, SAS or LAS if used Preferably, the improvement represents at least a 5% increase in solubility of these anionics in the wash solution over the solubility of the same surfactants if they were dissolved alone or without being contained in a detergent composition as defined herein More preferably, the solubility improvement is from about 10% to about 50% As those skilled in the art will appreciate, any compaπson of anionic surfactant solubility should be completed under the same laundenng conditions, e g water temperature, hardness and pH, stimng speed and time, and particle size Typical anionic surfactant solubility improvements are set forth in the Examples hereinafter Those skilled in the art should also appreciate the numerous ways in which the amount of the surfactant system in the washing solution can be determined For example, in the so-called "catS03" titration technique, samples of the aqueous laundenng solution containing the detergent composition can be taken after one minute and filtered with 0 45 mm nylon filter HPLC, after which the filtered solution can be titrated with a cationic titrant. which can be commercially purchased. e g from Sigma Chemical Company under the trade name Hyamine. in the presence of anionic dyes From the foregoing, the amount of anionic surfactant which was dissolved in the washing solution can be determined

Surfactant System The surfactant system in the detergent composition must include a sulfated surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates. and mixtures thereof As mentioned previously, the anionic surfactants in the surfactant system of the invention, i e AS, AES, and/or SAS, have improved solubility and more particularly on the order of 5% or higher Optionally, the surfactant system may contain one or more of additional surfactants, nonlimiting examples of which are provided hereinafter The surfactant system preferably includes conventional pnmary alkyl sulfate surfactants have the general formula

ROS0 ₃ -M ⁺

wherein R is typically a linear C10-C20 hydrocarbyl group and M is a water-solubihzing cation Branched-chain pπmary alkyl sulfate surfactants (1 e , branched-chain "PAS") having 10-20 carbon atoms can also be used herein, see, for example. European Patent Application 439,316, Smith et al filed 21 01 91, the disclosure of which is incorporated herein by reference (Included in the term "alkyl" is the alkyl portion of acyl groups) Included in the surfactant system are the C _j o-C _j alkyl alkoxy sulfates ("AE _X S", especially EO 1-7 ethoxy sulfates)

Conventional secondary alkyl sulfate surfactants can also be used herein and include those mateπals which have the sulfate moiety distπbuted randomly along the hydrocarbyl "backbone" of the molecule Such mateπals may be depicted by the structure CH ₃ (CH2) _n (CHOSθ3-M ⁺ )(CH ₂ ) _rn CH3 wherein m and n are integers of 2 or greater and the sum of + n is typically about 9 to 17, and M is a water-solubihzing cation

More preferably, a selected secondary (2,3) alkyl sulfate surfactant is used herein which compnses structures of formulas A and B (A) CH ₃ (CH ₂ ) _x (CHOS0 ₃ -M ⁺ ) CH ₃ and

(B) CH ₃ (CH ₂ ) _y (CH0S0 ₃ -M ⁺ )CH2CH ₃ for the 2-sulfate and 3-sulfate, respectively Mixtures of the 2- and 3-sulfate can be used herein In formulas A and B, x and (y+1) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about 10 to about 16 M is a cation, such as an alkali metal, ammonium, alkanolammonium, alkaline earth metal, or the like Sodium is typical for use as M to prepare the water-soluble (2,3) alkyl sulfates, but ethanolammomum, diethanolammonium, tnethanolammonium, potassium, ammonium, and the like, can also be used It is preferred that the secondary (2,3) alkyl sulfates be substantially free (1 e , contain less than about 20%. more preferably less than about 10%, most preferably less than about 5%) of such random secondary alkyl sulfates.

The preparation of the secondary (2,3) alkyl sulfates of the type useful herein can be earned out by the addition of H2SO4 to olefins A typical synthesis using α-olefins and sulfunc acid is disclosed in U.S. Patent 3,234,258, Morns, or in U S Patent 5,075,041, Lutz, granted December 24, 1991, both of which are incorporated herein by reference The synthesis, conducted in solvents which afford the secondary (2,3) alkyl sulfates on cooling, yields products which, when punfied to remove the unreacted mateπals, randomly sulfated mateπals, unsulfated by-products such as C JQ and higher alcohols, secondary olefin sulfonates, and the like, are typically 90+% pure mixtures of 2- and 3-sulfated materials (up to 10% sodium sulfate is typically present) and are white, non-tacky. apparently crystalline, solids Some 2,3-dιsulfates may also be present, but generally compπse no more than 5% of the mixture of secondary (2,3) alkyl mono-sulfates Such mateπals are available as under the name "DAN", e g , "DAN 200" from Shell Oil Company

If increased solubility of the "crvstallm- secondary (2 3) alkvl sulfate surfactants is desired, the formulator may wish to emplov mix.ures of such surfactants hav ing a mixture of alkyl chain lengths Thus, a mixture of C j^-C i g alky l chains will provide an increase in solubility over a secondary (2.3) alkyl sulfate wherein the alky l crr-n is, say, entirely Ci6 The solubility of the secondary (2,3) alkyl sulfates can also be enhant -> by the addition thereto of other surfactants such as the mateπal which decreases the crystallinity c the secondary (2,3) alkyl sulfates Such crystallimty-interrupting mateπals are typically effective at levels of 20%, or less, of the secondary (2,3) alkyl sulfate

H ^y drotrope The granular detergent composition of the present invention preferably includes a hydrotrope such a those commonly used in liquid detergents It has been found that the inclusion of a hydrotrope into the agglomerated detergent composition descπbed herein surprisingly aides in solubihzation of detergent agglomerates which are nch in sulfated surfactants (l e > 30% of the surfactant system) The hydrotrope regardless of form (I e solid, liquid or paste) is mixed with the surfactant paste pπor to, or dunng the agglomeration step Those skilled in the art will appreciate the wide vanety of hydrotropes useful for the instant detergent composition As mentioned previously, however, the hydrotrope used herein is preferably selected from the group consisting of sulfyl succinates, xylene sulfonates, cumene sulfonates and mixtures thereof Most prefeπed are the sodium salts of the aforementioned prefeπed hydrotropes such as sodium sulfyl succinate Other suitable hydrotropes include napthalene sulfonates, benzoates, salicylates. gallates, hydroxy naphthoates, picohnates These and other suitable hydrotropes for use herein are descπbed in known texts such as Mitijevic, "Surface and Colloid Science" Plenum Press, vol 15 (1993), the disclosure of which is incorporated herein by reference

Builder The detergent composition of the invention also includes a detergency builder matenal to assist in controlling mineral hardness Inorganic as well as organic builders can be used Builders are typically used in fabnc laundenng compositions to assist in the removal of paniculate soils Inorganic detergent builders include, but are not limited to. the alkali metal, ammonium and alkanolammonium salts of phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates

Examples of silicate builders are the alkali metal silicates, particularly those having a S1O2 Na2θ ratio in the range 1 6 1 to 3 2 1 and layered silicates, such as the layered sodium silicates descπbed in U S Patent 4,664,839 issued May 12, 1987 to H P Rieck NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6") Unlike zeolite builders, the Na SK.S-6 silicate builder does not contain aluminum NaSKS-6 has the delta-Na2Sιθ5 morphology form of layered silicate It can be prepared by methods such as those descπbed in German DE-A-3,417,649 and DE-A-3,742,043 SKS-6 is a

highly prefeπed layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSι _λ θ2 _x +ι-yH2θ wherein M is sodium or hydrogen, x is a number from 1 9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein Vanous other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaS S- 1 1. as the alpha, beta and gamma forms. As noted above, the delta-Na2Sιθ5 (NaSKS-6 form) is most prefeπed for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crisping agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No 2.321,001 published on November 15, 1973

Aluminosilicate builders are useful in the present invention Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations Aluminosilicate builders include those having the empirical formula M _z (zA10 ₂ )y]-xH ₂ 0 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1 0 to about 0.5, and x is an integer from about 15 to about 264

Useful aluminosilicate ion exchange materials are commercially available These aluminosilicates can be crystalline or amorphous in structure and can be natural ly-occurnng aluminosilicates or synthetically denved A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel. et al, issued October 12, 1976 Prefeπed synthetic crystalline aluminosilicate ion exchange mateπals useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially prefeπed embodiment, the crystalline aluminosilicate ion exchange material has the formula Na ₁ 2[(A10 ₂ ) ₁ 2(Siθ2)i2l H ₂ 0 wherein x is from about 20 to about 30, especially about 27 This mateπal is known as Zeolite A Dehydrated zeolites (x = 0 - 10) may also be used herein Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds As used herein, "poly- carboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred Included among the polycarboxylate builders are a vanety of categoπes of useful materials

One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate. as disclosed in Berg. U S Patent 3, 128,287, issued April 7, 1964. and

Lamberti et al, U S Patent 3.635,830, issued January 18. 1972 See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987 Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those descπbed in U S Patents 3,923,679, 3,835, 163, 4,158,635, 4, 120,874 and 4, 102,903 Other useful detergency builders include the ether hydrovypolycarboxylates. copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-tnhydroxy benzene-2. 4. 6- trisulphonic acid, and carboxymethyloxysuccinic acid, the vanous alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylιc acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e g., citnc acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability Citrates can also be used, however, in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations

Also suitable in the detergent compositions of the present invention are the 3,3-dιcarboxy- 4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly prefeπed compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include- laurylsuccinate. mynstyisucc ate. palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccιnate, and the like Laurylsuccinates are the prefeπed builders of this group, and are descπbed in European Patent Application 86200690.5/0,200,263, published November 5, 1986 Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S Patent 3,723,322

Fatty acids, e.g., Cι ₂ -Cι monocarboxylic acids, can also be incorporated into the compositions alone, or in combinatic with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator

Adiunct Surfactants One or more adjunct surfactants may be included generally at a level of from about 1% to about 50% of the surfactant system descnbed herein. Nonlimiting examples of surfactants useful in conjunction with the surfactants descπbed herein are the C i _Q -Cig alkyl alkoxy carboxy lates (especially the EO 1 -5 ethoxycarboxylates), the C _[ Q.18 glycerol ethers, the C 1 ₀ -C _j g alkyl polyglycosides and their coπesponding sulfated polyglycosides, and C ^-C j alpha-sulfonated fatty acid esters If desired, the conventional nonionic and amphoteric surfactants such as the C \j- [g

alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C ^ alkyl phenol alkoxylates (especially ethoxylates and ethow/propoxy), C _{j 2} -C ι betaines and sulfobetaines ("sultaines"), can also be included in the overall compositions The C JQ-C _[ g N-alkyI polyhydroxy fatty acid amides can also be used Typical examples include the C ^-C _j g N- methylglucamides See WO 9,206, 154 The N-propyl through N-hexyl C 1 ₂ -C ι g glucamides can be used for low sudsing C10-C20 conventional soaps may also be used If high sudsing is desired the branched-chain Cir _j -Cig soaps may be used

Also included in the surfactant system is the conventional C _j^ -C _j alkyl benzene sulfonates (also referenced herein as "LAS) While the biodegradability of the so-called "LAS" surfactants have been the subject of some concem, the surfactant system herein may include an optimum level, from about 0 1% to about 15% and more preferably from about 3% to about 8% by weight, for improving the overall solubility of the detergent composition without substantially decreasing the overall biodegradability of the present detergent composition Alternatively, the level of LAS may be included as from about 1% to about 40%. more preferably from about 10% to about 25%, by weight of the surfactant system in the detergent composition

The surfactant system may also include an amine oxide surfactant Nonlimiting examples include C _jQ .ig amine oxides, secondary amine oxides such as dimethyl amine oxide, and tertiary amine oxides having the general formula RR'R"NO in which R is a pnmary alkyl group containing 8 to 24 carbon atoms, R' is methyl, ethyl, or 2-hydroxyethyl, and R" is independently selected from methyl, ethyl, 2-hydroxyethly and pnmary alkyl groups containing 8 to 24 carbon atoms

Additionally, the tertiary amine oxide surfactant may be in hydrated form and have the general formula RR'R"NO 11H2O wherein R R' and R" are the same as above and n is 1 or 2 Examples of other tertiary amines suitable for use herein include those containing one or two short-chain groups independently selected from methyl, ethyl, and 2-hydroxyethyl groups, with the remaining valences of the amino nitrogen being satisfied with long-chain groups independently selected from pnmary alkyl groups containing 8-24 carbons, e g , octyl, decyl, dodecyl, tetradecyl, hexadecyl octadecyl, eicosyl, docosyl, and tetracosyl groups The pnmary alkyl groups may be branched-chain groups, but the prefeπed amines are those in which at least most of the pnmary alkyl groups have a straight chain Exemplary of these tert-amines are N-octyldimethylamine, N,N-dιdecylmethylamιne, N- decyl-N-dodecylethylamme, N-dodecyldimethylamine, N-tetradecyldimethylamine N-tetradecyl-N- ethylmethylamine, N-tetradecyl-N-ethyl-2-hydroxyethylamιne, N,N-dι-tetradecyl-2- hydroxyethylamine, N-hexadecyldimethylamine, N-hexadecyldι-2- hdroxyethylamine N- octadecyldimethylamine, N,N-dιeιcosylethylamιne, N-docosyl-N-2-hvdroxyethylmethylamιne, N- tetracosyldimethylamine, etc

Addmonal amine oxide surfactants and methods of making the same all of -e suitable for use herein, are disclosed by Borland et al. U S Patent No 5.071,594 and Tosaxa et al, U S Patent No 5.096,621, incorporated herein by reference

Mixtures of anionic and nomonic surfactants are especially useful Other conventional useful surfactants are listed in standard texts

Detergent Adiunct Ingredients The detergent composition can also include any number of additional ingredients These include detergency builders, bleaches, bleach activators, suds boosters or suds suppressers, anti-tarnish and anticoπosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents. non-builder alkalimty sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes See U S Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr et al , incorporated herein by reference Also, fabnc conditioning agents may be included as an adjunct mateπal such as those descnbed in U S Patent 4,861,502, issued August 29, 1989 to Caswell. incorporated herein by reference Bleaching agents and activators are descπbed in U S Patent 4,412,934. Chung et al , issued

November 1, 1983, and in U S Patent 4,483.781, Hartman, issued November 20. 1984. both of which are incorporated herein by reference Chelating agents are also descπbed in U S Patent 4,663,071, Bush et al , from Column 17, line 54 through Column 18, line 68, incorporated herein by reference Suds modifiers are also optional ingredients and are descπbed in U S Patents 3,933,672, issued January 20, 1976 to Bartoletta et al , and 4, 136,045, issued January 23, 1979 to Gault et al , both incorporated herein by reference

Suitable smectite clays for use herein are descπbed in U S Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference Suitable additional detergency builders for use herein are enumerated in the Baskerville patent. Column 13, line 54 through Column 16, line 16, and in U S Patent 4,663,071, Bush et al, issued May 5, 19b both incorporated herein by reference

Enzymes can be included in the formulations herein for a wide vanety of fabnc laundenng purposes, including removal of protein-based, carbohydrate-based, or tπglyceπde-based stains, for example, and for the prevention of refugee dye transfer, and for fabnc restoration The enzymes to be incorporated include proteases, amylases, Upases, cellulases, and peroxidases, as well as mixtures thereof Other types of enzymes may also be included They may be of any suitable oπgm, such as vegetable, animal, bacteπal, fungal and yeast oπgin However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents. builders and so on In this respect bacteπal or fungal enzymes are prefeπed, such as bacteπal amylases and proteases, and fungal cellulases

Suitable examples of proteases are the subtilisms which are obtained from particular strains of B subtilts and B lichemforms Another suitable protease is obtained from a strain of Bacillus

having maximum activity throughout the pH range of 8-12 developed and sold bv Novo Industπes A/S under the registered trade name ESPERASE The preparation of this enzv me and analogous enzymes is descπbed in Bπtish Patent Specification No 1.243,784 of Novo Proteolvtic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trade names ALCALASE and SAVINASE by Novo Industπes A/S (Denmark) and

MAXATASE by Intemationai Bio-Synthetics, Inc (The Netherlands) Other proteases include Protease A (see European Patent Application 130,756, published January 9 1985) and Protease B (see European Patent Application Seπal No 87303761 8, filed Apπl 28 1987 and European Patent Application 130,756, Bott et al, published January 9, 1985) Amylases include, for example, α-amylases descπbed in Bntish Patent Specification No

1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc and TERMAMYL, Novo Industπes

The cellulase usable in the present invention include both bacteπal or fungal cellulase Preferably, they will have a pH optimum of between 5 and 9 5 Suitable cellulases are disclosed in U S Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producmg fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a manne mollusk (Dolabella Auπcula Solander) suitable cellulases are also disclosed in GB-A- 2 075 028, GB-A-2 095 275 and DE-OS-2 247 832 Suitable lφase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeπ ATCC 19 154. as disclosed in Bπtish Patent 1,372,034 See also Upases in Japanese Patent Application 53,20487 laid open to public inspection on February 24, 1978 This lipase is available from Amano Pharmaceutical Co Ltd . Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter refeπed to as "Amano-P " Other commercial Upases include Amano-CES. Upases e\ Chromobacter viscosum, e g Chromobacter viscosum var lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co . Tagata, Japan, and further Chromobacter viscosum Upases from U S Biochemical Corp , U S A and Disoynth Co , The Netherlands, and Upases Pseudomonas gladioli The LIPOLASE enzyme denved from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a prefeπed lipase for use herein

Peroxidase enzymes are used in combination with oxygen sources, e g , percarbonate, perborate, persulfate, hydrogen peroxide, etc They are used for "solution bleaching," I e to prevent transfer of dyes or pigments removed from substrates dunng wash operations to other substrates in the wash solution Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, Ugninase, and haloperoxidase such as chloro- and bromo-peroxidase Peroxidase- containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O Kirk, assigned to Novo Industries A S

A wide range of enzvme mateπals and means for their incorporation into synthetic detergent compositions are also disclosed in U S Patent 3 553 139 issued January 5 1971 to McCarty et al Enzymes are further disclosed in U S Patent 4 101 457 Place et al issued July 18 1978, and in U S Patent 4 507,219 Hughes issued March 26 1985 both Enzyme mateπals useful for liquid detergent formulations, and their incorporation into such formulations are disclosed in U S Patent 4,261,868, Hora et al, issued Apπl 14, 1981 Enzymes for use in detergents can be stabilized by vanous techniques Enzyme stabilization techniques are disclosed and exemplified in U S Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No 0 199 405, Application No 86200586 5 published October 29 1986 Venegas Enzyme stabilization systems are also described, for example, in U S Patent 3,519,570 Additionally, dye transfer inhibiting agents may also be included for example, polyvinylpyπolidone, polyamine N-oxide, copolymers of N-vinylpyπolidone and N-vinylimidazole are a suitable dye transfer inhibiting polymers for use in the present detergent composition The level of such additional dye transfer inhibiting agents mav vary, but typicallv will be from about 0 01% to about 10% by weight of the detergent composition

Agglomeration Process The following descnbes exemplifies the agglomeration process by which the detergent composition of the invention is produced The parameters noted herein are exemplary only and should not be considered as limiting in any way Step A - Preparation of Surfactant Paste - The objective is to combine the surfactants and liquid in the compositions into a common mix in order to aid in surfactant soiubilization and agglomeration In this Step, the surfactants and other liquid components including the hydrotrope are mixed together in a Sigma Mixer at 140°F (60°C) at about 40 rpm to about 75 rpm for a penod of from 15 minutes to about 30 minutes to provide a paste having the general consistency of 20 000- 40,000 centipoise Once thoroughly mixed, the paste is stored at 140°F (60°C) until agglomeration Step (B) is ready to be conducted

Step B - Agglomeration of Powders with Surfactant Paste - The purpose of this Step is to transform the base formula ingredients into flowable detergent agglomerates having a mean particle size range of from about 800 microns to about 1600 microns In this Step, the powders (including mateπals such as zeolite, citrate, citπc acid builder, layered silicate builder (as SKS-6) sodium carbonate, ethylenediaminedisuccinate, magnesium sulfate and optical bπghtener) are charged into the Eiπch Mixer (R-Senes) and mixed briefly (ca 5 seconds - 10 seconds) at about 1500 rpm to about 3000 rpm In order to mix the vanous dry powders fully The surfactant paste from Step A is then charged into the mixer and the mixing is continued at about 1500 rpm to about 3000 rpm for a penod from about 1 minute to about 10 minutes preferably 1-3 minutes, at ambient temperature The mixing is stopped when course agglomerates (average particle size 800- 1600 microns) are formed

Step C - The purpose of this Step is to reduce the agglomerates' stickiness by removing/drying moisture and to aid in particle size reduction to the target panicle size (in the mean particle size range from about 800 to about 1600 microns, as measured by sieve analysis). In this Step, the wet agglomerates are charged into a fiuidized bed at an air stream temperature of from about 41°C to about 60°C and dried to a final moisture content of the particles from about 4% to about 10%.

Step D - Coat Agglomerates and Add Free-Flow Aids - The objective in this Step is to achieve the final target agglomerate size range of from about 800 microns to about 1600 microns, and to admix materials which coat the agglomerates, reduce the caking/lumping tendency of the particles and help maintain acceptable flowability. In this Step, the dried agglomerates from Step C are charged into the Eirich Mixer (R-Series) and mixed at a rate of about 1500 rpm to about 3000 rpm while adding 2-6% Zeolite A (median particle size 2-5μm) during the mixing. The mixing is continued until the desired median particle size is achieved (typically from about 5 seconds to about 45 seconds). At this point, from about 0.1% to about 1.5% by weight of precipitated silica (average particle size 1-3 microns) is added as a flow aid and the mixing is stopped.

In order to make the present invention more readily understood, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope.

EXAMPLE I Several detergent compositions (A-C) are made in accordance with the agglomeration process described above. Compositions A and B are within the scope of the invention and composition C is outside of the invention and is presented for purposes of comparison as described in Example II hereinafter. The relative proportions of compositions A-C. in agglomerate form, are listed in Table I below. A B C

Component Surfactants % (wt.) % (wt.) % (wt.)

Ci4_i5 primary alkyl sulfate 18.8 18.8 19.2

C ₁₂ -C!5 alkyl ethoxy (1-3) sulfate 10.6 10.6 10.8

Sulfyl succinate (Na) 2.0 Xylene sulfonate (Na) - 2.0

Builders

Zeolite 4A 39.2 39.2 40.0

Carbonate (Na) 15.8 15.8 16. 1

Additives Misc. (water, perfume and minors) 13.6 13.6 13.9

100.0 00.0 100.0

EXAMPLE II

This Example illustrates the surpπsinglv improv ed solubility achieved bv the detergent composition of the invention Specifically standard dosages of compositions A-C ( 1 170 ppm) are dissolved in an aqueous laundering solution having a water temperature of 10°C and a water hardness of 7 grains/gallon (Ca Mg ratio of 3 1) The laundeπng solution is continuously agitated at a rate of 75 rpm and samples of the wash solution were taken at vanous time intervals as shown in Table I below For purposes of illustrating the improved solubility of the detergent composition according to the invention, the amount of surfactant in the laundeπng solution is determined by conducting the well known "catS0 ₃ " titration technique on the samples taken from individual wash solutions containing one of the compositions A-C In particular, the amount of anionic surfactant in the laundeπng solution is determined by filteπng the samples through 0 45 ny lon filter paper to remove the insolubles and thereafter, titrating the filtered solution to which anionic dyes (dimidium bromide) have been added with a cationic titrant such as Hyamine™ commercially available from Sigma Chemical Company Accordingly, the relative amount of anionic surfactant dissolved in the wash solution _uι be determined This technique is well known and others may be used if desired The results are shown in Table II below

TABLE II

(% total of anionic dissolved)

Time (Minutes) A B C

0 0% 0% 0%

1 22% 37% 22%

3 29% 45% 34%

10 52% 58% 34%

From the results in Table II, it is quite clear that compositions A and B which are within the scope of the invention surpnsingly have improved solubility over composition C which is outside the scope of the invention

EXAMPLE III

Several laundry bars D and E, suitable for hand-washing soiled fabπcs are prepared bv standard extrusion processes and compπse the following ingredients listed in Table III

TABLE πi

D E

Component Surfactants % ( t.) % ( t.)

C14.15 pnmary alkyl sulfate 18 8 18 8 ^c 12" ^c 15 ^alkvl ethoxy (1-3) sulfate 10 6 10 6

Sulfyl succinate (Na) 2 0 -

Xylene sulfonate (Na) - 2 0

Builders

Zeolite 4A 39 2 39 2

Carbonate (Na) 15 8 15 8

Additives

Misc (water, perfume and minors) 13 6 13 6

100 0 100 0

Having thus descπbed the invention in detail, it will be obvious to those skilled in the an that vanous changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is descπbed in the specification