PH26460A - Spray dried base beads and detergent compositions - Google Patents

Description

' pentasodium tripolyphosphate, which had been used to a great extent in built laundry detergent compositions, : had been suspected in some quarters of being harmful, and accordingly, for years compositions containing BTA | were not marketed in the United States. There has ne- ver been any serious doubt that phosphates are safe for humans and recently disapproval by United States autho- rities of the use of NTA in detergents has been with- drawn. Accordingly, although certain non-phosphate de- ‘10 tergent formulations will continue to be manufactured for employment in areas that are located adjacent to lakes and rivers, wherein the phosphate tends to pro- : vide a needed nutrient for algae growth ang thereby may : cause some eutrophication of such waters, detergent com- positions containing phosphate and/or NTA are marketable once more.

Although the zeolites, preferably Zeolite A and especially preferably hydrated Zeolite La, had been build- er salts in phosphate-free and NTA-free detergent composi- tions, they have now also been found to be useful compo- ] nents of improved detergent and base bead compositions containing phosphat(s) and/or NTA. Normally about 6 to 12% of water soluble sodium silicate has been utilized in crutcher mixes from which spray dried bade beads or : detergent compositions were to be made. The silicate has - 3 = l

This invention relates to free flowing, spray dried base beads which are useful for the manufacture of a particulate built synthetic nonionic organic de- . teregent composition. It also relates to free flow- ing, spray dried detergent compositions. More parti- cularly, the invention relates to such beads and com- positions which contain certain proportions (within prescribed ranges) of a water softening aluminesili- cate, such as a zeolite, bentonite, and water soluble builder for detergents. The product made is of reduced zeolite deposition characteristics compared to prior art products containing similar proportions of the wa-~ ter softening aluminosilicate. Such prior art products would normally also have contained appreciable propor- tions of water soluble silicate and usually would not have contained bentpnite.

In recent years water softening insoluble alumi- nosilicates, such as hydrated zeodites, have been em- ployed as builder constituents in laundry detergent com- positions. Initially, renewed jnterest in the zeolites } appears to have been stimulated by the necessity of pro- ducing detergent formulations which did not contain phos- phates. Trisodium nitrilotriacetate and other salts of nitrilotriacetate acid (NTA), which had been suggested as potential replacements for the phosphates, especially for been employed for its binding effect on the other components of the beads, which binding results in stable beads, and it has been discovered to help to produce a reticulated inner bead structure. It also functions as an anti-corrosion additive which prevents chemical attack on aluminum parts of wash- ing machines and other appliances with which the de- tergent solution may come into contact. However, in proportions formerly employed, é.g., 8 to 10% in the finished product, it had been noted that the combi- nation of the water soluble silicate and the zeolite in the crutcher led to the production of aggregates of such materials in the spray dried beads, which ag- gregates objectionably deposited on washed materials, tending to adversely affect the appearances of colors thereof. By means of the present invention, utilizing certain proportions of zeolite, bentonite and water soluble builder, with little or no water soluple sili- cate, spray dried beads of sufficient mechanical stabi- lity to be commercially acceptable result and these are oo of reduced zeolite deposition characteristics (or reduc- ed zeolite-silicate agrregate deposition characteristics).

Even when a small proportion of gilicate is present it appears that the bentonite helps to counteract any tenden- | cy of the zeolite and silicate to react to produce a par-

ticle of larger size that that of the zeolite nromal- ly present, and thereby undesirable deposition of zeo- lite or zeolite-silicate particles on washed fabrics is prevented or lessened. Additionally, the composi- tions containing bentonite are much more readily disim- tegrated and distributed throuhout the wash water, again ‘apparently due to the presence of bentonite therein.

Another advantage of the invention, when little or no ’ gilicate is employed, is that formulations containing carbonate and/or bicarbonate do not require the presence of anti-gelling materials to prevent excessive thicken- ing of the crutcher mix. Such additives are not usually necessary when the principal builder of the detergent is a phosphate and when little or no carbonate and/or bi- carbonate are present, but for non-phosphate composi- tions, which often will contain appreciable quantities of carbonate and/or bicarbonate, the ommission of anti- gelling materials is decidedly advantageous, with res- pect to both processing and “rom an economic standpoint.

The prior art relating to detergent compositions, softening compositions and detergents softener composi- tions jncludes teachings that various detergent composi- tions can be made contafhing one or more of zeolite, ben- tonite, silicate, phosphate, NTA, quaternary ammonium compounds (softeners), and other compoments, usually with synthetic organic detergent, but although the : disclosure contain extensive recitations (sometimes referred to as "laundry lists") of almost all materials

Co which have been employed for any purpose in detergent and softener compositions, they do not include clear ’ teachings or suggestions of the detergent compositions of the present invention, and this is especially true with respect to those compositions containing little or no soluble silicate. The disclosure do not appear to recognize the importance of the bentonite containing sufficient "lubricating" water between the plates there- of, and they do not appreciate the combination of bind- ing and disintegrating effocts attributable to the "hydrat~4” bentcnite. Also, many of the "reference" ~ formulas contain appreciable proportions of sodium sul- . fate, a filler, possibly to improve the physical proper- ties of the product particles, but such is not needed to make the invented compositions, which therefore can be of greater active ingredients (including builder) contents. | In accordance with the present invention free- flowing, spray dried beads, useful as a deterget or for the manufacture of a particulate built synthetic nonie- nic organic detergent composition, which detergents are of reduced particle deposition characteristics due to 29 the presence of bentonite and a low content of water solu-

ble silicate or absence of such silicate in the spray ’ dried beads, compkise by weight from 5 to 60% water of softening aluminosilicate, 2 to 1% of bentonite, con- taining sufficient moisture to facilitate dispersion of the bentonite so as inhibit deposition of aluminosili- cate on laundry being washed, 5 to 60% of water &oluble builder or a mixture of such builders, O to 30% of water soluble synthetic organic detergent and O to 5% of water soluble silicate. The aluminosilicate may be a zeolite having a substantial exchange capacity for calcium ion, the bentonite is of appreciable swelling capacity in wa= . ter and includes a sufficient proportion of moisture to facilitate disintegration of the plate-to-plate bonds there- of when the detergent beads, alone or in mixture with other detergent components, are placed in water, the water soluble builder or builder mixture is a polyphosphate, nitriletri- ' acetate or carbonate, and there is no water soluble sili- cate present. Also within the invention are detergent com- positions made by spray drying the described bead formula with an anionic detergent present in the crutcher mix or by the spraying nonionic detergent in liquid form onto tumb- ling detergent-free beads or beads containing only rela- tively small proportions of anionic detergent or mixture of anionic detergents. Mixtures of such compositions, mix- ed anionic and nonionic detergent compositions, are also .

Ca useful and may possess superior washing properties.

The zeolites employed include crystalline, amorphous and mixed crystalline-amorphous zeolites, of both natural and synthetic origins, which of sa- :

S tisfactorily quick and sufficiently effective activi- ties in counteracting calcium hardness ions in wash waters. Preferably, such materials are capable of reacting sufficiently rapidly with the calcium ions so that, alone or in comjunction with other water softening compounds in the detergent, they soften the wash water before adverse reactions of such ions with other components of the synthetic organic deter- gents composition occur. The zeolites employed may be . characterized as having a high exchange capacity for | calcium ion, which is normally from about 200 to LOO or more milligram equivalent of calcium carbonate hard- ness per gram of the aluminoslicate, preferably 250 to 350 mg. eq./ge Also they vreferably have a hardness depletion rate residual harness of 0.02 to 0.05 mg.

Cacd,/1iter in one minute, preferably 0.02 to 0.03 mg./1., and less than 0.01 mg/l. in 10 minutes, all on an anhydrous zeolite basis.

Although other ion exchanging zeolites may also be utilized, normally the finely divided synthetic zeolite builder particles employed in the practice of this invent-

ion will be of the formula (Na 0) "(A1,04) "(8i0,) °¥ H,0 E wherein x is 1, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to 3.5, preferably 2 to 3 or about 2, and W is from O to 9, preferably 2.5 to 6.

The zeolite should be a univalent cation-ex- changing zeolite, i.e., it should be an aluminosili- cate of a univalent cation such as sodium, potassium, lithium (when practicable) or other alkali metal, am- monium or hydrogen (sometime). preferably the univalent cation of the zeolite molecular sieve is an alkali me- tal cation, especially sodium or potassium, and not most preferably it is sodium. . Crystalline types of zeolites utilizable as good jon exchangers in the invention, at least in part, in- clude zeolites of the following crystals structure groups

A, X, Y, L, mordenite and erionite, of which types A, X ro ahd Y are preferred. Mixtures of such molecular sieve zeolites can also be useful, especially when type A zeo- lite is present. These crystalline types of zeolites are well known in the art and more particularly des- cribed in the text Zeolite Molecular Sieves, by Donald

W. Breck, published in 1974 by John Wiley & Sons. Typi- : cal commercially available zeolites of the aformentioned . | 25 structural types are listed in Table 9.6 at pages 747-

—_ 749 of the Breck text. Such zeolites are known in the art. Some, and other such suitable zeolites have been described in many patents in recent years for use as detergent composition builders,

The zeolite used in the invention is usually synthetic and jt is often characterized by a ne twork of substantially uniformly sized pores in the range of about 3 to 10 Angstroms, often being about U4 : (normal), such size being uniquely determined by the unit structure of the geolite crystal. Prefer- ably it is of type A or similar structure, particular- ly described at page 133 of the aforementioned text.

Good results have been obtained when a type UA mole- cular sieve zeolite is employed, wherein the univalent cation of the zeolite is sodium and the pore zise of the zeolite is about 4 Angstroms, and such zeolites are pre- ferred. Such zeolite molecular sieves are described in

U.S. patent 2,882,243, which refers to them as Zeolite

A.

Molecular sieve zeolites of ion exchanging and water softening properties can be prepared in either a dehydrated or calculated form, which contains from about 0 or about 1.5% to about *® of moisture, or in a hydrated or water loaded form which contains additional bound wa- . ter in an amount from about 4% up to about 36% of the zeolite total weight, depending on the type of zeo- lite used.

The water containing hydrated for of the molecular sieve zeolite (preferably hydrated to about 15 to 70% of capacity) is preferred in the prac'ice of this invention when a crystalline pro- duct is to be used.

The manufacture of such crystal is well known in the art.

For example, in the prepa- ration of Zeolite A, referred to above, the hydrated zeolite crystals that are formed in the crystalliza- tion medium (such a a hydrous amorphous sodium alu- minosilicate gel) are used wi thont undergoing high ) temperature dehydration (calcining to 3% or less wa- ter content) that is normally practiced in preparing such crystals for use as catalyst, e.g., cracking } 15 catalysts.

The crrstalline zeolite, in either com- pletely hydrated or partially hydrated form, can be a . or recovered by filtering off the crystals from the crys- tallization medium and drying them in air at ambient temperature so that their water contents are in the range of ahout 5 to 30%, prafcorably about 10 or 15% to 25%, such as 17 to 22%, €<R«, 20%. However, the mois- ture content of the molecular sieve type zeolite being employed may be lower, as we previously described, in which case the zeolite can Ye hydrated during crutch-~ i . ing and other processing.

* } Preferably the zeolite should be in a finely divided state, with the ultimate particle diameters being up to 20 microns, e.g., 0.005 or 0.01 to 20 microns, more preferably being from 0.01 to 15 mic- rons, e.g., 5 to 12 microns, and especially prefer- so ably being Of 0.01 to 8 microns mean particle Bize, e.R., Ce 3 to 7 microns, if crystalline, and 0.01 to 0.1 microns, e.g., 0.01 to 0.05 micron, if amorphous. Although the uttimate particle sizes are much lower, usually the zeo- lite particles will be of sizes within the range of 100 to 400 mesh, preferably 140 to 325 mesh. Zeolites of : smaller sizes will often become objectionably dusty and those of larger sizes may not sufficiently and satisfac- . torily attach to carbonate, bicarbonate, phosphate and/ or NTA base particles nuclei on which they may be dis~- tributed with the bentonite, such as in a gel-like or film state, during spray drying of a crutcher mix to form base beads.

The bentonite employed is a colloidal clay (alu- minum silicate) containing montmorillonite. Montmoril- lonite is a hydrated aluminum silicate in which about 1/6th of the aluminum atoms may be replaced with magne- sium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, magnesium and other metals } . 25 may be loosely combined. The type of bentonite clay which is most useful in making the invented base beads is that which is known as sodium bentonite (or Wyoming or western bentonite), which is normal- ) ly a light to cream-colored impalpable powder which, in water, forms a colloidal suspension having strongly . thixotropic properties. In water the swelling capaci- ty of the clay will usually be in the range of 3 to 15 : ml./gram, preferably 7 to 15 ml./g., and its viscosity, at a 6% concentration in water, will usually be in the . range of 3 to 30 centipodses, preferably 8 to 30 centi- poises, Preferred swelling bentonites of this type are : sold under the trademark Mineral Colloid, as indust- rial bentonites, by Benton Clay Company, an affiliate . of Georgia Kaolin Co. These materials which are the | same as those formerly sold under the trademark THIXO-

JEL, are selectively mined and beneficiated bentonite, and those considered to be most useful are available as : Mineral Colloid No's. 101, etc., corresponding to THIXO- .JELS No's. 1,2, 3 and 4. Such materials have pH's (6% concentration in water) in the range of 8 to 9.4, maxi- mum free moisture contents of about 8% and specific gravities of about 2.6, and for the pulverized grade about 85% passes through a 200 mesh U.S. Sieve Series sieve. Beneficiated Wyoming bentonite is preferred as a component of the present compositions but other ben- :

tonites are also useful, especially when they form a minor proportion of the bentonite used.

Although it : js desirable to limit maximum free moisture content, as mentioned, it is even more important to make certain that the bentonite being employed includes enough free moisture, most of which is considered to be present be- tween adjacent plates of he bentonite, to facilitate quick disintcgration of the bentonite and any adjacent materials in the particles when such particles or de- tergent compositicns containing them are brought into contact with water, such as wash water.

It has been found that at least about 2%, preferably at least 3 and more preferably, about 4% or more of water should be present . in the bentonite initially, before it is admixed with the other bead components in the crutcher, and such proportion should also be present after spray drying.

In other words, overdrying to the point where the bentonite loses its "in- ternal" moisture can significantly diminish the utility of the present compositions.

When the bentonite moisture con- tent is too low the bentonite does not act to prevent si- licate-zeolite agglomerates being fotmed and it also does not aid in disintegrating the beads in the wash water.When the bentonite is of satisfactory moisture content it ex- hibite an exthangeable calcium oxide percentage in the range of about 1 to 18 and with respect to magnesium oxide - 1h - oo such percentage is normally in the range of 0.04 to 0.41, Typical chemical analyses of such materials are from 64.8 to 73.0% of 550, 1.4 to 1.8% of

A105, 1.6 to 2.7% of MgO, 1.3 to 3.1% of CaO, 2.3 to 3.4% of Fe, 05, 0.8 to 2.8% of Na,0 and Ok to 8.0% of K,0.

The water soluble builder or mixture thereof employed may be one or more of the conventional mate- rials that have been used as builders or suggested for } such purpose. These include inorganic and organic build- ers, and mixtures thereof. Among the inorganic builders those of preference are the various phosphates, prefer- ably polyphosphates, e.g., tripolyphosphates and pyro- . phosphates, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate. Trisodium nitrilotriacetate (NTA), preferably employed as the monohydrate, and pther nitrilotriacetates, such as disodium nitrilotriacetate, are preferred water soluble builders. Sodium tripoly- phosphate, sodium pyrophosphate and NTA may be utilized © 20 in hydrated forms but even when anhydrous compounds are : used the bentonite and zeolite appear to inhibit caking due to subsequent hydration. Of course, carbonates, such as sodium carbonate, are useful builders and may desirabzy be employed, alone or in conjunction with bicarbonates, such as sodium bicarbonate. When the polyphosphates are employed it may b: pr ferred to have sodium pyrophos-~ phate present with sodium tripolyphosphate in propor- tion from 1510 to 10:1, preferably 1:5 to 5:1 with : respect to it, with the total proportion of both build- ers being about the same as that mentioned herein for the sodium tripolyphosphate.

Other water soluble build- ers that are considered to be effective include the va- rious other inorganic and organic phosphates, borates, e.g.y borax, citrates, gluconates, EDTA and iminodi- acetates.

Preferably the various builders will be in the form of their alkali metals salts, either the sodium or potassium salts, or a mixture thereof, but sodium salts are normally more prefered.

In some instances, as when neutral or slightly acidic detergent compositions are . 15 being produced, acid forms of the builders, especially of the organic builders, may be preferable but normally the salts will either be neutral or basic in nature.

The silicates, preferably sodium silicate of Na,0:5i0, ratio within the range of 1:1.6 to 1:3.0, preferably }:2 to 132. 8, €.8.y 132.35 or 1:2.4, also serve as builder salts but because of their strong binding properties and their cha- racteristic of promoting aggregation or agglomeration with zeolite particles, they are special cases of builders and jt is preferred that they be omitted from the present com- positions.

However, because they do pos&ess anti-corrosion properties, especially important when the detergent solution is to be employed in washing machines or other appliances in contact with aluminum parts there- of, they may sometimes be present in limited small pro- portions. In such instances it nay be preferable for | - hydrated sodium silicate particles to be post-added, so that they do not react with or agglomerate with zeolite particles in the crutching and spray drying operations. Although sodium sulfate and sodium chlo- : ride and other filler salts possess no building properties they are somtimes utilized in detergent compositions for their filling characteristics. In addition to increasing the volume and weight of the product to facilitate measur- ing, they also sometimes improve bead stabilities and phy- sical properties of the detergent composition beads in which they are incorporated. Nevertheless, because the present compositions are satisfactory without any fillers being present, such are preferably avoided entirely or any proportion thernof present is minimized, usually to a practical minimum. :

Usually the detergent(s) employed will normally be either nonionic or ahionic or both but amphoteric or ampholytic detergents may also b: used, especially in conjunction with nonionics and/or anicnics in the pre- sent compositions. Cationic detergents may serve as fab- ric softeners in these products but normally will not be

- spray dried with anionic detergents, due to an unde - sirable interaction that can take place. These clas- ses of materials are well known and have been described repeatedly in the detergent art. Because they are not preferred components of the present compositions no fur- ther description thereof in this specification is con- sidered to be appropriate.

Although various nonionic detergents of satis- factory physical characteristics nay be utilized, in- cluding condensation products of ethylene oxide and propylene oxide with each other and with hydroxyl-con- taining bases, such as nonyl phenol and Oxo-type alco- . hols, it is highly preferred that the nonionic deter- gent be a condensation product of ethylene oxide and higher fatty alcohol. In such products the higher fatty alcohol is of 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and the nonionic detergent contains from about 3 to 20 or 30 ethylene oxide groups per mol, pre- ferably from 6 to 12. Most preferably, the nonionic de- tergent will be one in which the higher fatty alcohol is of about 12 to 13 or 15 carbon atoms and which contains : from 6 to 7 or 11 mols of ethylene oxide. Such deter- " gents are made by Shell Chemical Company and are avail- able under the the trade names teodor © 237645 and 25.7.

Among their specifically attractive properties, in addi- tion to good detergency with respect to oily marks on }

goods to be washed, is a comparatively low melting point, yet appreciably above room temperature, so that they may be sprayed onto base beads as a liquid which solidifies. 5 . Various anionic detergents, usually as sodium salts, may be employed but those which are most pre- ferred are linear higher alkyl benzene sulfonates, higher alkyl sulfates and higher fatty alcohol poly- ethoxylate sulfates. Preferably, in the higher alkyl - 10 benzene sulfonate the higher alkyl is linear and of 12 to 15 carbon atoms, e.g., 13, and is a sodium salt. ,

The alkyl sulfate is preferably a higher fatty alkyl sulfate of 10 to 18 carbon atoms, preferably 12 to 16 ’ carbon atoms, e.g., 12, and is also employed as the so- dium salt. The higher alkyl ethoxamer sulfates will . similarly be of 10 or 18 carbon atoms, e.g., 12, in the higher alkyl, which will preferably be a fatty alkyl, and the ethoxy content will normally be from 3 to 30 : ethoxy groups per mol, preferably 3 or 5 to 20. Again, the sodium salts are preferred. Thus, it will be seen that the alkyls are preferably linear or fatty higher alkyls of 10 to 18 carbon atoms, the cation is prefer- . ably sodium, and when a polyethoxy chain is present the sulfate is at the end thereof. Other useful anionic de- tergents include the higher olefin sulfonates and para-

ffin sulfonates, e.g., the sodium salts wherein the . olefin or paraffin groups are of 10 to 18 carbon atoms.

Specific examples of the preférred detergents are 8o- dium tridecyl benzene sulfonate, sodium tallow alcohol polyethoxy (3 Et0) sulfate, and sodium hydrogenated tal- : low alcohol sulfate. In addition ‘to the preferred anio- nic detergents mentioned, others of this well known group may also be present, especially in only minor proportions with respect to those previosuly described. Also, mixtures 10 . thereof may be employed and in some cases such mixtures can be superior to single detergents. The various anionic de- tergents are well known jn the art and are described at length at pages 25 to 138 of the text Surface Active Agents and Detcrgents, Vol. II, by Schwattz, Ferry and Berch, pub- lished in 1958 by Interscience Publishers, Inc. } Various adjuvants may be p ~gent in the crutcher mix frem which base beads or detergent compositions may be spray dried, or such adjuvants may be post-added, with the decision as to the mode of addition often being deter- mined by the physical properties of the adjuvant, its re- sistance to heat, its resistance to degradation in the aqueous crutcher medium, and its volatility. Among the more important of the adjuvants ie a polycrylate which has been found to be useful in controlling bead characte- ristics and bulk density, has dispersing, anti-deposition

V and anti- redeyposition effects in the present compo- sitions, and aids in maintaining the crutcher mix fluid and homogeneous. . The polyacrylate, present in preferred base beads of this invention, is a low molecular weight polyacrylate, such molecular weight usually being within the range of about 1,000 to 5,000, preferably 1,000 to 3,000, and most preferably 1,000 to 2,000 or about 2,000. The polyacrylate may be partially newtra- lized or completely neutralized, e.g., about 1/2 or 1/3 present as sodium polyacrylate. Although modified poly~ acrylates may be substituted for the described sodium polyacrylate, including some other alkali metal poly- acrylates and hydroxylated polyacrylates, it is pre- ferred that such substitutions be limited to a miner . proportion of the material and preferably the polyacry- . late will be an unsubstituted sodium polyacrylate. Such . materials are available from Alco Chemical Corporation : under the name Alcosperse ® The sodium polyacrylates . are available clear amber liquids or powders, with their solutions being of about 25 to 40% solids content, e.g., 30%, and with the pH of such solutions or of a 30% aqueous solutions of the powder being in the range of about 7.5 to 9.5, e.g., about 9. Such materials are completely soluble in water and have been employed as

_— dispersants.

They have been shown to possess the capability of binding calcium ion and have been used to prevent depositing out of insoluble calcium com- pounds from aqueous solutions.

In the present spray drying process small quantities (or percentages) there- of help to make the resulting beads of improved poro- sity.

. When the crutcher mix includes carbonate and/or bicarbonate and silicate, even if the amount of the si-

licate is small, there may be a tendency for the mix to gel or "freeze" in the crutcher, especially if, due to delays in processing, the crutcher mix is held longer than the normal 30 minutes or so.

In such cases, when silicate is present processing aids are preferably also present in the mix ( and consrquently, in the finished base beads and detergent composition) to prvent prema- ture solidification or gelation.

Most preferably, such include citric acid and magnesium sulfate.

Instead of citric acid, soluble citrates, such as sodium citrate,

may be used and while it is preferable to employ anhy- . drous magnesium sulfate, various hydrates thereof, such as epsom salts, may also be used.

Also, magnesium ci-

trate can be substituted.

In place of the preferred anti- gelling system other means and suitable systems for main- taining the crutcher mix fluid may be substituted, such as sodium sesquicarbonate, employ~d in replacement ’ of someof the sodium carbonate and sodium bicarbonate. ‘ However, while such processing aids are useful in many cases, it is a feature of this invention that they are not needed in manufacturing the preferred base beads from which silicate is omitted.

Although some adjuvants, such as fluorescent brightener, pigment, e.g., ultramarine blue, titanium . dioxide, and inorganic filler salt may be added in the i crutcher, others, such as perfumes, enzymes, bleaches, some colorants, bactericides, fungicides, fabric soft- : eners and flow promoting agents -may often be sprayed : onto or otherwise mixed with the base beads or spray dried detergent composition, with any nonionic deter- gent and/or independently, so that they will not be ad- versely affected by the elevated temperatures of the apray drying operation and also so that their presence in the spray dried beads does not inhibit absorption of nonionic detergent, when such is to be post-sprayed onto the beads. However, for stable and normally solid adjuvants, mixing with the starting slurry in the crut- : cher is also feasible. Thus, it is contemplated that pigments and fluorescent brighteners, when employed, "will normally be present in the crutcher mix from which the present base beads are sprayed. The preferred color-

ee — — ing agent .is ultramarine blue but other stable pig- ments and dyes may be used with tt or in replacement of it. Because the spray dried base beads of ‘this invention sometimes may be off-color, usually due to employment of naturally occurring minerals, the hue from such coloring agent may be adversely affected.

It has been found that incorporating a small proportion of titanium dioxide in the crutcher mix helps to retain the desired hue of the coloring agent and the presence of the titanium dioxide does not appear to have ahy ad- . . verse affect on the appearance of laundry washed with detergent compositions made from base beads containing it.

Among the fluorescent brighteners the most pre- ferred is Tinopal S5BM, especially in extra concentrated form. However, various other cotton brighteners, such as those sometimes referred to as CC/DAS brighteners, derived from the reacticn product of cyanuric chloride and the disodium salt of diaminostilbene disulfonic acid, may also be employed, including variations thereof with respect to substituents on the triazine and aromatic rings. This class of brighteners is known in the deter- gent art and will most often be used when bleaching com- ponents are not present in the final product. When it is desired for the detergent composition to include a - 2h -

bleach, such as sodium perborate or other oxidizing bleach, bleach stable brighteners will usually be incorporated in the crutcher mix. Among these there may be mentioned the benzidine sulfone disulfonic acide, naphthotriazol stilbene sulfonic acids and : benzimidazolyl derivatives. Polyamide brighteners, ‘ which also may be present, include aminocoumarin or diphenyl pyrazoline derivatives, and polyester bright- eners, which can also be used, include naphthotriazo- ‘10 1yl stilbenes. Such brighteners are normally used as their soluble balts but they may be charged as the cor- responding acids. The cotton brighteners will usually comprise major proportions of the brightener systems employed.

Enzyme preparations, which normally are post- added to the base beads because they are heat sensitive, may be any of a variety of commercially available pro- } ducts, included amon which are Alcalase, manufactured by .

Novo Industri, A/S, and Maxatase, both of which are al- kaline proteases (subtilisin). Maxazyme 375 bs geme- : , times preferred. Although the alkaline proteases are h most frbgquently employed, amylotic enzymes, such as al- . pha-atylase, may also be utilized. The mentioned com- : postions usually contain active enzymes in combination with an inert powdered vehicle, such as sodium or cal-

NES nn SSS cium sulfate, and the proportion of active enzyme may vary widely, usually being from 2 to 80% of the com- mercial preparation. In this specification proportions referred to are of the enzyme preparations, not the ac- tive part thereof only. Ferfumes employed, which are : usually heat sensitive and may contain volatiles, in- i cluding a solvent, such as alcohol, are normally of syn- thetic perfumery materials, sometimes mixed with natural components, and generally will include alcohols, aldehyde terpenes, fixatives and other normal peffume components.

Flow promoting agents, such as special clays, which are sometimes added to detergent products, while often use- ful to improve flowability and to diminish tackiness of } various compositions, are unnecessary in the present case, possibly in part due to the presence of the bentonite and the absence or very limited presence of silicate. However, they may be added if desired, to further increase flow~- ability. While it has been found that detergent compo- sitions made from the present base beads do not require the presence of any ahti-corrosion additive to replace the omitted silicate, it is within the invention to util- jze suitable such materials and it will be preferred to employ those which are stable under crutching and spray drying conditions and which do not adversely affect such operations. Such anti-corrosion additives or antioxi-

dants may be organic or inorganic, with inorganic materials normally being preferred, and they will preferably be chosen for suitably for preventing corrosion of aluminum parts of washing machines. If it is desired to continue to utilize a silicate for such purpose or to employ a silicate for its magne- sium ion hardness treatment effect, a powdered sili- cate will normally be preferably, such as hydrous so- dium silicate, which is commercially available under + 10 the name Britesil ® manufactured by Philadelphis

Quartz Co. (Na,0:810 = 1:2.4), and such will prefer- be post-added. However, other normally solid solubles : silicates, preferably of alkali metals, may also be post-added to the beads of this invention, preferably } 15 after any absorption of nonionic detergent that is to be effected. ;

When it is desired for the product made to pos- sess textile softening characteristics, softendéng mate- : rials, preferably in dry powder form, may also be post- added to the base beads in suitable manner. This class of materials is well known and most generally such soft- eners are cationic compounds, particularly quaternary ammonium compounds, such as quaternary amtonium halides.

Especially preferred are the higher alkyl-, alkylaryl- and arylalkyl-lower alkyl quaternary ammonium chlorides and bromides, such as distraryl dimethyl armonium : chloride. Of commercial softening materials that which is most preferred is sold under the trade name Arosurf

TA-100, manufactured by Sherex Chemical Company, Inc.

Such compounds possess anti-static and antibacterial . properties too but if desired, other antibacterial ad-~ . juvants may also be employed, preferably also incorpo~- rated in the product by post-addition. '

Of course, water is present in the crutcher to serve as the medium for dispersing the various other beads components, and some water, in both free and hy- drate form, is in the product. During drying of the beads the initial moisture content thereof, which will pe about 25 to 60% may be lowered to about 5 to 15%, with such moisture content being sufficient so that the bentonite in the dried beads contains at least 2% and preferably at least 4% of moisture. It is preferred to employ deionized water, 80 that the hardness ion contents thereof may be very low and so that metallic ions that can promote decomposition of any organic materials which may be present in the crutcher mix, base beads and deter- ] gent are minimized, but city or tap water may usmndlly be employed instead. Normally the hardness content of such water will be less than 150 p.p.m., a8 CaCO, more pre- | ferably the hardness content will be less than 100 p.p.m.

and most preferably it will be less than 50 p.p.m. i}

The proportions of the various components in the hase beads and in the spray dried detergent composition beads will be such as to result in their being free flowing and, for the base beads, suffi- } ciently absorptive of a nonionic detergent applied ‘thereto in liquid state so that the detergent compo- ~ sitions will be satisfactorily free-flowing. Also, of : course , the detergent compositions will be effective cleaning agents, with the builders present acting to assist the organic detergent in its detersive effect in : aqueous solutions of the compositions, and it is import- ant that the resulting products be such that they do not : cause objentionable depositions of zeolite particles (or zeolite-silicate ageregates) wn washed materials.

The zeolite particles and the bentonite particles, al- though insoluble, will not objectionably discolor or lighten colored laundry as charged, because of their } small particle sizes, but such discoloration can occur when zeolite aggregates are formed which are sufficient- ly large so as to be held to fabrics and also to be readi~ ly noticeable to the eye, especially when substantial pro- portions thereof are not removed from the laudered materials by being exhausted with the drying air during automatic dry- ing. It is also desirable for the base beads and deterpent } composition beads made to be of appropriate bulk density and

— color.

It has been found that satisfactory beads to accomplish the aformentioned purposes comprise by weight from 5 to 60% of water softening aluminosili- cate (zeolite), 2 to 40% of bentonite (of the desired moisture content) and 5 to 60% of water soluble build- er or mixture of such builders. From O to 30% of wa- : ter soluble synthetic organic detergent and/or from © to 5% of water soluble silicate may also be present but often are preferably omitted. Preferably, the spray dried beads will contain from 3 to 15% of moisture, more preferably from 5 to 12% thereof and usually from 7 to 10% thereof, including any water of hydration present.

Such water of hydration may be present in the zeolite,

NTA, phosphate, carbonate, bicarbonate and magnesium sul- fate, when such are in the formula, in addition to that between the plates of the bentonite. The recited mois- ture content includes even strongly held water of hydra- tion, such as that still retained by the zeolite even after several hours of distillation of a toluene dis- persion. In some jnstahces, as when the concentration of zeolite in the product is high, so that up to about 12 to 15% of moisture could be present in the zeolite as water of hydration, the moisture content in the spray dried beads may be as high as 20% and occasionally, may go up to about 25%. Normally, however, for good flow- ’ ability of the product and to monimize tackiness and lumping, such upper limit will be about 15%, especial- ly when the final detergent composition contains an ap- preciable proportion of nonionic detergent.

The pers centage of zeolite given includes the water of hydra- ‘ tion therein.

It is possible to make useful spray dried of moisture contents less than 3% providing that the ben- tonite has sufficient water associated with it, for the reasons previously given, but due to the strong attract- jon for moisture of the zeolite and due to the actions of the other hydratable materials that may be present it has usually been found that a minimum of 3% of moisture is needed to avoid loss of the desired internal moisture of the bentonite, which apprars to tiubricate" the plates and facilitate their separation when a product contaim- ing them is dispersed in water.

Also, when anhydrous products are made, even when sufficient moisture is re- tained in the bentonite, they are liable to be physical- ly unstable, powdering more readily and being subject to attrition and disintegration. © The bulk density of the spray dried beads may be within the range of 0.2 to 0.9 g./cc.

Bulk densities in the lower part of this range are more readily obtain- able when there is no sili€até in the crutcher mix being . - on -

. spray dried and when little or no nonionic detergent is absorbed by the beads. The higher bulk densities result when nonionic detergent is applied to porous beads and when some silicate is present in the beads.

Such lighter products have bulk densities in the 0.2 to 0.5 g./cc, range , often 0.3 to 0.4 g./cc., and the heavier particles are of bulk densities in the 0.6 to 0.9 g./cc. range, usually 0.6 to 0.8 g./cc. The bead particle sizes will usually be in the range of No's 10 to 100 (through No. 10 and on No. 100), U.S. Sieve

Series, more preferably 10 to 60, U.S. Sieve Series.

In preferred formulations the proportion of bentonite to zeolite is in the range of 1:4 to 1:1, the proportion of water soluble builder to zeolite is within the range of 1:2 to 3:1 and the proportion of bentonite to water soluble builder is within the range of 1:10 to 1:1. More preferably, such ranges of ratios are 1:3 to 2:3 to 2:1, 1:6 to 1:2, respectively. Percentagewise, the composi- tions preferably comprise from 10 to 40% of a partially ) hydrated sodium zeolite, preferably containing from 15 . , to 25% by weight thereof of water of hydration and with an exbhange capacity for calcium ion in the range of 200 to 400 milligram equivalents of calcium carbonate hard- . ness per gram of anhydrous zeolite, 2 to 35% of bentonite which is of a type which has a swelling capacity in the

¢ " \ range of 7 to 15 ml./g. and is of a viscosity in the range of 8 to 30 cp. at 6% concentration of water, 10 to 50% of water soluble alkali metal build- er salt or mixture thereof, O to 25% of water soluble synthetic anionic organic detergent and O to 3% of wa- ter soluble silicate, which silicate, when present,is an alkali metal silicate of alkali metal oxide : silicon dioxide ratio in the range pfl:1.6 to 1:3 more prefer- ably 1:2 to 1:2.8. More preferred bead formulas in- clude 15 to 35% of zeolite A, 5 to 20% of beneficiated

Wyoming bentonite, 20 to 50% of water soluble sodium builder salt or mixture thereof, 0 to 20% of water 80~ luble synthetic anionic organic detergent and 0% of so- dium silicate.

Although carbonate and bicarbonate builders are useful in making base beads within this invention, es- pecially those onto which nonionic detergent is to be : sprayed, polyphosphate and/or nitrilotriacetate build- oo er are often preferably for the spray dried beads, whe ther such include anionic detergent or not, and wheether or not intended to have nonionic detergent applied to them. Fre- ‘ ferred formulas of base beads based on NTA as the sole or main soluble builder include from 15 to 35 or Lot of hydrated zeolite, 5 or 10 to 20% of bentonite, and 20 to: 50 or 60% of NTA. When a phosphate, such as sodium tri-

: polyphosphate, is to be the principal or basic water soluble builder, the same proportions of zeolite and bentonite may be employed, but usually more phosphate can be present (than NTA). Preferably, for such base beads onto which nonionic detergent is to be sprayed or for comparable compositions based on carbonate or a or a mixture of bicarbonate and carbonate (with the ratio of carbonate:bicarbonate in the spray dried base beads being within the range of about 1 to 3), there will be no water soluble synthetic organic detergent and little or no water soluble silicate present.

When bicarbonate and carbonate together are employed in such formulations they will usually total from 20 to 40% of . the base beads and when carbonate alone is employed it will normally be 10 to 30% thereof. when an anionic det-rgent or other suitable or- panic detergent is included in the crutcher so as to pro- . duce a spray dried detergent product preferred propor- tions thereof will bs: 3 or 5 30%, more preferably 5S to 25%, and most preferably 10 to 25%, e.g., 10%, 15%, of such product, and the detergent will pref rably be ‘'se- lected from the group consisting of sodium linear alkyl benzene sulfonate wherein the alkyl is of 10 to 18 car- } bon atoms, sodium fatty alcohol sulfate wherein the al- cohol is from 10 to 18 carbon atoms and sodium fatty al- - 3h - . ¥ cohol ethoxylate sulfate wherein the fatty alcohol is of 10 to 18 carbon atoms and which contains from 3 to 30 ethylene oxide groups per mole, and mixture ‘=: thereof. At present, the most preferred of the de- tergents is sodium linear tridecyl benzene sulfonate, and alkyls are preferably of 12 to 16 carbon atoms.

When a nonionic detergent is absorbed into the spray dried base brads (and sometimes a small propor- : tion may be absorbed into the spray dried detergent beads) the proportion thereof will usually be within : the range of 5 or 8 to 30%, preferably 10 to 25%, e.g., 15%, 20%. In such case the preferred nonionic deter- - gent is a condensation product of 6 to 12 mols of ethyl- ene oxide and one mol of a higher fatty alcohol of 12 to 16 carbon atoms.

When polyacrylate is present in any of the deter- gent compotitions or base brads it will normally be from 0.05 to 1% thereof and its molecular weight is preferably ° within the range of 1,000 to 5,000,

Because the presence of anionic detergent in the spray dri-d detergent beads may inhibit the production : of a bead structure which will be absorptive of a de- sired proportion of nanionic detergent it may be pre- pared to produce spray dried detergent beads of a type within this invention and mix them with invented base beads onto which nonionic detergent has been spray- . ed, so that a higher proportivn of nonionic deter- gent may be present in the finished product. To do ' this varying ranges of proportions may be ~mployed, e.g., 1:10 to 10:1, 1:5 to 5:1 and %:2 to 2:1 of the - mentioned components, depending on the characteris- } tics wanted in the final product. It will be desire- able for the bulk densities of the beads before mixing to be approximately the same, preferably within 0.1 g./cc. of each other and the particle sizes should be approximately the same, normally being within the No. . 10 to 100, U.S. Sieve Serics range, to prevent sifting and separation of the final mix .

Froportions of adjuvants and processing aids in the base beads and spray dried detergent will normally be limited to 20% thereof, preferably being 1 to 10% and more preferably being 3 to 9% thereof. The propor- tions of processing aids, when magnesium sulfate and . . citric acid are employed, will normally be from 0.5 to 2% of magnesium sulfate, preferably 1 to 1.5% thereof, and 0.1 to 0.5% of sodium citrate, preferably 0.1 to 0. i 3% thereof. With respe~t to coloring, pigmenting and fluorescent brightening agents, when respect, the pro- portions will normally pe from 0.05 to 0.6% of coloring pigment, such as ultramarine blue, preferably 0.2 to 0.4%,

and 0.1 to 4% of fluorescent brightener, preferbaly 1 to 3% thereof.

The proportion of titanium dioxide (a whitening pigment) will normally be from 1 to 3%, preferably 1.5 to 2.5. If a coloring dye or dyes . : 5 are used instead of a coloring pigment, proportions : will usually be 1 to 50%, especially 5 to 20% of those of the coloring pigments. : For preferred spray dried beads within this in- : vention, which may contain NTA or polyphosphate build- ers with or without synthetic organic detergent, or may contain such detergent with any of a previously given list of preferred water soluble builder salts, the bulk density is in the range of 0.2 to 0.8 g./cc., the aluminosilicate is hydrated zeolite A, the bentonite in- cludes at lcast * moisture on an anhydrous bentonite ba- sis, the water soluble silicate, if present, is sodium silicate of Na,0:810, ratio in the range of 1:2 to 1:2.8, and the moisture content of the beads is from 3 to 12% thereof.

When the beads contain NTA or other sodium salt 20. of nitrilotriacetic acid, with or without synthetic orga- nic detergent, proportion of bentonite: zeolite is in the range of 1:6 to 1:2, that of NTA; zeolite is in the range of 1:2 to 2:1, and that of bentonite;NTA is in the range of 1:6 to 1:2, and the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate, and silicate are res-

pectively, within the ranges of 10 to hot, 2 to 25%, 10 to 4O%n and O to 5%.

When the preferred NTA-containing beads also contain a synthetic anionic organic deterrent, with the aformcentioned zeolite A, bentonite and moisture, and - with or without soluble sili‘:ate, they pr-oferably com=- prise 5 to 30% of synthetic anionic organic detergent, which wil! be sodium linear alkyl benzene sulfonate where- in the alkyl is of 10 to 18 carbon atoms, sodium fatty al- cohol sulfate wherein the alcohol is of 10 to 18 carbon atoms, or sodium fatty alcohol ethoxylate sulfate wherein the fatty alcohol is of 10 to 18 carbon atoms and which contain from 3 to 30 ethylene oxide groups per mol, or a mixture comprising two or more thereof, the water soluble builder is a sodium salt of nitrilotriacetic acid (NTA), the proportion of bentonite; zeolite is in the range of 1:6 to 1:1, that of NTA: zeolite is in the range of 1:3 . to 3:1, that of bentonite: NTA i5 in the range of 1:10 to 1:1, and that of synthetic anionic organic detergent: zeo- lite is in the range of 1:1 to Ltl, and the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate, synthetic anionic organic detergent, and silicate are res- pectively, within the ranges of 10 to 40%, 2 to 25%, 10 to 40%, 16 to 25% (more preferred range), and 0 to 5%.

For phosphate-containing beads, with or without the synthetic detergent the materials and ratios are the same as for the corresponding NTA-containing beads, with pentasodium tripolyphosphate or tetra- ’ " sodium pyrophosphate or a mixture thereof substitu-

S ted for NTA, but the percentages are within the ranges of 15 to 35%, § to 20%, 15 to LO¥% and O to 5%, respectively, instead. Similarly, for the phosphate containing beads with anionic detergent also present, the materials and ratios are the same as for the cor- responding NTA-containing beads and the Percentage ranges are the same except for that for total poly- phosphate, which is 10 to 50%. :

The ranges of proportions of the various base . bead components in the final detergent composition, + when nonionic detergent (possibly with other materials) is post-added may readily be calculated from those gi- ven for the base beads, diminished by proportions of the detergent and other materials that are post-added to th- beads. Conversely, the bead component propor- tions (and from them the crutcher mix formula ) may be calculated back from the final product formulation.Thus = for example, calculating the final product formula ranges : from the bead ranges, if the final detergent composition had only nonionic detergent added to it so that the final product contains 20% of nonionic detergent, from the va-

. rious ranges given for components in the base beads ranges of proportions thereof in the final deter- gent composition product may be calculated by multi- plying by 0.8, which is (100-20 )/100. Similarly, when the proportion of nonionic detergent (in formu- ias wherein it is the only additive to the beads) may range from 8 to 25% of the detergent composition, the multipliers will be fro, 0.92 to 0.75. The final per- centage of nonionic detergent in the product will be in the 8 to 30% range, preferably being 10 to 25% and more preferably being 15 to 22%, e.g., about 20%, but in some situations, for certain types of products, . proportions in the 8 to 13% range may be preferred. Nor- mally, the percentage of perfume in the final product : 15 will be in the range of 0.1] to 1%, preferably 0.2 to 0.4%, the percentage of enzyme will be from 8.5 to 3%, preferably 1 to 2%, and if a hydrous sodium silicate is to be post-added the proportions thereof will usually be no less than 1% and is preferably limited to about 5% , although in some cases as much as 10% has been used. When a softening compound is present in the final product the ’ proportion thereof will normally be in the range of 3 to 12%, preferably 5 to 10%.

The base beads and the spray dried detergent beads of the invention are spray dried from an aqueous crutcher mix which normally will contain from about 40 to about 70 or 75% of solids, preferably 50 to 65% thereof, with the balance being water, preferably deionized water, as previously described (but city water may alsc be employed). The crutéher mix is preferably made by sequentially adding various com- ponents thereof pumpable and non-setting slurry for spray drying.

The order of addition of the materials may be varied, depending on the circumstances, but it is highly desirable to add the silicate solution (if any) last, and if not last, at least after the addi- ’ tion of any gel- or "freeze'-preventing combination ’ of materials or processing aids, such as citric acid and magnesium sulfate.

Normally it is preferable for all or almost all of the water to be added to the crut- cher first, preferably at about the processing tempera- . ture, after which the processing aids (if present) and other minor components, including pigment, and fluores- cent brightener and polyacrylate, if present, are added, 2d followed by the zeolite, water soluble builder, anionic detergent (if present), hentonite and silicate (if pre- sent). Usually during such additions each component will be mixed in thoroughly before addition of the next com- ponent but methods of addition may be varied, depending } on the circumstances, so as to allow-co-additions when - 4h

» such are feasible.

Some times component additions may be in two or more parts and sometimes differ- ent components may be pre-mixed before addition, to speed the mixing process.

Normally, mixing speed and power will be increased as the materials aread- ‘ ded.

For example, low speeds may be used until afser admixing in of the last of the zeolite or soluble builder, after which the speed may be increased to medium and then to high, at which it will preferably ‘10 be before, during and after addition of any silicate solution. ) : . The temperature of the aqueous medium in the ’ crutcher will usually be about room temperature or elevated, normally being in the 20 to 80%, range,pre- ferably from 30 to 73 or 20%., and more preferably 40 to 70%¢. MHuating the crutcher medium may promote so solution of the water soluble salts of the mix and : thereby increase miscihility but the heating opera- tion, when effected in the crutcher, can dow product- ion rates and can sometimes promote setting of the mix.

An advantage of having processing aiding materials present in the mix (especially if any soluble silicate js present) is that they ensure that at higher and Low- er temperatures non-gelling slurries will result.

Tem- } 25 peratures higher than 80°c. (and sometimes those higher - ha - ’

than 70°C.) will usually be avoided because of the possibility of decomposition of one or more of the crutcher mix components, e.g.; sodium bicarbonate.

Also, in some cases lower crutcher temperatures in- ot crease the upper limits of crutcher solids contents, probably due to insolubilizing of normally gelling or setting components.

Crutcher mixing times to obtain good slurries can vary widely, from as little as five minutes in small crutchers and for slurries of higher moisture contents, to as much as four hours, in some cases. The : mixing times needed to bring all the crutcher mix com- ponents substantially homogeneously together in one medium may be as little as ten minutes but in some cases ~ can take up to an hour, although 30 minutes is a prefer- able upper limit. Counting any such initial admixing times, normally crutching periods will be from 15 mi- nutes to two hours, e.g., 20 minutes to one hour, but : the crutcher mix should be such as to be mobile, not | gelled or set, for at least one hours, preferably for two hours, and more preferably for four hours pr longer after completion of the making of the mix, and prefer- ably will be mobile for as long as 10 to 30 hours be- fore pump-out to the spray tower, to allow for situations " wherein other manufacturing problems may be encountered.

Sow.

The crutched slurry, with the various salts i and any other components thereof dissolved or in particulate form, uniformly distpibuted therein, is transferred in usual manner to a spray drying tower ‘which is normally located near the crutcher. The ‘ slurry is dropped from the bottom of the crutcher to a positive displacement pump, which forces it at high pressure through spray nozzles at the top of a conven- tional spray tower (countercurrent or concurrent) wherein the droplets of the slurry fall through a hot . drying gas, usually the combustion products of fuel oil or natural gas, in which the droplets are dried to desired bead form. During the drying, part of the bi- : carbonate (if present) may be converted to carbonate, . 15 with the relase of carbon dioxide, which, in conjunction with any of the polyacrylate present in the mix being

Co | spray dried, improves the physical characteristics of the beads made, so that they become more absorptive of liquids, such as liquid nonionic detergent, which may be post-sprayed onto them subsequently. However, the zeolite, bentonite and polyphosphate (when present) components of the base beads made also appear to favor absorption of liquid and the production of a strong bead, and the polyacrylate improves bead characteristics and promotes faster drying, thereby increasing tower - bh -

throughout."

After drying, the product is screened to de- sired size, e.g., 10 to 60 or 100, U.S. Sieve Series, . and is ready for application of nonionic detergent spray thereto, if it is a base bead formula, with the beads being either in warm or cooled ( to room tempera- oo ture) condition. However, the nonionic detergent will usually will usually be at an elevated temperatures,such : as 30 to 60°C., e.g., 50°C., to ensure that it will be : liquid; yet, upon cooling to room temperature, it will desirably be solid, often resembling a waxy solid. Even if at room temperature the nonionic detergent is some- . what tacky, this characteristic does not make the tinal : composition poorly flowing because the detergent penetra- trates to below (or within) the bead surface. The nonio- nic detergent, applied to moving or tumbling beads in known manner, @& a spray or as droplets, is preferably a condensation product of ethylene oxide and higher fatty alcohol, such as was previously described, but other no- nionics may alsi be operative. The enzyme preparation (herein referred to as enzyme, although it is recognized that it includes a carrier material, too), hydrous sili- cates and any other powdered adjuvants may be dusted onto the detergent particlesm, and perfume and any other 1li- quids to be post-added may be sprayed on at a suitable

Cus -

: point b~fore or after addition(s) of the powder(s).

The spray dried det-rgent, the spray dried base beads and the det-rgent compositions made from them include little or no silicate from the crutcher mix, although some silicate in solid form may be post- added. The post-added powdered silicate, if employed, $ does not seem to react with the zeolite as much, so zeolite-silicate arplomerations that tend to deposit on laundered articles are reduced, compared to such de-~ ‘ 10 posits from products wherein silicate was added in the crutcher. Although, without the bentonite being pre- sent, silicates would normally be used for its bead con- . trolling and anti-corrosion effrcts, the prosent deter- gent compositions produce acceptable beads and have not been found to cause the corrosion of aluminum articles. : Furthermore, the bentonite docs not adversely affect the stability of the product and in fact, appears to help to ’ hold the beads together, making them resistant to. crushing - and powdering during shipment and use. The presence of the bentonite significantly improves the properties of the final detergent composition, resulting in higher calcim jon binding rates and in less zeolite being deposited on jaundered fabrics. When the low molecular weight poly- acrylate is present the pase beads become more porous and better absorb the nonionic detergent in liquid state, oo - be -

without unduly lowering the bulk density of the pro- duct. Considering that bentonite is a clay and serves as a binder, it might be expected to create deposition and gelation problems of its own. Therefore, the low- ered depostion characterictics, absence of gelation, 8 and ready product dispersion ard surprising, and they : are important results of the present invention. Also considered to be important results of the presence of the small proportion of polyacrylate in the spray dried beads is the improved spray drying of the present base beads and detergent compositions, and the improved sorption of liquid nonionic detergent by the base beads.

The following examples illustrate but do not 1i- mit the invention. Unless otherwise indicated, all tem- peratures are in °c. and all parts are by weight in the examples and throughout the specification. When weights and proportions of zeolite are given, these are intended to be for the normal hydrate being used, because it is considered that the zeolite water of hydration does not jeave the zeolite and does not become part of the aqueous solvent medium in the present crutching operations. Also, part of the water present in the base beads and the deter- gent compositicns is present as water of hydration of the zeolite. Similarly, the moisture associated with the ben- tonite may also be considered not to be free moisture but because of the lesser percentage present this dis- : tinction can often be neglected, as a practical mat- ter.

EXAMPLE 1(Comparative)

A 100 parts batch of crutcher mix for spray dry- ‘ ing base beads considered as satisfactory for subsequent conversion to a detergent composition by addition of synthetic nonionic organic detergent thereto is made by . adding to the crutcher 47 parts of deionized water at a "temperature of about 27°c. (80°F.), and then sequentially, and initially with low speed crutcher mixing, admixing with it 1.0b parts of Tinopal 5BM fxtra Conc. (CIBA-Geigy), 0.13 part of ultramarine blue powddr, 0.07 part of sodium rolyacrylate (Alcosperse 107D), 21.11 parts of Linde hy- drated zeolite 4A (20% water of crystallization), 6.25 parts of Mineral Colloid No. 1 (bentonite), 15.75 parts of sodium bicarbonate (industrial grade), 7.74 parts of sodium carbonate (natural soda#ash) and 0.91 part of ti- nium dioxide (anatase). During mixing of the various com- ponents the mixer speed is increased to medium and ulti- mately to high and after additicn of all the constituents, which takes approximately fifteen minutes, mixing is con- continued for about an hour (in some cases as four hours of mixing may occur), during which time some of the water present , f.ge, about two to six parts, may be lost by evaporation, and may be replenished, if desired.

During the mixing time the crutcher slurry is con- : tinuously mobile and does not gel, set or cake. Be- cause bicarbonate partially decomposes to carbonate during spray drying, the amounts of bicarbonate and "carbonate in the crutcher formulation may be varied, depending on the spray tower operating characteristics.

Starting about five minutes after all the com- ponents of the crutcher mix are present, the mix is dropped from the crutcher to a pump, which pumps it at a pressure of about 21 kg./sq. cm. into the top of a countercurrent spray tower wherein the initial tempera- ture is about 430°. and the final temperature is about 105°. The essentially inorganic base beads resulting are of a bulk density of about 0.6 to 0.7 g./cc., an : initial adhesion less than 10%, a particle size range subs- tantially between 10 and 60 mesh, U.S. Sieve series (they - are screened to such range), and a fines characterdstic ’ (through U.S. Sieve Ro. 50) of about 15%. The moisture con- tent of the beads is in the range of 1 to 10%, normally being closer to 10%, e.g., & to 10%. Th» basc beads are found to be free flowing (80% flow rate), non-tacky, gdatis- factorily porous, yet firm ofi the surfaces thereof. They are capable of readily absorbing significant proportions of liquid nonionic detergent without becoming objectionably - ko ~

. tacky. }

Det=reent products are made from the spray dried brads by sprayine onto the tumbling bead surfaces thereof a normally waxy nonionic detergent. Neodol 23- 6.5 is used but Neecdol 23-7 or Neodol 25-7 (and sometimes

Neodol 15-11) may be substituted. The nonionic detergent ' is in heated liquid state (at a temperature of about 45%.) ‘ The quantity sprayed is such as to result in a final pro- duet containing about 20% of nonionic detergent. Proteo- lytic enzyme (Alcalase 1.7T or Maxazyme 375) is applied in powdered form to result in about a 1.5% concentration ' in the product, and perfume is sprayed onto the product to produce a 0.25% concentration therein. The resulting detergent compositions are of a bulk density of about 0.7 to 0.8 g./mi. and contain about 32.45% of zeolite (hydra- ted), 19.7% of the nonionic detergent, 18.5% of sodium car- bonate (some of which was produced by decomposition of so- dium bicarbonate), 13.5% of sodium bicarbonate, 1.3% of free water, 1.4% of enzyme , 1.6% of fluor~scent brighten- ’ er, 0.25% of perfume, 0.2% of ultramarine blue, 9.6% of : bentonite, 0.1% of sodium polyacrylate and 1.5 % of tita- nium dioxide.

The detergent made, of the above formula, is an excellent heavy duty laundry detergent and is especially usa ful for washing household laundry in automatic wash- ) ing machines. It is physically and aesthetically advan-

tageous and attrative because it is non-dusting and extremely freely flowing, which allows it to be pack- : aged in narrownecked glass and plastic bottles, from which it flows readily for dispensing. The detergent compositions produced, containing bentonite, as des- cribed, are of improved calcium ion binding rates but more importantly, thry leave less zeolite residue on : laundry washed with them (in an automatic washing ma- . chine at usual concentrations for such products and at "10 normal wash temperaturcs), especially When such laund- ry is line dried, than do similar compositions contain- ing less bentonite and with sodium silicate in the spray dried base beads. This difference is accentuated when i the wash water is high in hardness, e.g., 200 p.p.m., as calcium carbonate, the wash water is cold, and a grntle ¢ agitation cycle is employed.

The base beads and detergents composition made are acceptable standards against which the other des- cribed brads and detergent compositions of the follow- 20 . ing examples may be measured, and to whi ch they compare favorably. Also, the manufacturing methods are essen- tially the same and are consider~d to be satisfactory.

Following normal procedure, crutcher mixes will be made quickly and may be emptied from the crutcher = equally fast, sometimes being made within a period of as little as five minutes and being pumpred out of the crutcher in as little as ton minutes. Yet, it is often important that the present mixes be able to withstand . at lcast an hour in the crutcher without gelling or solidifying becanse some imes holdups of such lengths ’ of time are encountersd in commercial production. The described crutchar mix is capable of heing held for as * long as four hours, and often apyreciably longer, with- out gelling or solidifying, which is attributed, at least in part, to the content of bentonite and the absence of silicate. This action of the bentonite is unexpected because it also has a thickening effect on the crut- cher mix, but although the mix may thicken appre- ciably it remains pumpable. Minor components of the crutcher mix, such as the fluorescent brightener and pigment, may be omitted therefrom and enzyme and per- fume may be omitted from the final product, although it js highly preferable for all such materials to be pre- sent. The crutcher mix temperature may be modified, as by elevation to 52°C. , and the proportions of the va- rious components may be varied + 10%, + 20% and + 30%, while still maintaining them within the ranges previously given, and workable mixes that result in the desired beads and detergent compositions will be obtainable.

The cructher mix solids contents may be varied over the range recited, e.g., to 45% and 65%, and good mix- ing and Spray drying result.

Other orders of addition to the crutcher of components may be employed but nor- mally it will be desired to add any silicate last or ’ 5 near the end, and it is preferred that the bentonite . also be added late in the process, preferably just be- fore thr silicate.

Instead of using Zeolite 4A, Ceo- lites X and Y may be substituted, as may be other types of Zeolite A.

While it is preferred to employ the ap- proximately 80% hydratsd Zeolite UA (about 20% moist- ure content) of this example, various degre~s of hy- : i dration of the zeolite are acceptable and in some ins- tacnes nearly anhy:rous crystalline zeclites or amor phous zeolits may be employed.

Varying the amount of ’ bentonite within the range given, to 7%, 13% and 19% in the base bead, for example , still results in useful products, but those containing the larger yroportions of bentonite will usually be more effective in helping to prevent zeolite deposition on laundry.

In some ins- tances it may be desirable to utilize even higher per- centages of bentonite, within the ranges set forth in this specification, taking care that the other components of : "the base bead will be such that the beads will be free flowing and effective detergents.

The proportion of bentonite suitable to be employed commercially depends on a number of factors and normally will represent a balance struck between the desired diminution of zeolite residue and the desired building and other functional effects of other detergent composi tion components that could be incorporated in place of an increased amount of pan tonite. : : The improvenrnt noted in the detergent compo- sition of this example depositing less residue on wash- ed laundry is verified by testing the described product against a control product of essentially the same for- mula, with no bentonite present and containin~ about 8% of sodium silicate in the final product. In this evalua- tion a Whirlpool Suds Saver model washing machine is em- ‘ ployed, with the washing periods being eight minutes at a gnetle was cycle. The detergent composition concentra- tion is 0.06%, the wash water is of mixed calcium and magnesium hardness with a total of 200 p.p.m. harness, as calcium carbonate, and the water temperature is 24°C. :

The items washed are: 100% cotton; 100% polyester; 85% acetate and 15% nylon; and 65% polyester and 35% cotton.

The wash is observed wet and after line drying (line . drying usually results in more visible residue than does automatic dryer drying). No residue is obeerved in either such case. When the control formula deter- gent composition is tested, moderate residue is observed

. ‘ on all washed specimens. } “.

The results of the ptactical residue test des- cribed above are verified by weighing residue deposit-~ ed on a denim t<st material. In such test, the deter- gent composition of this invention is filtered through a sample of denim material, with the detergent being in solution -suspension at 0.12% concentration in 200 p.p.m. (as Caco) hardness water at 24°C., and the weight of re- sidue on th: cloth is noted, and compared. By such test percentage of residue, compared to the control, is about 75%, which is considered to represent a significant dif- : ference in appearance of washed products.

The adhesion test, previously referred to, which measures tackiness of detergent product, is one in which 10 grams of base beads (or detergent composition, in some cases) are placed evenly between two watch glasses, both of which are 23 cm. in diameter, with a weight of 500 grams on top of the upper watch glass (both watch glasses being concave side up). After standing there five minutes, the weight and top watch glass are removed and the bottom watch rlass is inverted, after which the product remain- ing stuck to such watch glass is weighed. The percentage adhesion is the number of grams of product remaining on ’ such watch glass multiplied by 10. © 25 The flow index is that resulting from a flow test ;

_ ee ——————— whegein the volumetric flow rates of base beads (and in some cases final product) and® standardized Ottawa sand (-20 +60, U.S. Sieve Series) are compared by measuring the times required for complete emtying of a 1.9 liter Mason jar through a 2.2 cm. diameter cir- cular hole in a nozzle attached to the cap thereof.

The flow index % is the time for the sand flow divided ’ by the time for the test product flow, times 100.

Base beads like those of Lixample 1 but with NTA jncluded therein in place of some of the carbonate and bicarbonate are made by essentially the same me thod des- cribed in that example. The formula is chaned only by replacing 5 parts of the zeolite, 12 parts of the sodium bicarbonate and 3 parts of the sodium carbonate in the _crutcher with 20 parts of NTA, as the trisodium salt monohydrate. The NTA is added after the sodium carbonate during the mixing operation. The base beads obtained are not as crisp as those of Example 1 but are sufficiently satisfactorily free flowing. Instead of the final deter- gent composition containing 19.7% of the nonionic deter- . gent, it is sufficient for it to hold 12%, with the final percentages of the other components being increased accord- ingly. The resulting product is a satisfac ory heavy duty } 25 particulate detergent,

In variations of this formula, 2.5% of hydrous sodium silicate is post-added to the product for its anti-corrosion properties and for its utility in tying up magnesium ions in the wash water. Providing that the silicate is of about the same particle size and density it does not shift or segregate from the other } detergent bead components during shipping and storage, and the resulting product meets specifications for a zeolite~silicate aggregate may be noted on washed mate- rials.

In another alternative formula, 3% of sodium sili- cate of Na,0:5i0, ratio of about 1:2.4 is included in the final yprodu~t by addition of an aqu: ous solution thereof in the crutcher, together with 1.5% of magnesium sulfate and 0.4% of citric acid to prevent gelation or setting in the crutcher. The finished product iB a good heavy duty . detergent but does ddposit more zeolite-silicate aggregate on wabBhed materials that are line dried than does a compan- . able formula to which the hy 'rous sodium silicate is post- added.

EXAMPLE 3

The procedure of Example 2 is repeated but with pen- tasodium tripoly hosYhate being substituted for the NTA.

The products obtained are good detergents, of a bulk density of about 0.8g./cc. (as are those of Example 2) but such den-

sities may be varied by adjustment of spray tower conditions and formulas so as to be within the range ! of 0.7 to 0.9, and in some cases the densities may be lowered to 0.3. With the post-added silicate the densities may be slightly higher, especially for those in the lower portion of the range. The product is more free flowing than that of Example 2 but is about equi- ’ valent to it washing power.

In the above formula and those of the previous examples an additicnal proporticen of bentonite may be added in the crutcher to make products containing 15% (or ‘more) of the bentonite. Such products are even bet- ‘ter in binding effects, dispersibility and other desir- able properties attributable to the bentonite and are good det:rgent (and vase bead) preparaticns. Also, the ; tripolyphosphate may be rerlaced, either in whole or in part, e.g., 1/2, by tetrabodium pyrophosphate, and simi- lar good products result.

EXAMPLE 4 :

A final detergent product is made essentially by the method of Examples 1 and 2 containing 30 parts of the zeolite, 30 parts of NTA, 20 parts of the nonionic, 10 parts of bentonite, 5 parts of sodium carbonate, 5 parts of sodium carbonate, 5 parts of water and 1.3 parts of enzyme. This product has a density of about 0.5 g./cc. and is a satisfactory detergent. However, to improve flowability of the product it is desirable for the nonionic detergent content to be decreased to 15% and preferably to 12%. To increase the bulk density to about 0.7, half of the bentonite may be re- placed by sodium silicate (Na 0: 810, ratio of 1:2.4), added as the last component in the crutcher as a 47.5% : aqurous solution, and 1.5 parts of magnesium sulfate . 10 and 0.4 parts of citric acid may be correspondingly added as anti-ge'!ling agents earlier in the making of . the crutcher mix. The resulting product is of about oo 0.7 g./cc. bulk density and can absorb about 20 parts of nonionic detergent without becoming tacky or of diminished flowability. While it deposits less zeo- lite-silicate aprlomerate than formulations with con- ventional greater proportions of silicate present from crutcher additions the agglomerate can be detected on laundry washed with the product and line dried. | EXAMPLE 5

Instead of manufacturing base beads to which de- tergent is applied to form a detergent composition the composition may be spray dried directly from the crutcher : with a suitable synthetic organic detergent being includ- ed in the crutcher mix. Using essentially the same proce-

dupes as described in Example 1, a crutcher mix is made which is spray dried to detergent beads con- taining 16 parts of linear tridecyl benzene sulfo- nate; 20 parts of the zeolite, 12.5 rarts of bento- : 5 . nite, 15 parts of NTA, 10 parts of sodium carbonate and conventional adjuvants (colorants fluorescent brightener). The bulk density of the spray dried . product will be in the 0.3 to 0.8 range, nromally being in the lower portion of such rarvge and sometimes being : 10 as low as C.2 g./cc . In the manufacturing process the organic detergent will normally be added after the water.

Drying will usually be to a moisture content of about 8 to 12%. The resulting product preferably has about 3 parts of hydrcus sodium silicate post added, together with other normal adjuvants, such as enzyme and perfume. It is a satisfactory heavy duty detersent which does not deposit objectionable amounts of zeolite or zeolite-silicate ag- gregate on washed fabrics. Dye to the presence of the bentonite the detergent appears to disperse very quickly when added to the wash water and it is considered that at least in part this quick dispersibility, together with the presence of the bentonite, tends to inhibit zeolite deposition.

EXAMPLE _6

The procedure of Fxample 5 is followed but f the NTA is replaced by an equal weight of soda ash.

Such product is also a satisfactory heavy duty de- tergent.,

FXAMPLES 7

The procedure of Example 6 is followed but pentasodium tripolyphosphate is included in place of

NTA. The product made is especially free flowing and is a good heavy duty synthetic organic detergent compo- sition. Although when silicate is to be present it is preferred that it be post- added as a hydrous sodium silicate, up to 5 parts of silicate may be added in the crutcher, together with the apyrropriate proportions of magnesium sulfate and citric acid, as described in pre- vious examples, and useful detergent compositions will result, although some zeolite-silicate deposition will ’ : occur. .

In addition to the conventicnal materials which may be post-added, there may be added to the product of this example (and to the products of other examples), softening proportions of a cationic material, e.g., 8% of dimethyl distearyl ammonium chloride, an amphoteric detergent, e.g., 5% of Miranol CM (1-carboxymethyl-1-

carboxyethoxyethyl-2-coco-imidazolinium betaineg, or a bleach, r.g., 15% of sodium perborate (preferably activated). Of course, the additions of such mate- i 5 rials will diminish the proportions of the other com- ponents in the final composition and thereby will change the properties of the comvoisitions somewhat, sometimes requiring the use of more of the product in the wash wa- ter to obtain the same cleaning effect. .

In Examples 5-7 the linear tridecyl benzene sul- fonate may be reylaced with an equal weight of sodium lauryl sulfate or sodium lauryl polyethoxy sulfate (3 to 10 Et0) or mixtures of such materials in equal parts and the products obtained are also useful as detergent compoisitions. Similarly, instead of the NTA, carbonate, carbonate and bicarbonate, and polyphosphate, sodium ci~ trate and/or sodium glucomate may be substituted, at least in part, €.g., 1/4, 1/2, and good detergents result.

EXAMPLE 8

The proivcts of Example 1 and Fxample 7 (the pri- mary products first described) are mixed in equal propor- tion to obtain a final product with the characteristics of both such constituent parts. Prior to mixing the ma- terials to be mixed are both of approximately the same bulk density, about 0.5 g./cc. and of about the same par-

ticle sizes, in the No's 10 to 60 range, U.S. Sicve

Series, s0 as to prevent separation during shipping and storage. The mixed product is especially useful for the removal of both oil-based and clay -based on +5 laundry, and is free flowing, stable and attractive.

In some cases one of the particulate starting mate- rials may be dyed or pigmented and the other left na- tural in color to obtain special appearante effects, ,

In addition to the particle sizes and densities being about the same it is preferred that the moisture con- tents also be about the same, e.g. about 10%, so that there will be little migration of moisture between the ' different beads. } In the Example 7 materials used the anionic de- tergent may be changed from sodium alkylbenzene sulfo- } nate to a sodium alpha-olefin sulfonate (14-15 carbon atoms in the olefins) or to a sodium paraffin sulfonate By (12-15 carbon atoms in the paraffin) and the mixtures made will also be useful detergents. pe

EXAMPLE 9

Following substantially the procedure described in Example 1 a crutcher mix is made from 36.9 parts of . water, 1.2 parts of fluorescent brightener (Tinopal SBM, extra concentrated) 0.1 part of ultramarine blue, 2.1.

parts of magnesium sulfate (heptahydrate), 0.3 part "of sodium citrate, 22.4 parts of zeolite UA powder . (partially hydrated, to about 20% moisture content), : 20 .9 parts of trisodium nitrilotriacetate monohydrate, 7.4 parts of a 47.5% solids soluticn of sodium sili- cate (Na,0:8i0,= 1:2.4), 3.7 parts of sodium bentonite (formerly marketed as THIXO-JEL No. 2), 2.8 parts of natural soda ash and 2.1 parts of a mineral type com- pound, which may act to increase bead porosity, and as a building agent . The crutcher mix is syray dried in a manner like that previously described, with the moist~ ure loss in drying being about 45.2%.

Onto 78.4 parts of the spray dried base beads, of particle sizes in the No. 10 to 100 range (screened), are sprayed 20 parts of Neodol 23%3-6.5, after which the beads are mixed with 1.3% parts of high activity proteo- = lytic enzyme, and 0.3 part of detergent perfume is spray- ed onto them. The final product has a zeclite content of 25%, an NTA content of 30%, a sodium bentonite content of 5% and a water soluble sodium silicate solids content of 5%. The moisture content is 5% and the active deter- sive ingredient (polyethoxylated higher fatty alcohol) content is 20%. The bulk density is about 0.7 g./cc. "and the pH of its 1% solution is about 10. | The detergent composition made by this method is a satisfabtory heavy duty nonionic det rgent but does de-

‘rosit somewhat more zeolite-silicate aggregate on washed clothing that is line dried than does a corres- . ponding composition made without any water soluble si- licate solids.

It is preferred that in such corres- ponding composition there is also present about 0.1 to 0.5% of low molecular weight sodium polyacrylate, of the tvpe previously described herein.

Both pro- ducts wash laundry well and are especially effective in cold water washing, due at least in part to the bentonite contents thereof and the almost instanta- neous dispersion that is observable when the deter- gent is added to wash water (which dispersion also di- minishes time for any reaction between soluble sili- . cate and zeolite to form objectionable aggregates).

Claims (20)

WHAT IS CLAIMED IS:

1. Free flowing, spray dried beads, uscful as a deterrent or for the manufacture of a parti- culate built synthatic organic det2rrent compo#i- tion, which detergents are of reduced particle de- position characteristics due to the presence of ben- tonite and a low content of water soluble silicate or absence of such silicate in the spray dried beads comprising by weight from 5 to 60% of water softening zeolite which is a hydrated water softening zeolite containing from 15 to 25% by weight of water of hydra- tion and having an ion exchange capacity for calcium ion which is in the range of 200 to 400 milligram equi- : valents of calcium carbonate hardness per gram of an- hydrous zeolite. 2 to LO% of swelling bentonite, con- . taining sufficient moisture to facilitate dispersion of } the bentonite so as to inhibit deposition of zeolite on the laundry being washed, 5 to 60% of water soluble builder or a mixture of such builders O or 30% of water soluble synthetic organic det rgent and 0 to 5% of water soluble silicate.

2. B.ads according to claim wherein when water soluble synthetic detergent is not present the water soluble builder comprises polyphosphate, rhosphate, borate, nitrilotriacetate, gluconate or citrate or a mixture of two or more thereof.

3, Beads according to claim 2, of a bulk den- sity in the range of 0.2 to 0.9 g./cc. and particle sizes in the range of No. 10 to 100: U.S. Sieve Series wherein the water softening zeolite which is a hydrated water softening zeolite containing from 15 to 25% by weight of water of hydration and having an ion ex&hange capacity for calcium ion which is in the rar ge of 200 to 400 milligram equivalents of calcium carbrnate hardness per gram of anhydrous zeolite, is a hydrated water soften- ing seolite containing from 15 te 75% by weight thereof of water of hydration and has an exchange capacity for cal- : cium ions which is in the range of 200 to 400 milligram a equivalents of calcium carbonate Hardness per gram of an- hydrous zeolite, the swelling bentonite is a swelling clay having a swelling capacity, in water, of 3 to 15 ml./g. . and a viscosity of 3 to 30 centipoises at 6% concentra- tion in water, and includes at least 2% of moisture on an anhydrous bentonite basis, a water soluble, builder ‘ is present which is polyphosphate, pyrosyhosphate, phos- phate, borate, nitrilotriacetate, citrate, gluconate, carbonate or bicarbonate or a mixture of two or more there- of, and the water soluble silicate is an alkali metal (M) silicate of M,0:510, ratio in the range of 1:1.6 to 1:3.

L,. Beads according to claim 3 wherein the propor- tion of swelling bentonite to zeolite which is a hydrated water softening zeolite containing frem 15 to 25% by weight of water of hydration and having an ion exthangecapacity for calcium jon which is in the ranger of 200 to Lop millig- ram equivalents of calcium carbonate hardness per gram of anhydrous zeolite is a hydrated water softening zeolite con- taining from 15 tec 25% by weight thercof of water of hydra- tion and has an exchange capacity for calcium ions which is in the range of 200 to 400 milligram equivalents of calcium ’ carbonate hardness rer gram of anhydrous zeolite, the swell-

ing ®entonite is a swelling clay having a swelling capacity, in water, of 3 to 15 ml./g. and a viscosity of 3 to 30 centi- poises at 6% concentration in water, and includes at least 2% of moisture on an anhydrous bantonite basis, a water solu- ble builder is present which is polyphosrhate, ryrosrhos-

phate, phosphate, borate, nitrilotriacetate, citrate, giuco- nate, carbonate or bicarbonate or a mixture of two or more thereof, and the water soluble silicate is an alkali metal (M) silicate of M,0: 510, ratio in the range of 1:1.6 to 1:3.

4, Beads according to claim 3 wherein the propor--

tion of swelling bentonite to zeolite which is a hydrated water softening zeolite containing from 15 to 25% by weight . of water of hydration and having an ion exchange capacity for calcium ion which is in the range of 200 to L400 millig- ram equivalents of calcium carbonate hardness per gram of

"anhydrous zeolite is in the range of 1:4 to 1:1, the pro-

portion of water soluble builder to zeolite is within the mange of 1:2 to 3:1 and the preporticn of swelling bentenite to water soluble is within the range of 1:10 to 1:1.

5. Beads according to claim 4 comprising from to 0% of hydrated sodium zeolite, 2 to 35% of swell- ing bentonite, which bentonite is of a type which has a swelling capacity in the range of 7 to 15 ml/g. and is of i a viscosity in the range of 8 to 30 cp at 6% concentra- 10 tion in water, 10 to 50% of water soluble alkali metal ) builder salt or mixture thereof, O to 25% of water solu- ble synthetic anionic organic detergent and O to 3% of water soluble silicate.

6. Beads according to claim 5 comprising from 15 to 35% of zeolite A, 5 to 20% of beneficiated Wyoming bentonite, 20 to 50% of water soluble sodium builder salt or mixture thereof, O to 20% of water soluble syn- thetic anionic organic detergent and 0% of sodium sili- cate, and in which the proportion of bentonite; zeolite is in the range of 1:3 to 2:3, that of water soluble builder; zeolite is within the range of 2:3 to 2:1 and that of bentonite; water soluble builder is within the range of 136 to I:2.

7. Beads according to claim 2 wherein the water soluble builder is selected from the group consisting of carbonate, bicarbonate , polyphosphate or nitrilo- triacetate, or a mixture thereof, and the swelling bentonite includes at least 2% of moisture on an an- hydrous swelling bentonite basis. : 5 |

8. Beads according to claim 7 wherein the swelling b-ntonite includes at least 4% of moisture , the water scluble builder comprises a nitrilotri- ! acetate and no water soluble synthetic organic de- : tergent nor any water soluble silicate is present. ,

9. Beads according to claim 8 comprising from to 40% of hydrated zeolite A containing 15 to 25% by weight thereof of water of hydration and having an exchange capacity for calcium ions which is the range of 200 to BGO milligram equivalents of calcium carbo- 15 nate hardness per gram of anhydrous zeolite, 10 to 20% . of swelling bentonite which is a beneficiated Wyoming bentonite of swnlling capacity in the range of 7 to 15 ml./g. and of a viscosity in the range of 3 to 30 cp at 4 concentration in water, and 20 to 60% of NTA.

10. Beads according to claim 7 wherein the swell- ing bentonite includes at least 4% of moisture, the water " goluble builder comprises a polyphosythate and no water soluble synthetic organic detergent nor water soluble silicate is present. . 25 11. Beads according to claim 10 wherein the anio-

nic detergent is sodium linear alkylbenzene sulfonate ’ wherein the alkyl is of 10 to 18 carbon atoms, sodium fatty alcohol sulfate wherein the alcohol is of 10 to ‘ 18 carbon atoms, or sodium fatty alcohol ethoxylate sulfate wherein the fatty alcohol is of 10 to 18 carbon : atoms and which contains from 3 to 30 ethylrne oxide groups per mol, or a mixture of two or more thereof, and the pro- rortion of such anionic detrrrent(s) in the beads is from 5 to 25%.

12. Brads according to claim 7 which comrrises from 3 to 30 of water scluble synthetic anionic organic detergent.

13. Beads according to claim 12 wherein the anio- nic deterrent is sodium lincar alkylbensene sulfonate wherein the alkyl is of 10 to 18 carbon atoms, sodium fatty alcohol sulfate wherrin the alcohol is of 10 to 18 . carbon atoms, or sodium fatty alcohol ethoxylate sulfate wherein the fatty alcohol is of 10 to 18 carbon atoms and which contains from % to 30 ethyl-ne oxide groups p r mol, | or a mixture of two or more th-reof, and the proportion of such anionic deterpgent(s) in the beads is from 5 to 25%.

14%. Beads according to claim 2 which comprise from

0.05 to 1% of polyacrylate of molecular weight in the range of 1,000 to 5,000,

BB ’ - I ———————— ——

15. Beads according to claim 3, of a bulk density in the range of 0.2 to 0.8 g./cc., wherein , the zeolite is hydrated zeolite A , the swelling bentonite includes at least 3% moisture on an anhy- drous swelling bentonite basis, the water soluble build- er is a sodium salt of nitrilotriacetatéc acid, the wa- ter soluble silicate, if present, is sodium silicate of . Na,0: 5i0,, ratio in the range of E:2 to 1:2.8, the mojs- ture content of the beads is from 3 to 12% thereof, the proportion of swrlling bentonite: zeolite is in the range of 1:6 to 1:2, that NTA; zeolite is in the range of 1:2 to 2:1, and that of swelling bentonite: NTA is in the : range of 1:6 to 1:2, and the percentages of hydrated ) zeolite swelling bentonite, sodium nitrilotriacetate, and sildcate are respectively, within the ranges of 10 to Lo%, 2 to 25%, 10 to 40%, and 0 to 5%.

16. Beads according to claim 3, of a bulk density in the ranpe of 0.2 to 0.8 g./cc. which comprises 5 to 30% oo of synthetic anionic organic detergent and in which the zeolite is hydrated zeclite A, the awelling bentonite in- cludes at least 3% moisture on an anhydrous swelling ben- tonite basis, the water soluble builder is a sodium salt of nitrilotriacetic acid, the synthetic anionic organic detergent is sodium linear alkyl benzene sulfonate where- ) in the alkyl is of 10 to 18 carbon atoms, sodium fatty al-

cohol sulfate wherein the alcohol is of 10 to 18 carbon atoms, or sodium fatty alcohol ethoxylate ; sulfate wherein the fatty alcohol is of 10 to 18 carbon atoms and which contains from 3 to 30 ethyl- ene oxide groups per mol, br a mixture comprising two or more thereof, the water soluble silicate, is sodium silicate of Na,0:510, ratio in the range of 1:2 to 1:2.8, the moisture content of the beads is from 3 : to 12% thereof, the proportion of swelling bentonite: zeolite is in the range of 1:6 to 1:1, that of NTA : : zeolite is in the range of 1:3 to 3:1, that of bento- nite: NTA is in the range of 1:10 to 1:1, and that of synthetic anionic organic detergent : zeolite is in the range of 1:1 to 1:4 and the percentages of hydrated zeolite, swelling bentonite, sodium nitrilotriacetate, synthetic anionic organic detergent, and silicate are respectively, within the manges of 10 to 40%, 2 to 25%, 10 to 4o%, 10 to 25%, and O to 5%. . : -.

17. Beads according to claim 3, of a bulk densi- ty in the range of 0.2 to 0.8 g./cc., wherein the zeo- ‘ 1ite is hydrated zeolite A, the swelling bentonite inelud-

1 .es at least 3% moisture on an anhydrous swelling bentonite . basis, the water soluble builder is rentasodium tripolyphos- phate or tetrasodium pyrophosphate or a mixture thereof, the water soluble silicate, is sodium silicate of Na ,0:510, ra- tio in the range of 132 to 1¢2.8, the moisture content of the beads is from 3 to 12% ther-of, the proportion . swelling bentonite: zeolite is in the range of 1:6 to 1:2, that of total polyphosrhate: zeclite is in the range of 1:2 to 2:1, and that of bentonite: total polyphosphate is in the range of 1:~ to 1:2 and the percentages of hydrated zeclite swelling bentonite total polyphosphate, and silicate are respectively, within the ranges of 15 to 35%, 5 to 20%, 15 to Log : and 0 to 5%.

18. Beads according to claim 3, of a bulk den- : sity in the range of 0.2 to 0.8 g./cc. which comprise 5 to 30% of synthetic anionic ormanic detergent and in which the zeolite is hydrated zeolite A, swelling ben- tonite includes at lrast 7% moisture on an anhydrous : 15 swelling bentcnite basis, the water soluble builder is pentasodium trijolyphosihate or tetrasodium pyro phos- phate or a mixture thereof, the synthetic anionic or- -. ganic detergent is sodium linear alkyl benzene sulfo- nate wherein the alkyl is of 10 to 18 carbon atoms, so- dium fatty alcohol sulfate wherein the alcohol is of 10 : to 18 carbon atoms, or sodium fatty alcohol ethoxylate sulfate wherein the fatty alcohol is of 10 to 18 car- bon atoms and which contains from 3 to 30 ethylene ‘ oxide groups per mol , or a mixture comprising two or more thereof, the water soluble silicate, if present, - 7h = is sodium silicate of Na,0:8i0, ratio in the range of 1:2 to 1:2.8, the moisture content of the beads is from 3 to 12% thereof, the proportion of Swell- ing bentonite; zeolite is in the range of 1:6 to 1:1, that of total polyphosphate: zeolite is in the range of 1:3 to 3:1, that of swelling bentonite: total poly- phosphate is in the range of 1:10 to 1:1, and that of : synthetic anionic organic detergent :tzeolite is in the range of 1:1 to 1:4 and the percentages of hydrated . 10 zeolite swelling bentonite, total polyphosphate, syn- thetic anionic organic detergent, and silicate are rés- : pectively, within the ranges of 10 to Lox, 2 to 25%, to 50%, 10 to 25%, and O to S%.

19. A detergent composition which comprises Co 15 beads of claim 1 having absorbed in them a nonionic de- tergent so that the percentage of such nonionic deter- : gent in the composition is within the range of 8 to 30%.

20. A detergent composition comprising a mixture } of beads of claim 7 and of particle sizes in the range of

No. 10 to 100 , U.S. Sieve Beries, in a proportion, by weight, in the range of 1:10 to 10:1 and with the bulk densities of the beads before mixing thereof being within

0.1 g./cc. of such other and of the final composition bulk density, which is in the range of 0,2 to 0.9 g./cc. Inventor