CA1188953A - Base beads for manufacture of detergent compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Free-flowing base beads, into which nonionic detergent in liquid form may be absorbed to make a free-flowing particulate built syn-thetic nonionic organic detergent product of improved washing properties, include 15 to 30% of sodium carbonate, 10 to 22% of sodium bicarbonate, 10 to 50% of water softening aluminum silicate (zeolite), O to 18% of sodium silicate, 1 to 20% of bentonite and/or 0.05 to 2% of polyacrylate of molecular weight in the range of 1,000 to 5,000, and 1 to 15% of moisture, together with suitable adjuvants and processing aids in small proportions (normally totalling less than 10% and preferably less than 5%).
The presence of bentonite causes the nonionic organic detergent product to leave reduced amounts of deposits, after rinsing, on fabrics washed with such products, while the presence of polyacrylate makes the base beads more absorptive to liquid nonionic detergent and provides improved spray drying operations.

Description

~8~3 BASE BEADS FOR MANUFACTURE OF
DETERGENT COMPOSITIONS

This lnvention relates ~o base beads which are useful for the manufacture of built nonionic detergent composi~ions. ~ore particularly, it relates to such beads which are essentially inorganic in nature and include sodium carbonate, sodium bicarbonate, zeolite, sodium silicate and bentonite and/or polyacrylate and which can absorb nonionic detergent, in li~uid form, to make freely flowing, particulate, built nonionic detergent compositions. The invention also relates to manufacturing processes, crutcher slurries and detergent compositions made, which compositions are of improved washing properties, depositing less residue on washed materials despite the presences of ~eolite and silicate.
Synthe~ic organic detergent compositions containing water softening aluminum silicates, such as zeolites, have been invented and marketed in recent years. In such composi-tions, which also include 2 synthetic organic detergent or surface active agent component, the zeolite acts as a calcium sequestrant and as a builder for the organic detergent, improving its cleaning e~fects, especially in hard water.
In such compositions sodium silicate has also been employed as a builder and as a corrosion proventing additive, to protect aluminum parts of washing equipment with which aqueous solutions of the detergent composition come in 38~53 contact during washing operations. The silicates also may be useful in counteracting adverse effects magnesium ions in the wash water could have on the washing activity of the detergent composition. Additionally, it is considered that the silicate helps to produce more stable detergent beads, especially when such are made by spray drying of a crutcher mix of detergent composition components. However, it is well recognized that zeolites often tend to deposit as a notice-able residue on laundry washed in aqueous cleaning media containing them, and various investigators have reported that the presence of a silicate in such a medium with zeolite increases the amount of residue deposited.
Bentonite, a swelling clay, with comparatively minor hardness ion exchange capacity, has been suggested for lS use in various detergent products, such as soap bars and laundry detergents, wherein it has often served primarily as a filler. However, in some instances it is alleged to perform other functions. For example, in U.S. patent ~ 4,1~6,039 it is taught to aid in the production oE homo-geneous det.ergent slurries when such slurries contain phosphate(s). Normally however, the incorporation of clays in detergent compositions is avoided because they are insoluble and might be expected ~o deposit on the materials being laundered. In fact, clay soil removal is one of the tests utilized to rate detergent effectiveness. Despite the ~8~3~S3 fact that it might be expected that the addition of bentoni-te would only exacerbate residue problems encountered when wash-ing laundry with aqueous media containing detergent composi-tions incorporating zeolite and silicate, surprisingly it has been found that residue deposition is diminished. Also, calcium ion binding rates are increased.
Polyacrylates, often of comparatively high molecular weight, have been suggested as detergent composition components.
They have been disclosed to be components of powdered and slurried detergents and have been suggested as replacements for phosphate builders in non-phosphate deteryents. It is known that the polyacrylates possess dispersing properties and a manufacturer of these materials has suggested them for use in dispersing applications, as in maintaining the suspension of pigments in paints. Additionally, it is known that in certain aqueous media they tend to inhibit deposition of insoluble calcium compounds and redeposition of insoluble materials on washed laundry. Although polyacrylates have been included in detergent formulations, the present crutcher mixes, base beads and detergent compositions are considered to be novel and unobvious. The presence of the very small quantity of a particular type of polyacrylate in the specified formulations, in cooperation with the other components of such formulations, has been found to result in an improved product of better cleaning characteristics, which can be made using practicable manufacturing operat.ions, In accordance wi-th the present invention free flowing hase beads, on which nonionic deter~ent may be absorbed to make particulate built synthetic nonionic organic 5 deteryent products of improved washins properties, which, after rinsing, leave lesser amounts of deposits on fabrics washed with such products, cc~mprise by weight from about 15 to 3Q~ of sodium carbonatel 10 to 22~ of sodium bicarbonate, 10 to 50~ of water softenincl aluminum silicate, 0 to 18% of sod.ium sil.icate, and 1 to 20% of bentonite and/or 0.05 to 2 of polyacrylate of molecular weight in the range of 1,000 to 5~000. Such products will normally contaln from 1 to 15%
of moisture and may be made into organic detergent composi-tions by application of liquid state nonion.ic detergent to them so that the detergent is absorbed and the product result-ing is still free flowin~. The proportion of detergent utili~ed will normally be such that the final detergent composition will contain about 8 to 30% thereof, by weight. The presence of the polyacrylate helps to make the bas beads more absorptive of he liquid nonionic detergent. Also, it often improves spray drying operations, resulting in less material adhering to the dryer w~115 and thereby increasing spray tow~r through-put rates and diminishing the number of cleanouts which may be required.
~5 The various components of the base beads of this ~l38~S~

invention, except for water, are norma~ly in the solid state, although, when added to the crutcher, some may be in the forms of hydrates or may be dissolved or dispersed in an aqueous medium~ su~h as water. The sodium bicarbonate is S anhydrous and sodium carbonate is generally utilized as soda ash. Yet, the carbonate hydrates, such a~ the monohydrate, may be employed, if desired, and in some cases it may be possible to utilize other carbonates and bicarbonates, such as othex alkali metal salts, e.g., the potassium salts, in replacement of at least some of the sodium salt, although the sodium salts are highly preferred. The silicate, when present, is usually added to the crutcher as an aqueous solution, which is normally of 40 to 50% solids conten-t, e.g., 47.5%, and preferably its addition is near the end of the mixing process.
The silicate employed will usually be of Na~O:SiO~ ratio within the range of 1:1.4 to 103, preferably 1:1.6 to 1:2.4 or 1:~.6 and more preferably 1:2 to 1:2~4. Although sodium silicate is the preferred silicate, a portion of the sodium silicate may be xeplaced b~ potassium silicate or other suitable soluble alkali metal ~ilicate salt.
The zeolites employed include cry~talline, amorphous and mixed crystalline-amorphous zeolites of both na~ural and synthetic origins which are of satisfactorily quick and sufficiently effective activities in counteracting calci~m hardness ions in wash waters. Preferably, such materials 39~3 are capable of reacting sufficiently rapidly with the calcium ions so that, alone or in conjunction with other water softening compounds in the detergent, they soften the wash water before adverse reactions of such ions with other components of t~e synthetic organic detergent composition occur. The zeolites employed may be characteriæed as having a high exchange capacity for calcium ion, which is nor~ally from abou~ 200 to 400 or more milligram equi~alents of calcium carbonate hardness per gram of the aluminosilicate, preferably 250 to 350 mg. eq./g. Also they preferably have a hardness depletion rate residual hardness of 0.02 to 0.05 mg. CaCO3/liter in one minute, preferably 0.02 to 0.03 mg./l., and less than 0.01 mg~/l. in lO minutes, all on an anhydrous zeolite ba~is.
Althouyh other ion exchanging zeolites may also be utilized, normally the finely divided synthetic zeolite builder particles employed in the practice of this invention will be of the formula ~Na20)x 1A1203)y- ~Si2)Z

wherein x is l, y is from 0.8 to 1.2, preferably about l, z is from l.S to 3.5, preferably 2 to 3 or about 2 and w is from 0 to 9, preferably 2.5 to 6.
The zeolite should be a univalent cation-exch~nging zeolite, i.e., it should be an alurninosilicate o a univalent cation such as sodium, potassi~t,lithium (when practicable) or other alkali metal, ammonium or hydrogen (sometimes).
Pxeferably the univalen~ cation of the zeolite that is em-polyedi~ an alkali metal cation, especially sodium or potas-sium, and ntost preferably is sodit~t~
Crystalline types of zeolites utili~able as good ion exchangers in the invention, at least in part, include zeolites oE the following crystal strtlcture groups: A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of such molecular sieve zeolites can also be useful, especially when type A zeolite is present.
These crystalline types of zeolites are well known in the art and are more particularly described in the text Zeolite Molecular Sleves by Donald W. Breck, published in 197~ by John Wiley & Sons. Typical comtttercially available zeolites of the aforementioned structural types are listed in Table 9.~ 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 detexgent composition builders.
The æeolite used in the invention is usually synthetic and it is often characterized by having a network of substantially uniforntly sized pores in the range of about 3 to 10 Angstroms, often beirtg about 4 A (normal), such size being uniquely determined by the unit structure of the zeolite i;3 crystal. Preferably it is of type A or similar structure, particularly described at page 133 of the aforementioned text.
Good results have been obtained when a type 4A molecular sieve zeolite is employed, wherein the univalent cation of the zeolite is sodium and the pore size of the zeolite is about 4 Angstroms. Such zeolite molecular sieves are described in U.S. patent 2,882,243, which refers to ~hem as ~eolite A.
Moleculax sieve zeolites can be prepared in elther a dehydrated or calcined form wh.ich contains from about 0 or about 1.5~ to about 3~ of moisture ox in a hydrated or wa~er loaded form which contains additional bound water in an amount from about 4% up to about 36% of the zeolite total weight, depending on the type of zeolite used. The water~
containing hydrated form of the molecular sieve zeolite (preferably about 15 to 70% hydrated) is preferred in the prackice of ~his invention when such crystalline pxoduct is used. The manufacture of such cxystals is well known in the art. For ~xample, in the preparation of Zeoli~e A, reEerred to above, the hydrated zeolite crystals that a.re formed in the crys~allization medium (such as a hydrous amorphous sodium alum.inosilic~te gel) are used withol1t the high temperature dehydration (calcining to 3~ or less water content) that is normally practiced in pxeparing such crystals for use as ca~alysts, e.g.l cracking catalysts.
The crystalline zeolite, in either completely hydrated or partially hydrated form, can be recovered by filtering off the crys-tals from the crystallization medium and drying ~hem in air at ambient ~emp~rature so that their water contents are in the range of about 5 to 30% moistuxe, preferably about 10 to 25%, such as 17 to 22%. However, the moisture content of the molecular sieve zeolite being employed may be much lower, as was previously described, in which case the 7.eolite will usually be hydrated during crutehing and other processing.
Preferably the zeolite should be in a finely divided state with the ultimate particle diameters being up ko 20 microns, e.g., 0.005 or 0.01 to 20 miorons, preferably being from 0.01 to 15 microns and especially preferably of 0.01 to 8 microns mean particle size, e.g., 3 to 7 or 12 lS microns~ if crystalline, and 0.01 to 0.1 micron, e.g., 0.01 to 0.05 micron, if amorphous. Although the ultimate particle sizes are much lowar t usually the zeolite particles will be of sizes withinthe range of 100 ko 400 mesh, preferably 140 to 325 mesh. Zeolites of smaller sizes will often become objeckionably dusty and those of larger sizes may not sufficiently and satisfactorily cover the carbonate-bicarbonake base particle nuclei on which khey may be deposited during spray drying of a crutche~ mix ~o form the ba~e beads.
The bentonite employed i~ a colloidal clay (alumi-5 num silicate) con~aining montmorilloni~e. Montmorillonite is a hydrated aluminum silicate in which about l/6th of thealuminum atoms may be replaced with magneslum atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, magnesium and other metals may be loosely combined. The type of bentoni~e clay which is specifically described herein for making the invented basa beads is that which i~ known as sodium bentonite ~or Wyoming or western bentonite), which is normally a light to cream-colored impalpable powder which, in water, forms a colloidal suspension having strongly thixo-tropic properties. In water the swelling capacity of the claywill usually be in the range of 3 to 15 mlO/gram, preferably 7 to 15 ml./g. and its viscoslty, at a 6~ concentration in water, will usually be in the range of 3 ~o 30 centipoises, preferably 8 to 30 c~ntipoises. PreEerred swelling bentonites of this type are those which have been sold under the trade-mark THIX0-JEI" as industrial bentonites r by ~enton Clay Company, an affiliate of Georgia Kaolin Co. Such ma~erials are sQlectively mined and beneficiated bentonites, and those considered ~o ~e most useful are those which have been 20 identified as THIX0-JEL's. No'sO 1, 2, 3 and 4. Such materials are o pH's (6~ concentration in water~ in the range of 8 to 9~4, maximum free moisture contents of about 8~ and specific gravities of about 2.6, and for the pulveri2ed grade about 85% passes thro~gh a 200 mesh U.S. Sieve Series si~ve. Such materials exhibit an exchangeable calcium oxide percentage 3~3 in the range of about 1 to 1~8 and with respect to magnesium oxide such percentage is normally in -the range o~ 0.04 to 0.41. Typical chemical analyses of such materials are from 64.B to 73.0~ of SiO2, 1.4 to 1.8% of A12O3, 1.6 to 2.73 of MgO, 1.3 to 3.1% of CaO, 2.3 to 3.4% of Fe2O3, 0~8 to

2.8~ of Na2O and 0.4 to 7.0% of K2O. Although such bentonites are preferred,equ~valent materials from other sources may be substituted.
The polyacrylate, present in preferred base beads of this invention, .is a low molecular weight polyacrylate, such moleclllar weiyht usually being within the range o 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 neutralized or completely neutralized, e.g., about 1/~ or 1/3 Na salt. Although modified polyacrylates may be substituted for the described sodium polyacrylate~
including some other alkali metal polyacr~lates and hydroxylated pGlyacrylates t it iS preferxed that such substitutions be limited to a minor proportion of the ~0 material and preferably the polyacrylate will be an unsub-stituted sodium polyacrylate. Such materials are ava.ilable from Alco Chemical Corporation under the name Alcosperse.
The sodium polyacrylates are available as clear ambex liquids or powder~, with the solutions being of about 25 to ~o% solids content~ e.g., 30%, and wi~h ~he pH of such sol.uti4ns or of a 30% aqueous solution of the powder being in the range of about 7.5 to 9.5, e.y~, 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 compounds from aqueou~ solutions.
The presence of the polyacrylate, even in very small quantity, helps to ~etter mix the various crutcher mix components, including, in pr~ferred formu:la~ions, ultramarine blue, which, when poorly distributed, can stain laundry washed with detergent made from the base beads. The poly~
acrylate al~o helps to evenly distribute any fluorescent brightener throughout the crutcher mix and the detergent composition~ thereby aiding the uniform brightening of the wash. Additionally, th~ polyacrylate makes ~he total end product (except ~or the nonionic detergent content) more homogeneousO Processing aids which may be present to prevent gelation and setting of the inorganic materials in the crutcher during mixing and standing thereof are more uniformly dispersed in the crutcher mix, increasing their eficiency of operation.
The polyacrylate helps to make the base beads produced by spray drying more absorptive of the liquid state nonionic detergentwhich is spxayed onto the beads. In som~ cases it increases the detergent holding capacity of the beads, while still allowing them to flow freely. Spray drying operations are improved due to less of the sprayed material adhering to the dryer walls, thereby increasing spray tower throughpu-t rates and diminishing the number of cleanouts required~
The only other mater.ial necessary for making ~he present beads is water, and during drying of the beads the moisture content thereof may be decreased so that the product is almos~ anhydrous. While it is preferred to employ deioni~ed water, so that tbe hardness ion contents thereof may be very low and ~o that metallic ions than can promote decompositi.on o any oxganic materials wh.ich may be present in the fin~l beads and detergent are minimized, norma~lycity or tap water may be used insteadO Normally the hardness content of such water will be less than 150 p.p.m., as CaCO3, more preferably the hardness content will be less than 100 p.p.m. and most preferably it will be less than 50 p.p~m.
Because fairly concentxated aqueou3 crutcher mixes of silicate, carhonate, bicarbonate, zeolite and bentonite and/or polyacrylate present, may "freeze'~ in the crutcher due to interactions of the components thereof, if held beyond a permissiblé time, processing aids are preferably present in ~he crutcher when silicate is present, and consaquently, in the finished base b~ad and detergent composition; to prevent pr0mature solidification or gelation of the mix. Most preferably, such include citric acid and magnesium sulfate.
Instead of citric acid, soluble citrates, such as so~ium t-~

citrate, may be used and ~hile it is preferable to employ anhyd.rous magnesium sulfate, various hydrates thereof, such as epsom salts, may also be used. Also, rnagnesium c.itrate ~dn be substituted. In place of the preferred anti-gelling system other means and suitable systems for maintaining the crutcher mix fluid may be substituted, such as sodium sesqui carbonate, employed in replacement o~ some of the sodium carbonate and sodium bic~rbonat2.
Various adjuvants, such as perfumes, enzymes, 1~ coloxants, bleaches and flow promoting agenks may often be sprayed onto or otherwise mixed with the base beads after the manufacture thereof, with the nonionic detergent ox separate from i~, so that they are not adversely af~ected by the spray drying operation and al50, S0 that their p.resence in the spray dried beads does not inhibit absorption of nonionic detergen~. However, for stable and norm~lly solid adjuvants, mixin~ in with the inorganic salt~ slurry in the crutcher is also feasible. Thus, it is contemplated that coloring agents and fluorescent brightener will normally be present in the crutcher mix from which the present base beads are sprayed. The preferred coloring agent is ultra-marine blue but other stable pigments and dyes may be used with it or in replacement of it. Among the fluorescent brighteners the most preferred is Tinopal 5BM. ~owever, various other cotton brighten~rs, such a5 those some~imes referred to as CC/DAS brighteners,derived from the reaction 14 ~

product of cyanuric chloride and ~he disodium salt of diamino-stil~ene disulfonic acid, may also be employed, including variations thereof with respect to substituents on the triazine and aromatic r.ings~ This class of briyhteners is known in the det~rgent art and will most of~en be used when bleaching components are not present in the final product. In such instances bleacll stable brighteners may he employed.
Among these may be mentioned the benzid.ine sulfon~ disulfonic acids, naphthotriazolyl stilbene sulfonic acids and benz-imidazolyl derivatives~ Polyamide brighteners, which alsomay be present, include aminocoumarin or diphenyl pyrazoline derivatives,and polyester brightenersl which can also be used, include naphthotriazolyl s~ilbenes. All such bright-ener~ are normally used as their soluble salts but they may also be eharge~ as the corresponding acids. The cotton bri~hteners will usually comprise major proportion~ o~ the brightener systems.
Of the materials that may be post-added to the spray dried base b~ads the most important, of course, is th~
nonionic detergent. Although various nonionic detergen~s of satisfactory physical charac-teris~ics may be utili~ed~
including condensation products of e~h~lene oxide and propylene oxide with e~ch other and with hydroxyl-containing basesl such as nonyl phenol and Oxo t~pe alcohols, it is usually pref~rred that the nonionic detergent be a condensa~ion 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 detergenk contains from about 3 to 20 ethylene oxide groups per mol, preferably from 6 ~o 12. Such detergents are made by Shell Chemical Company and are available under the trade names Neodol 23-6.5 and 23-7.
The enzyme preparations, which normally a:re post-added to the base beads, may be any of a variety of commer-cially available products, included among which are Alcalase,manufactured by Novo Industri, A/S, and Maxatase, both of which are alkaline proteases (subtilisin). Although the alkaline proteases axe preferred, amylolytic enzymes, such as alpha~amylase, as well as proteolytic enzymes, may be utilized.
The mentioned compositions usually contain active enzym~s in combination with an inert powdered vehicle, such as sodium or calcium sulfate, and ~he proportion of active en~yme may vary widely, usually being from 2 to ~0~ of the co~nercial prepara~
tion. The perfumes employed, which are usually heat sensitive and may include some volatile solvent material, such a~ alcohol, are normally of synthe~ic perfumery materials, sometimes mixed with natural components, and generally will include alcohols, aldehydes, terpenes, fixative~ and other normal perfume components. Flow pxomo~ing agents, such as ~pecial clays~
which are sometimes added to detergent products, while often - 16 ~

useul to improve Elowability and to diminish tackiness of various compositions, are unnecessary in the present cases, possibly in part due to the presence of the bentonite and/or polyacrylate. HoweverJ they may be added if desired, to further increase flowability.
The proportions of the various components in the base beads will be such as to result in their being free-flowing and sufficiently ahsorptive o a nonionic detergent applied thereto in li~uid state so that the dekergent composi-tion made from them by incorporation of such detergent willalso be satisfactorily free-flowing. Also, of course, the detergent composition made from the base beads must be an effective cleaning agent, with the builders present acting to assist the organic detergent in aqueous solutions of the composition, and it is important ~hat the resulting product be one which does not cause objectionable depositi.on of zeolite particles (possibly wi~h other substances, such a~
normally water soluble silicates) on washed materials~ It has been found that fairly satisactory base beads ~o accomplish this purpose, when silicate is present, may comprlses, by weight, rom 15 to 30~ o sodium carbonate, 10 to 22% of ~odium bicarbonate, 20 to 40~ of water softening aluminum silicate (zeolite), 3 or 4 to 12% o~ sodium silicate and 1 to 15% of bentonite, as the ac-tive components, and 1 to 15%
of water. In such beads the aluminum silicate will preferably be a sodium z~olite containing from 15 to 25% by weight thereof of water of hydra~ion and more preferably, such zeolite will be Zeolite A. The preferred weight ratio of sodium carbonate :
sodium bicarbonate in the product is within -the range of about 1 to 3, the beads made have a bulk density in tha range of 0~6 to 0.9 g./cc., more preferably 0.7 to 0.8 g./cc. and the bead particle sizes are in the range of No's. 10 to 100 (through No. 10 and on No. 100), U.S. Sieve Series, more pre:Eerably 10 to 60, U.S. Sieve Series. Further preferred proportions of 10 components are from 20 to 25~ of sodium carbonate, 13 to 1~%
of sodium bicarbonatel 30 to 37% of hydrated zeolite, 5 to 8 or 10% of sodium silicate, 5 to 8% of bentonite and 4 to 10~ of water, exclusive of the water of hydration of the æeolite.
In such more preferred products the weight ratio of sodium ~arbonate : sodium bi.carbonate is within the range of 1 to 2.
When a polyacrylate is present together with the zeolite in the base bead composition the proportion thereof will normally be in the range of 0.1 to 2~, preferably 0.2 to 1.6~ and more preferably 0.8 to 1.4~ Proportions of ~0 adjuvants and processing aids and fillers, if any, in the base beads, will normally be limited to 20~ thereof, preferably being 1 to 10~ and more preferably being 3 to 7% therecf.
The proportions of processing aids, when magnesium sulfate and citric acid are employed, will normally be rom 1 to 3~ of magnesium sulfate, more preferabiy 1O5 to ~.5~ ~hereof, and ~8~5i3 Oo2 to 1% of sodium citrate, mo~e prefexably 0~2 to 0.5%
thereof. With r~spect ~o pigmenting and fluorescent bright-ening agents the proportlons will preferably be from 0.05 to 0.6% of pigment, such as ultr~marine blue, more prefer-ably 0.2 to 0~4%, and 0.1 ~o 4~ of fluorescent brightener,more preferably 1 or 1.5 -to 3% thereof. Such proportions of processing'aids and adjuvants apply to the various types of beads of this invention, when such ~ids or adjuvants are employed.
The proporti.ons of the various components in the crutcher mix and in the base beads when making beads compris-ing polyacrylate but omitting bentonite will be such as to result in the mix being uniform or nearly ~o, and the beads being ree-flowing and sufficiently absorptive of a nonionic deterg~nt applied theret,o in liquid state so that the deter-gen~ composition made from them b~ incorporaiion of such detergent will also be satisfactorily free-flowing. It has been found that satisractory base beads to accomplish this purpose comprise, by weight, from 15 to 30% of sodi~m carbonate, 10 to 22~ of -sodium bicaronate, 20 to 40% of water softening aluminum silicate ~2eolite), 3 or 4 to 18~ of ~odium silicate and 0.1 to 2% of polyacrylate, as the ac~ive components, and 1 to 12 or 15% of water~ The preferr~d weight ratio of ~odium carbonate : sodium bicarbonate in the product is within the range of about 1 to 3, the beads made have a bulk _ ] ~ _ density in the range of 005 to 0~8 g./cc., preferably 0.7 -to 0.8 g./cc. and the bead particle sizes are 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. Further S preferred proportions of components are from ~0 to 25?~ of sodiurn carbonate, 13 to 19% of sodium bicarbonate, 30 to 37%
of hydrated xeolite, 7 to 15~ of sodium silicate, 0.5 -to 1.5~ of sodium polyacryla~e and 3 to 10~ o~ water, exc:Lusive of the water of hydration of the ~eolite. In more pre~erred products of such type the weight ratio of sodium carbonate :
sodium bicarbonate is within the range of 1 to 2.
When the beads to be made will have little or no water soluble silicate present, as was previously indicated when referring to other types of the inven~ed beads, the proportions of the various components in the base beads will be such as to result in their being Eree-flowing and sufEiciently absorptive of a nonionic detergent applied ther~to in liquid state 50 that the deteryent composition made Erom them by incorporation o such detergent will also be satisEactorily free-flowing. Also, it is important that the resulting product be one which does not cause objectionable deposition of zeolite particles (possibly with other substances) on washed materials. It is also desirable for the base beads made ~o be of appropriate bulk density and color. It ha been found tha~ satisfac~ory such base bead~ to accomplish these - ~0 3g5~

purposes comprise, by weightr from 15 to 30~ of sodium carbonate, 10 to 22% of sodium bicarbonate, 10 to 50% of water softening aluminl~n silicate (zeolite), 0 to 3~ of sodium silicate and 3 ~o 20~ of hentonite, as the active S components, and 1 to 15% of water. The percentage of water gi~en is free water and does not include the water of hydration of the zeoli.~e. Correspondin~ly, the percentage of zeolite does i.nc~ude wat2r of h~dration. ~n some instances th~ product may be anhydrous, with respect to free moi~ture content, but such cases are rare and it is normally desirable for at least a small proportion of water to be in the base beads to prevent undesirable pvwdering thereof, which could sometimes otherwise occur with part.icular anhydrous formulas.
The preferred weight ratio of sod:ium carbonate : sodium bicarbonate in the product is within the range of about 1 to

3 J the beads made have a bulk density in the range of 0.6 to 0~9 g./cc., more preferably 0.6 or 0.7 to 0.8 g./cc., and the bead particle si2es are in the range of No's. 10 to 100 (through No. 10 and on No~ 100), U.S. Sieve Series, more pre~erably i0 to 60, U.S. Sieve SeriPs. Further preferred proportions of componen~s are from ~0 to ~7% of sodium carbonate, 14 ~o 21% of sodium bicarbonate, 20 to 50~ of hydra~ed 2eolite, 0~ of sodium ~ilicate, 5 to 20~ of bentonite and 1 to 5% vf water, exclusivP of the water of hydration of the zeolite. In such more preerred products the weight - 21 ~

5~3 of sodium carbonate : sodium bicarbona~e i~ within the range of 1 to 2. When si.licate is present ln such base beads it wi.ll be prefe.rred ~o limit its conten-t to 2%, more pxeferably -to 0.5 to 1~ Other preferred ranges o:E pxoportiolls of important components of this invention are 35 to 45~ of hydrated zeoli.t~ and 5 to 15~, more preferably 10 to 15~-~, of bentoni~e~
When a polyacrylate is presellt in such base bead composition the proportion thereo:E will. normally be ln tne ]0 range o~ 0.05 to 0 5%, preferably 0.05 to 0.3% and more pref~rably 0.1 to 0.2%. Pxoportions of adjuvants and process-in(7 aids and fillers, i any, in such base beads, will normal-ly be limited to 20~ thexeof, prefeL-ably bei.ns 1 to 10% and more preferably bcing 3 co 7% thereof, and -the proportions will be like those previously given.
While it has been found that detergent compositions made from the present base beads do not requir~ the pre~ence of any anti.-corro~.ion additive to replace the s:ili.cate, it is within the invention to utilize suitable such materials and it will be preferred to e~lploy those which are stable under crutching and spray dxying conditions and which do not adversely a~fect such operations. Such anti-corrosion additive~ or antioxidants may be organi~ or inorganic, wi~h inorganic materials normally being pxe-ferred~ and they will 2~ preferably be c~osen for suitability for preventing corroC;ion 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 magnesium ion hardness treatment effect, a powdered silicate will normally be preferable, such as hydrous sodium silicate, which is commercially available under the name Britesil, manufactured by Philadelphia Quart~ Co.(Na20:SiO~ 2.4), and such will be post~-added.
However, other normally solid soluble silicates, preferably of alkali metals, may also be post-added to the beads of this :lO invention into which nonionic detergent has previously been absorbedO
When it is desired for the product made to possess texkile softening characteristics, softening materials, 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 softeners are cationic compounds, particularly quaternary ammonium compounds, such as quaternary a~onium halides. Especially preferred are the h~gher alkyl~, alkylaryl- and arylalkyl-lower alkyl quaternary ammonium chlorides and bromides, such as distearyl dimethyl ammonium chloride. Of commercial softening materials that which is most preferrd is sold under the trad name Arosurf TA-100, manufactured by Sherex Chemical Company, Inc. Such compounds possess antistatic and antibacterial properties, too, but if desired9 other antibacterial adjuvants may also be employed, preferably also incorporated in the product by post-addition.
It is an important feature of the present ;nventioll that an effective built detergent composition based on nonionic detergent alo~e,` may be made by a commercially fea~ible process but sometimes it may be desirable to also have an anionic ~urface active or detergent component present in the final product, usually for its contribution to the product of foaminy characteri~tics and supplementary cleaning effects. Normally it will be. preferred not to incorporate such anionic deteryPnt material(s) in the crutcher, so if such is/are to b~ employed it will preferably be by pos~-addition to the spray dried base beads, and normally such post-addition will take place after absorption by the beads of the liquid state nonionic detergent.
While various types of anionic de~ergents, preferably complete-ly ln powder form, and/or sometimes mixed with builder material, may be utilized, those which are preferred are the linear higher alkylbenzene sulfonates, higher Eatty alcohol sulEates and polyethoxylated higher fatty alcohol sulfates. In such products the higher alkyl and higher alcohol portions will normally be of 8 to 20, pr~ferably 12 to 15 carbon atoms, and the detergent~ will be present as their water soluble alkali metal salts, preferably as sodium ~alts~ The ethoxylated alcohol sulfate will no~mally contain from 3 to 20 mols of ethylene ox~de per mol of fa~y alcohol.

- 2~ -i3 The ranges of proportions of the various bead components in the f.inal detergent cornposition rnay readily be cal.culated from those gi.ven for the base beads, diminished by proportions of detergent and other materials post-added to the beads. Thus, if the final detergent composition had only nonionic detergent added to it sv that the final product contains 20~ o~ nonionic detergent, from the various ranges given for components in the base beads ranges of proportions thereof may be calculated by multiplying by 0.8, which is tlOO - 20)/lOO. Similary, when the proportion oE nonionic detergent (in formulas wherein it is the only additive to the beads) may range :~rom 8 to 25% of the deteryent composi-tion, the multipliers will be from 0.75 to 0.92. Usually the f.inal percentage of nonionic detergent in the product will be in the 8 to 25~ range, preferab].y being 15 to 22~ and more preferably being about 20%, but in some s.ituations, for certain types of produc-ts, propor~.i.ons i.n the 8 to 13% range may be pre~rred. Normally the percentage of perfume in the final prGduct will b~ in the range of 0.1 to 1%, prefer-ably O.2 to O.4~l the percentage of enzyme will be from 0.5to 3~, preferably l or 1.5 to 2.5~ and the percentage of flow improving agent, which may be post-added, will be less than 2%~ preferably less than 1~. Of course, to calculate the ranges o~ bead components :in the final composition, in addition to basing such calculations on the percentage of - ~5 ~

nonionic detergent in the final product (post-aclded) the percentages of other post-acljllvants will also have to be considerecl. ~lso~ i~ some post-additions are made hy mPans of aqueous solu~ions of ~he additiveg, ~his will affect the moisture content too, which will oft.en be kep~ in the 1 to 12%, range but sometimes may be extended to 15%.
When-polyacry.late i 5 employed and bentonite is omitted, the ranges of proportio.ns of the various detergent composition components are 13 to 28% of sodium carbonate, 8 10 to 18% of sodium bicarbonate, 15 to 35~ of water softening aluminum silicate, 3 to 40% of sodium silicater 0.1 to 1.6~
of polyacrylate, 8 to 30~ of nonionic de~ergent and 1 ~o 10%
of waterO Preferably, such ranges are 16 to 21% cf sodium carbonate, 10 to 15% of sodium bicarbonate, 22 to 32% of 15 hydrated ~eolite, 8 to 13~ of sodium silicate~ 0.5 to 1~5~
of sodium polyacrylate, 3 to 6~ (a.nd some~i.mes 3 to 10~) of moisture and 10 to 2.2 or 25~ of noll.iorlic detergent. The processing aids, bri.ghtener and colorant percentaye~ in the final detergent compo~ition will be approximately the same as in the base beads F pxeferab.ly being in th~ range of Q.~
to 0.6% for sodium citrate ~resulting from the addition of citric acid) and 1 to 2% for the magn~siwn sul~ate, 0.1 to n 03% for ~he ultramarine blue and 105 to 2% for the fluorescen~ brightening agent~ The enz.yme content will be 25 in the 0.5 to 3~ rang~, usually ~eing 1 to 2%, and the perfwne ~8~

content will be 0.1 to 1%, preEerably 0.2 to 0.4-~.
The ranges of proportion.s of the various bead components in the spray dried part of the fi~al detergent composition, when little or no silicate is present, may be calcula-ted in the manner previously described~ As to post~
- added components, the percentages of non.ionic detergent will be the same as-yiven earliert the percentage of perfume in the final product w.ill be in the range of 0.1 to 1%, prefer-ably 0.2 to 0.4%, the pe.rcentage of enæyme will be from 0.5 to 3~, preferably 1 to 2~, and if a hydrous sil.icate is post-added the proportion thereof will normally be from 2 to 10%, preferably 3 to 8%, e.g., about 5~. When a softening compound is p.resent in the final produGt the proportion there-of will normally be in the range of 3 to 12~, preferably 5 to 10~, and when anion.ic detergent~s) i.s/are utilized, the pro-portion thereof will be limited to no more than that oE the nonionic detergent and th~ total weight of anionic and nonionic detexgents in the final product will be within the ranges previously given for nonionic detergent alone. If a~ionic detergent is employed, the amount thereof present will normal-ly be within the range o 0.2 to 0.8 times the weight of the nonionic detergent. Of course, to calculate the ranges of bead components in the final composition, in addition to basing such calculations on the percen~age of nonion~c de~er-gent in the final product (post-added~ the percentage~ of - ~7 -~ a~l8g~53 other post-adjuvants will also have to be considere~. Alsv, if some po~t-additions are made by means of aqueous solutions of the additives, this wi]l aff~ct the moisture content too, but such will usually be kept in the 1 to 12~ range for the S final product, which sometimes rnay be extended to 15%.
The base beads of the invention are spray dried Erom an aqueous cru-tcher mix which normally will contain ~rom about 40 to about 70 or 75~ of solids, preferably 50 to 65% thereof, with the balance being water, preEerably deionized water as previously described, but city water may also be employed. The crutcher mix composition ranges may be calculated back from the desired base beads composition ranges on the basis of the moisture contents of the beads and the mix. Thus~ fox example, in a crutcher mix to contain 50~ of moisture, from which mix a base bead contain-ing 5% moisture is to be produced (neylecting water of hydratiorl in the zeolite), the percentages of components in the base bead should be multiplied by 10/19, which is (100/2[100 - 5~3. The above calculat-ions are satisfactory for components which do not decompose in the spray drying operation but it is known that a portion of the bicaxbonate changes to carbonata when dried at elevated temperakures in a spray tower. ~ccordingly, knowing the characteristics of the tower and the drying condition~, ~o that the ext~nt of bicarbonate decomposition is predictable, one can calcula~e ~:~L8~

the proportion of carbonate and bicarbonate to ha~e in the crutcher mi~. Thus, for example, ~hen lt is desired to make a product containing about 22% of sod.i~n carbonate and about 16% of sodiurn b1carbonate, in those cases wherein abou~
one-~hird of the bicarbonate decomposes t~o carbonate in the spray tower (with two parts of carbonate resulting from three parts of decomposed bicarbonate), one might charge 2~%
bicarbonate and 17% carbonate to the crutcher (dry basis).
With respect to the various formulations and calculations it will be considered that the zeolite in the crutcher mix and in the spray dried base beads and detergent composition is hydrated to the extent of about 20% water of hydration but it is recognized that the degree of hydration might vary. However, for consistency and for the purpose of such calculations such constant degree of hydration will be assumed.
The crutcher mix from which the base beads of the present invention are most preferably made by spray drying is one which is primarily inorganic and the content of organic material is usually limited to 10%, preferably to 7%, and more prefera~ly, to 4%, on a solids basls~ Among such organic materials which may be present are citric materials (citric acid and soluble citrates), fluorescent brightener, polyacrylate, dye~ and pigments. Other organic materials may also be pre~ent, including hydrotropic salts, chelating ~53 agents and polyelectrolytes, but, as is evident, the crutcher mix will remain primarily of inorganic materials and wa-ter.
For the polyacrylate-containing beads, without bentonite, on a 100% solids basis, the crutcher mix will S noxmally be about 10 to ~5% of sodium carbonate, 15 to 30%
of sodium bicarbonate, with the weight ratio of sodium bicarbonate : sodium carbonate heing within t~e range oE 0~5 to 2, 20 to 40~ of water softening aluminum silicate, 4 to 18% of sodium silicate and 0.1 to 2% o~ polyacrylate. When processing aids are present the proportions thereof, on the same basis, will usually be from 1 to 3% of magnesium sulfate and 0O2 to 1~ of sodium citrate. Preferably, in such crutcher slurries, th~ content oE sodium polyacrylate will be from 0.5 to 1.5% and, when processing aids and colorants are also present the proportions thereof will be from 1.5 to 2.5~ oE
magnesium sulfate, 0.2 to 0.5~ of sodium citrate, 0.2 to 0.4% of ultramarine blue and 1.5 to 3% o fluorescent bright~
ening agent, on a solids basis.
The crutcher mix is preferably made by sequen-tially adding various components thereof in the manner which will result in the most miscible, readily pumpable and non~setting slurry for spray drying. The order oE addition of the various components may be varied, depending on the circumstances, but it is highly desirable to add ~he silicate solution ~if any) last, and if not last, at least aEter the addition of any gel or set preventing combination of materials or processing aids.
Normally it is preferable for all or almost all of the water to be added to the crutcher first, preferably at about the processing temperature, after which the processing aidc (if present) and other minor components, including pigments and fluorescent brighteners,and polyacrylates tif present), are added, followed by the bentonite (if present) ~eolite, bi~
carbonate, carbonate and silicate (if present). Usually during such additions each component will be mixed in thor-oughly before addition of the next component but methods ofaddition may be vaxied, depending on the circumstances, so as to allow co-additions when such are feasible. Sometimes component additions, ~uch as silicate additions, may be in two or moxe parts. Different components may be pre-mixed before addition, to speed the mixing process. Normally, mixing speed and power will be increased as the materials are added.
For example, low speeds may be used until after admixing in o the last of the bentonite or zeolita, after whîch the speed may be increased to medium and then to high,beore, during and after addition of any silicate solutiQn.
The temperature of the aqueous medium in the crutcher will usually be about room temperature or elevated, noxmally being in the 20 to 80C. range, preferably from 30 to 75C. and more preerably, 40 to 70~Co Heating the crutcher medium may promote solution of the water soluble 3~

salts of the mix and thereby increase miscibility but the heating operation, when effected in the crutcher, can slow production rates, and can promote setting of the mix. There-fore, an advantage of having processing aiding materials present in the mix lS that they ensure that the desir-able non-gelling slurries will result at both lower and high-er temperatures. Temperatures higher than 80C. (and sometimes 70C.) will usually be avoided because of the possibility o~
decomposition of one or more crutcher mix components, e.g.
sodium hicarbonate. Also, in some cases, lower crutcher temperatures increase the upper limi~s of crutcher solids contents, probably due to insolubilizing 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 a~
four hours, in ~ome cases. The mixing times needed to bring all the crutcher mix components substantially homogeneously together in ona medium may be as little as ten minu~es but in some cases can take up to an hour, although 3~ minutes is a preferable upper limitO Counting any such initial admixing times, normal crutching periods will be from 15 minute~ 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 hour, preferably for two hours, and more prefexably - 3~ -~8~ ;3 for four hours or lon~er, after completion of the making of ~he mix, and may even be mobile for as much as 10 to 30 hours before pump-out to the spray tower, for situations wherein other manufactuxing problems may bP encoun~ered.
The crutched slurry, with the various sal~s and any other components thereof dissolved or in particulate form, uniformly distributed therein, is trans~erred in usual manner to a spray dxying 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 absorpti~e bead form. During the drying, part of the bicarbonate (often 1~4 to 1/2, e.g., 1/3) may be converted to carbonate, with ~he xelease of carbon dioxide, which, in conjunction wi~h the content of polyacrylate which may be present in the mix being spray ~ried, can improve the physical characteristic 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, zeolite and ben~oni~e components of base beads made also appear to favor absorption o~ liquid, and the polyasrylate also promotes faster dryingt thereby increasing tower throughput.
After drying, the product is screened to desired size, e.g., 10 to 60 or 100, U.S. Siev~ Series, and is ready fox application of nonionic detergent spray thereto, with the beads being either in warm or cooled (to room temperature) condition. However, the nonionic detergent will usually be at an elevated temperature, such as 30 to 60C., e.g., 50C., to assure that it will be liquid; yet, upon cooling to room temperature, desirably it will be a solid, often resembling a waxy ~olid. Even if at room temperature the nonionic deter~ent is somewhat tacky, this characteristic does not malce the final composition poorly flowing because the deter-gent penetrates to below (or within) the bead surface. The nonionic detergent, applied to moving or tumbling beads in known manner, as a spray or as drQplets, is preferably a condensation product of ethylene oxide and higher fatty alcohol, such as was previously describedl but other nonionics may also be operative. The enzyme preparation (herein referred to as enz~me, although it is recogni~ed that it includes a carrier material, too), hydrous silicate and any other powdered adjuvants to be po~added may b~ dusted on~o the detergent particles, and perfum~ and any other li~uids may be sprayed on at a suitable point, before or after addition~s) of the powder( 5 ) .
The spray dried base beads and the detergent - 3~ -compositions made from thern may include little or no silicate Erom the crutcher mix and in such case 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 agglomerations that tend ~o deposit on l~undered articles are red~lced~ Although, without the bentonite being present, silicate would normally be used, at least for its anti-corrosion effects, the present detergent compositions have not been found to corrode aluminum articles, even without the silicate. Furthermore, bentonite does not ad~ersely a~fect the stability of the product and in fact, appears to help to hold the bèads together, making them resistant to crushing and powderiny during shipment and use.
The presence of bentonite and/or polyacrylate significantly improves the properties of the final detergent composition, with the bentonite producing higher calcium ion binding rates and resultiny in less zeolite being deposited on laundered fabrics. When the low molecular wei~ht polyacrylate is present the beads become more porous and better absorb the nonionic detergent in liquid s~ate, without unduly lowering the bulk density o the produc-t. Consideriny that bentonite i5 a clay and might be expected to ~reate depositicn and gelation problems of its own, ~hP low~red deposi~ion of zeolite and absence of gelation are surprising,~ and are important resultq of the present invention.

The following examples illustrate but do no~ limit the invention. Unless otherwise indicated all tPmperatures are in C. and all parts are by weight in the examples and throu~hout th~ specification. Also, when weigh~s and propor-tions of zeoli~e ar~ given, -these are intended to be for the normal hydrate ~einy u~ed, because it i3 considered that the zeolite water of hydration does not leave ~he zeolite and does not become part of the aqueous solvent medium in the prPsent crutching operations, and al~o because some of the water present in the base bead~ and the detergent compositions is present as wate.r of hydration of the zeolite.

A 4536 kg. ba~ch of crutcher mi.x for spray drying to base beads of this invention and conversion to a detergent composition is made by adding to the crutcher 183.~ kg. of deioni~ed water at a temperature of about 27C., and se~uen-tially and with low speed crutcher mixing, admixing with it 51~3 kg~ of anhydrou~ magnesi.um sul~ate.~105.5 kg. of epsom salts may be used in~tead, in which situation the wa~er charged initially will be reduced to 1777,4 kg~ o7 kg.
of citric acid, 57.6 l;g. of Tinopal 5BM Extra Conc~ (CIBA-Geigy), 68 kg. of ultramarine blue powder, 169.6 3cg. of Thixo-Jel No. 1 (bentonite), 914 kg~ o Linde hydratPd Zeolite 4A (20% water o cry~talli~ation), 636.9 kg. of sodium bicarbonate and 456.3 kg. of sodi~m carbonate (soda ash)0 3g53 The mixer speed is then increased to high (in some cases it may be increased to medium speed at an earlier time if the mix is not blending as well as desired) and 189.6 kg. of sodium silicate of Na2O:SiO2 ratio of 1:2.4) are admixed (as 399.2 kg. of 47.5% of aqueous solution). Mixiny of the entire batch then continues for a`Dout an hour ~in some cases ~s long as four hours mixincJ may be used~, ~uring which time about 90.7 to 272.~ kg. of water may be los~ by evaporation, which watex may be replenish~d if desired~ During the mixiny time the crutcher slurry .i~ c~ntlnuously mobile and does ~ot gel, set or cake. Because bicarbonate. partially decomposes to carbonate ~uring spray drylng, t.he amounts thereof may ~e varied~ depend,ing on the spray tower operating characteristics.
Startlng about five minutes ~fter all the components of the crutche.r m.ix are present, the ~ix is dropped from the crutcher to a pump, which ~UIIlpS it at a pressure which .is about 21 kg.jsq. cm. into th~ top of a courlter-curren,t ~pray tower wherein the initial t.emperature is at ~ aboùt 430C. an~ the final temperature is about 105C. l'he essentiall~ inorganic base ~eads r~sulting are of a bulk density of about 0.6 to 0.7 g./mlO~ an initial adhesion approxlmating 40%, of particle sixe ra~ge subst3,ntial-ly between 10 and 100 mesh, U.S. Sieve Series (they are screened ~o such range), and of a fines charac~-eristic (through UOS. Sieve No. 50) of abou-~ 15%~ ~he moisture ~ 37 ~

~ 39S3 content of the beads is about 7%. The base beads are found to be free-flowing, non-tacky, satisfactorily porous, yet firm on the surfaces thereof, and are capable of readily absorbing significant proportions of liquid nonionic deter-gent without becoming objectionably tacky.
Detergent products are made from the spray dried beads by spraying onto the tumbling bead surfaces thereof a normally waxy nonionic detergent, either Neodol 23-6.5 or Neodol 23-7, in heated liquid state, in such quantity as to result in a final product containing 20% of nonionic deter gent, and proteolytic enzyme (Alcalase) is applied in powdered form to result in a lo 99~ concentration in the product.
Perfume is sprayed onto the product to produce a 0.25%
concentration therein. The resulting detergent products are 15 of a bulk densi~y of about 0.7 or 0.8 g./ml. and contain 27.3 of zeolite (hydrated), 20.1~ of the nonionic detergent 17.8%
of sodium carbonate (some of which is produced by decomposi-tion of sodium bicarbonate), 12.7~ of sodium bicarbonate, 5.6~ of sodium silicate, 5.45~ of water, 2.0% of enzyme, 1.7%
of fluorescent brightener, 1.5~ of magnesium sulfate, 0.4%
of citric acid (in citrate form), 0.25% of per-fume, 0.~% of ultramarine blue, 5.0~ of bentonite (ThixQ-Jel). The detergent made~ of the above formula, is an excell~nt heavy duty laundry detergent and is especially useful for washing household laundry in au~omatic washing machines. It is physically and aesthetically advantageous and attractive because it is non-dusting and extremely freely flowing, which allows ik to be packaged in narrow-necked glass and plastic bottles, from which it flows readily for dispensing. The detPrgent compo-sitions of the invention, containing bentonite, as described,are found to be of significantly improved calcium ion binding rates but more importan~ly, ~hey leave less residue on laundry washed with them (in an automatic washing machine at usual concentrations for such product and at normal washiny tempera-tures) than do similar compositions not containing the bentonite.This difference i5 accentuated when the wash water is high in hardness, e.g., 200 p.p.m., as calcium carbonate, the wash water is co~d, and a gentle agitation cycle is employed.
In a control experiment base beads are made in which the bentoni~e is omitted from the crutcher mix, being replaced by equal weights o sodium carbonate and sodium bicarbonate, the total of the added matexials e~ualling the weight of the bentonite replaced. The crutcher mix is spray dried and converted to a detergent composition in the same way used to make the invented detergent composition. Such "control" product, while useful as a detergent, re~ults in more residue being deposited on washed laundry than wi~h the experimental product of this inventlon and is of a low~r calcium binding rate. Similarly, when the content o silica~e in the control beads is increased to 10~7%, with sodium - 3~ -carbonate and sodium hicarbonate concentrations being decreased -to compensate Eor the silicate increase, -the residue deposition is even worse than with ~he control.
Following normal procedure, crutcher mixes will be made quickly and ma~ be emptied from ~he crutc:her equally fast, sometimes being made within a period of as little as five minutes and being pumped out of the crutcher in as 1ittle a~ ten minutes. Yet, i-t is often important that the present mixes be able to withstand at least an hour in the crutcher without gelling or solidifying because sometimes holdups of such times are encoun-tered in commercial produc-tion. The described crutcher mix is capable o being held for as long as four hours, and often appreciably lonyer, with-out gelling or solidifying, which is attributed, at least in part, to the content of magnesium sulfate and citric acid processiny aids therein. HowPver, other processing aids intended to prevent gelation and s~tting cf the crutcher mixes may be substituted, and under some conditions the proportions thereo~ may be decreased and one or both may be omitted.- Similarly, other minor components of the crutcher mix, such as the fluorescent brightener and pigment~
may be omitted therefrom and enzyme and perfume may be omitted rom the final product, although it is highly preerable for all such materials to be present. The crutchex mix temperature may be modified, as by elevation to 52C., ~ 4G -~8~3 and the proportions of the various components may be vari~d 10%, t20% and +30%, while still maintaining them withi~l the ranges previously given, and workable crutcher mixes that result in the desired beads and detergent compositions will be obtainable.
Inste~d of employing anhydrous magne~ium sulfate an e~uivalent propor-tion of epsom salts may be substitllted and various other components may be added as aqueous solutions, providing that the amounts o moisture added with them are subtracted from that added to the crutcher. Other orders of addition may be employed but normally it will le desired to have the proces~ing aids added early in the manufacturing procedure, with the silicate being added last or near the end thereof. Instead of using Zeolite 4A, Zeolites X and Y
may be substituted, as may be other types o Zeoli~e A.
While it is preferred to employ the hydrated Zeolite 4A of this example, various degrees of hydration of the zeolite are acceptable and in some instances nearly anhydrous crystalline zeolites or amorphous zeolites may be employed.
Varying the amount of bentonite within the range given, to 3% and 10~, for example, still re~ults in useful products but those containing larger proportions of bentonite will usually be more effective in preventing zeolite deposition on laundry. However, the proportion employed commercially depends on a number of factors and normally will represent a

- 4~ -balance struck between the desired diminution of zeolite residue and the desired building and other functional effects of other detergent composition components.

EXAMPLE ~
A product like that of Example 1 is made but wi~h the addition of low molecular weigh~ polyacrylate (M~ = 1,000 to 2,000) in the crutcher mix, added early in the production thereof, before the bentonite, so as to re~uit in a comparable product conkaining 1% of the poly-acrylate (Alcosperse 107D). The only formula change to compensate for the addition of th~ polyacrylate is a decrease in the sodium bicarbonate content in the crutcher mix by an equal weight. Additionally, the batch made is smaller, using a pilot plan~ crutcher. The base beads resulting from spray drying~ which is effected in the same manner as previously described in Example 1, are converted to a final detergent product of the same type as in Exampl~ 1, with the e~ception of the addition of the polyacrylate. The composition i5 tested and the properties thereof are observed. It is found to be an excellent free flowing de~ergent, wi~h l~ss zeolite residue on washed laundry than controls of the types mentioned in Example 1. Additicnally, the presence of the ~lcosperse noticeably improves the absorption characteris~ics of thP
beads made so khat they more readily absorb liquid nonionic de~ergentp which may be of the ethoxylated alcohol type or other types mentioned in the speci~ica~ion. Y~t, the bulk densities of the beads anrl the product are not lowered appreciably, which is significant when it is desired to manufacture a comparatively high bulk density, concentrated particulate detergent. It has been observed that when the S described polyacrylate is present in the crutcher mix better spray drying operations result and less material is lost by deposition on the spray tower walls, which processing advantages are important in speeding commercial production and in avoiding waste and reworking of off-grade material.
As with Example 1, the proportions of components in this example may also be varied, wi~hin the limits given in the speci~ication, to produce base beads and detergent compositions of improved properties. ~hile it appears that about 1% of the described polyacrylate is an optimum propor~
tion to utili~e in the detergent compositions, from 0.1 to 2~ thereof will have good effects, with use of the greater proportions resulting in greater porosity improvements of the beads. For example, instead o 1%, 0.5% and 1.5% are also desirable proportions of the polyacrylate~ In some cases it may be desirable to utilize polyacrylates of higher molecular weights within the ranges given, e.gO, 4,000-

5,000, but in most cases the lowex portion of the range will be preferred. As with Example 1, in some instances processing aids, perfume, en~yme~ fluorescent brightener and pigment may be omitted or changed but in all such instances the 395~

mentioned zeolite, caxbonate, bicarbonate, silicate and bentonite, together with polyacrylate, w:ill be pre~ent in the given proportions in the base beads~ and nonionic deter-gent will also be pr~sent in the final detergent composition, which, like the others, is of the non phosphate type.

Using pilot plant equipment, detergent base beads are made comprising 23.37% of sodium car~onate, 16.60% of sodium bicarbonate, 34.74~ of zeolite 4~, 13.64% of sod.i~
silicate (Na20:SiO~ ratio of 1:2.41, 0.26~, of ultramarine blue, 2~20% of Tinopal 5BM Ext.ra Conc. (CIBA Geigy), 1.95%
of magnesium sulfate, 0.32% of citric acid (present as sodium citrate), 1.29% of sodium polyacrylate of molecular weight .in the range of 1,000 to 2,000 ~Alcosperse 107D) and 5.64% of moi~ture. Such a pxoduct is made by spray drying of a pilot plant crutcher batch containing 50% solids and 50%
water, including water added in the aqueous silicate solution, with the polyacrylate (as when an a~u~ous sollltion thereof, such as Alcosperse 107 is utilized~ and with epsom salts, i used. The other solid components comprise ~he o~her 50% of the crutcher mix and are present m the same relative propor-ti.ons as ~iven with respect to the base beads, with the excep-tion of the sodium carbonate and ssdium bicarbonate, in which sases, assuming 1/3 decomposition of the bicarbonate to carbonate, 24.90 parts of sodium bicarbonate (proportionately) and 17.84 parts of sodium carbonate (propo~tionately) are employed.
The water charged to the crutcher is d~.ionized water and it is.at a tem~erature of 27C. The magnesium sulfate charged is anhydrou~, although an equivalent proportion oE epsom salts m~y be used .instead. After charg-ing of the water the magnesium sulfate~ citric acid, Tinopal 5BM E.xtra Conc., ultramarine blue powder and AlcGsperse 107D
are added to the crutcher, normally wi.t.h the mixer at relative ly ~low spe~d, a~ter which the Li:nde hydrat~d ~eolite 4A (.20%
water of crystalli~ation), sodi~ bicaxbonate and sod.ium carbonate may be charged, with the mixer at slow or medium speed. The mixer speed is then increased o high and the sodium sllicate is added as a 47.5% aqueous solution. Mixing O:e the ~ntire ba~ch then continues for about an hour ~in some cases as long as four hours mixing may be employed)~
during which time an apprec.iabl.e proportion of water, some-times 2 to 6~ may be lost by evaporation. Such water may be replenisbed, if des.ired. During th~ mixing t~me the crutcher slurry is cont.inuously mobile and does not gel, set or cake, Because bicarbonate decomposition may vary depend-ing on spray drying condition~ the amounts of bicarbonate and carbonate charged may also be varled accordingly to ob~ain the deslxed base bead composit.ion.

5~

Starting about ~ive Tninutes after all the components of the crutcher mix are p.resent, the rni~ .is dropped rom the crutcher to a pump, which pump~ i-t at a pres5ure which is main~
tained to ke about 21 kg./sq~ ~m. into ~ha top o: a counter--current spray tower wherein the ini-tial temperature is about 4 30 C r and the final temperature is about 10~C Q The essen-tially inorganic base beads resulting are of a bulk densi-ty o about 0.6 to 0.7 y./ml., low adhesion, o:~ particle size range substantially between 10 and 100 me~h, UOS~ Sieve Series (they are screened to such range), and do not include ~n objectionable proportion o~ finesO The moistuxe content of the beads is about 5.6~. The base bPads are found to be ree flowing, non tacky, satisfactorily porous and yet of d~sired physical strength, and are capable of readily absorbing increased proportions, e.~., 2 to 5~ moxe, of liqu.id nonlonic detergent sprayed onto them, withQut becoming objectionably tacky.
In addition t.o the desirable propexties of the base beads made, it is noted that the bui.lclup of p.roduct on th~ internal walls of the spray tower .is less, o~ten about 20 to 50% less, than when the polyacryl~te is not pre~ent in the formula~ The tower throughput is increased and it appears that the ines content of the product is diminished.
The diminut_on of buildup and of ~ines production results in a significantly lower proportion o f recycling required.

Detergent products are made from the spray dried beads by spraying onto the tumbling bead surfaces thereof a normally wa~y nonionic detergent~ either Neodol 23 6.5 or Neodol 2~-7, in heated liquid s~ate, in such ~uan~ity as to result in a final product ~ontaining 20.7% of nonionic deter-gent, and pxoteoly~ic enzyme (Alcalase) is applied in powdered form to result in a 1.32% concen~ration in the product.
Perfume is sprayed onto the product to produce a 0.25%
concentra~ion therein. The resulting detergent producks are of a bulk density of about 0.7 g./ml. and contain 27.0% of zeolite (hydrate), 20.7% of the nonionic detergent, 18.17%
of sodium carbonate (some of which is produced by decomposi-tion of sodium bicarbonate), 12.9% of sodium bicarbonate, 10.6% of sodium ~ilicate, ~.39% of mGis~ure ~ 1 . 32~ of enzyme, 1.71% of fluorescent brightener, 1.51% of magnesium sulfate, 0.25% of citric acid (in citrate form~ 0.25~ of perfume, 0.2~ of ultramarine blue and 1~0% of sodium poly-acrylate. The detergent made, of such formula, i~ an excel-lent h~avy duty laundry detergent and is ~specially useful for washing household laundry in aukomatic washing machines.
It is physically and aesthetically advantageo~s and attrac-ti~e because it is non-dus~ing and ex~remely freely flowing, allowing it to be packaged in narrow-necked glass and plastic bottles from which it may flow xeadily for dispensing.
In comparakive tests against similar composikions nok ~7 containing the polyacrylate, the compositions o~ this inven tion are found to exhl.bit improved soil removal and stain removal activities whe.n ~este~ on vari.ous -tes~:. soils and stai.ns on a wide vareity of tes~ abrics, includ.ing cot~on, polyester-cotton mixturesl polyester~ and other syntheti~s.
With respect to stain remo~al, it has often ~een found that the polyacrylates are of~en more effective aga:ins~. stains than larger quantities o~ more expensive en~ymes, which a.re u~ually more specific in stain removal action and therefore a:re not as effPctive against combinations of stain~ found in many wash loads. Compositions oE the invention containing tha polyacry-late also exhibit excellent ant.i-redeposition effects, helping to prevent dirtying of the laundry by redeposition o~ removed soil.
The manufacturing procedures may be like those described in Example 1 and different processing aids and adjuvant~ may be employe~, as set for~h .in that axample.
Also, certain adjuvants may be omitted, as mentioned in Example 1. The cru~cher mix temperature may be modified, as by elevation to 52C., and the proportion~ of the various components may be varied *10%, -~20% and ~30~, while ~till maintaining them within the ranses previou~ly gi~en, and workable crutcher mixes tha~ result in the desired beads and detergent compositions will be obtainable, ~arious compounas may be added as aque~us solutions J providing that 4~ ~

~8~5~

the amounts of moisture added with them are subtracted from the crutcher formula amount. Other orders of addition may be employed. Insteacl of Zeolite 4A, Zeolites X and Y may be substituted, as may be other typés of Zeolite A, While it is preferred to employ the hydrated Zeolite 4A of this example, various degrees of hydration of the zeolite are acceptable and in some instances nearly anhydrous crystalline zeolites or amorphous zeolites may be employed. Varying the amount o polyacrylate within the range given, to 1.0 and 1.7~ in the base b~ads, for example, still results in useful products but those containing larger proportions of the sodium poly-acrylat~ will usually be more effective in cleaning, absorbing nonionic detergent and promoting of improved tower processings.
It will usually not be desirable to util;ze more than about 2~ of the polyacrylate because its effectiveness decreases at higher concen-tration~ and the gains obtained are not economically desirable.

EX~MPLE 4 A product like that of Example 3 is made but by utilizing Alcosperse 107, a sodium polyacrylate solution wherein the polyacxylate is of a molecular weight of about 1,000 or 1,000 to 2,000 t and which is a clear amb~r liquid of 30% solids content. The proportion of Alcosperse 107 employed is equivalent in solids content ~o the Alcosperse _ ~9 _ 39~;~

107D utilized in Example 1. Instead of Alcosperse 107, proportionate amounts on a solids basis of Alcosperses 104 (25~ solids) and 149 ~40% solids content~ are substituted but the results with the 107 type product are better and therefore the Alcosperse 10~ is preferred. No other signi-ficant changes are made in the formula, compared to Example 3, nor in the processing method.
The base beads resulting from the spray drying of the crutcher mix made are converted by the method described to finished product, employing Meodol 23-6.5 as the nonionic detergent. Th~ product made when Alcosperse 107 is utilized is an excellent non-phosphate d~tergent, useful as a heavy duty built laundry detergent, which is effective against a wide variety o~ stains, including liquid cosmetic make-up and synthetic sPbum (Spangler type). A ten-member test panel also significantly prefers such a product to a comparabl~
one from which the Alcosperse 107 has been omitted. Similar-ly, such preference is indicated by instrumental measurements of washed materialsO The tests describP~ are performed on cotton, Dacron-cotton and nylon fabrics, and test conditions include machine washing in 150 pOpOm. hardness water with a detergent composition concentration of 0O07% by weight and with the water temperature at 49Co The same processing advantages mentioned in Example 3 are observable, including excellen~ dispersion of mat~rials in the crutcher and clean spraying of the product. The base beads are of a measurably greater porosity than controls (minus polyacrylate). Yet, bulk dens.~ty is not lowered more than a few percent, e.g., 3~, important for such concentrated products. Simila~ rasults are obtainable by varying the formula contents of the va.rious other essential components ~15% and +30%, keeping the proportlons within the ranges specified. Also, such results are obtainable when other Zeolite A's are utilized, of different degrees of hydration, e.g., 15 and 22%, and when polyacrylates within the molecular weight range of 1,000 to 5,000 are employed. Preferably such polyacrylates are sodium neutralized, either completely or to at least about 50% t but less neutralized ones can be used.
Results similar to those reported herein are also obtainable when fluorescent brightener~ perfume, enzyme and processing aids (citric acid and magnesium sulfate) are eliminated but in such cases care should be taken that spray drying is effec~ed soon after manufacture of ~he crutcher mix so that such mix does not set in the crutcher. Also, as is evident, the individual contributions of the omitted ma~erials will be lost, but. the product will still be a good laundry deterge~t, as de~cribed, the crutcher mix will be well dispersed and will be dried easily, and the base beads will be of improved porosity~

~ 51 A 4536 kg. batch of crutcher mix for spray drying base beads of this invention which do not ~ontain water soluble silicate is made by adding to a crutcher 2,132 kg.
of deionized water at a temperature of abou~. 27C. and sequentially, and initially with low speed cru-tcher mixing, admixing with it 47.2 kg. of Tinopal 5~M Extra Conc. (CIBA-Geigy), 5.9 kgO of ultramarine blue powder, 3.2 kg. of sodium polyacrylate (Alcosperse 107D), 957.5 kg. of Linde hydrated zeolite 4A (20% water of crystallizakion), 283.5 kg. of Th-xo-Jel No. 1 (bentonite), 714~4 kg. of sodium bicarbonate (industrial grade), 351.1 kg. of sodium carbonate (natural soda ash) and 41.3 kg. o titanium dioxide (Anatase). During mixing of the various components the mixer speed is increased to medium and ultimately to high and after addition of all the constituents, which takes approximately fifteen minutes, mixing is continued for about an hour (in some cases as long as four hours of mixing may occur) t during which time ~ome ~ of the water present, e.g~, about 90.7 to 272~2 ~g. may be lost by evaporation, and may be replenished, if desired.
During the mixing time the crutcher slurry is continuously mohile and does not gel, set or cake. Because bicarbonate partially decomposes ~o carbonate during spray drying, the amounts of bicarbonate and carbonake in`th~ crutcher formula~
tion may be varied, depending on the spray tower operating characteristics.

.

- 5~ -Starting about five minutes after all the components of the crutcher mix are present, the mix i5 dropp~d from -the crutcher to a pump, which pumps i~ at a pressure which i5 at about 21 kg./sq. cmO into the top of a counter-current spray tower wherein the initial temperature is about430C. and the final temperature is about 105C. The essen-tially inorganic base beads resulting are of a bulk density of about 0.6 to 0.7 g./ml., an initial adhesion less than 10%, of a particle size range substantially between 10 and 60 mesh, U.S. Sieve Series (they are screened to such range), and of a fines characteristic (through U.S. Sieve No. 50) of about 15%. The mois~ure content of the beads is in the range of 1 to 10%. The ba~e beads are found to be free-flowing (80% flow rate), non-tacky, satisfactorily porous, yet firm on the surfaces thereof, and are capable o readily absorbing significant propoxtions of liquid nonionic detergent without becoming objectionably tackyO
Detergent products are made from the spray dried beads by spraying onto the tumbling bead surfaces thereof a normally waxy nonionic detergent. Neodol 23-6.5 is used but Neodol 23~7 or Neodol 25-7 may be substitut~d. The nonionic detergent is in h~ated liguid s~ate (at a temperature of about 45DC. ) D The quantity sprayed is such as to result in a final product containing about 20% of nonionic detergen~.
Prot~olyti~ enzyme ~lcalase) is applied in powdered form to ~ 53 -9~

result in about a 1~5% concentxation in the product, and perfume is sprayed onto the product to produce a 0.25%
concentration therein. The resulting detergent composiiions are of a bulk density o~ about 0.7 to 0.8 g./ml. and contain 32.45% of zeolite (hydrated~, 19.7% of the nonionic detergent, 18.5% of sodium carbonate (some of which was produced by deçomposition o~ sodium bicarbonate), 13.5% of sodium bi-carbonate, 1.3% of free water, 1.4% of enzyme, l~6% of fluorescent brightener, 0.25% of perfume, 0.2% of ultra-marine blue, 9.6% of bentonite (Thixo-Jel), 0.1~ oE sodium polyacrylate and 1.4% of titanium dioxide. The detergent made, of the above formula, is an excellent heavy duty laundry detergent, useful for washing household laundry in automatic washing machines. It is non-dusting and extremely free flowing. Detergent compositions like that of this example containing bentonite 9 as described, are found to be of significantly improved calc.ium ion bindin~ rates but more importantly, they leave less zeolite residue on laundry washed with them in an automatic washing machine, especially when such laundry is line dried, than do similar compositions containing less bentonite and with ~odium silica e in the spray dried hase beads. This difference is accentuat~d when the wash water is high in hardness, e.g., 200 pOp.m., as calcium carbonate, the wash water is cold, and a gentle agitation cycle is employedO

- 5~ -Manufacturing procedures, with variati~ns, such as are described in Example :L, may be followed and certain adjuvants may be omi~ted, as therein mentioned n Proportiorls of the various components may be varied ~10~, ~20% and ~30%, while still maintaining them within the range~ previously given, and workable crutcher mixes that result in the desired beads and detergent compositions will be obtainable. The crutcher mix solids contents may be varied over the range recited, e.g., to 45% and 65~, and yood mixing ancl spray drying are obtainable. Instead of using Xeolite 4A, Zeoli-tes X and Y may be substituted, as may be other types of Zeolite A.
While it is preferred to employ the hydrated Zeolite 4A of this example, various degrees of hydration o the zeolite are acceptable and in some instances nearly anhydrous crystalline 2eolites or amorphous zeolites may ba employed. Varying the amount of bentonite within the range given, to 10 and 17~, for example, still results in sueful products but those containing the larger proportions of bentonite ~ill usually be more effective in helping to prevent zeolite deposition on laundry.
The improvement noted in the low solubl~ silicate or non-silicate deterg~nt compositions of this in~ention depositing less residue on washed laundry is veri~ied by testing the describad produc~ agaiIlst a control product o~
essentially the same formula, with no bentoni~e present and con~aining about 8% of sodium silicate. In such evaluation a ~ 55 -Whirlpool Suds ~ave model washing machine is employed, with the washing periods being eight minutes at a gentle wash cycle. The detergent composition concentration is 0~06%, the wash water is of mixed calcium and magnesium hardness with a total of 200 p.p.m. hardness, as calcium carbonate, and the water temperature is ~4C~ Th~ items washe-1 are.
100% cotton; 100% polyester; 85~ acetate and 15~ nylon; an~
65% polyester and 35% cotton. The wash is observed wet and after line drying. No residue is observed in any such case.
When the control formula detergent compositiorl is tested, moderate residue is observed on all test specimens.
The results of -the practical residue test described above are verified by weighing residue deposited on a denim test material. In such test, the detergent 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 CaCO3) hardness water at 24~C. The weight of residue on the cloth is noted, and com-pared to that in a control test. By such testing -the percen-tage of residue, compared to the control, is about 75~ whichis considered to be a significant improvement.
The adhesion ~est, previously referred to t which measures tackiness of detergent products, is one in which lO
grams oE basé beads (or detergent compo~ition, in some cases) are placed evenly between two watch glasses, both of which are about 23 cm. in diameter, with a weigh~ of 500 grams on top of the upper watch glass (both watch glasses being concave side up). After standing about five minutes, the weight and top watch glass are removed and the bo-~tom watch glass is inverted, after which the product remaining stuck to such watch glass is weighed. The percentage adhesion is the number of grams of product xemaining on such wa~ch glass divided by 10 and multiplied by 100.
The flow index is that resulting from a flow test wherein the volumetric flow rates of base beads (and in some cases final product) and standardized Ottawa sand (-20 ~60, U.S. Siev~ Series sieve) are compared by measuring the times required for complete emptying of a 1.9 liter Mason jar through a 2.2 cm. diameter hole in a nozzle attached to the cap thereQf. The index is the time for the sand flow divided by the time for ~hetest product flow, expressed as a percentage.

EXAMPL~ 6 The experiment of Example 5 is repeated, on a reduced scale, without the polyacrylate being present in the crutcher mix. The throughput rate thrsugh the spray tower is appreciably diminished and the capability of the base beads for absorbing nonionic detergent is also less (or the product made is somewhat tackier if the same proportion of 89~3 nonionic detergent is applied). However, the crutcher mix does not freeze in the crutcher, the base beads can be manufactured by spray drying and the resulting detergent composition, although lower in nonionic detergent content, e.g., 17~ nonionic detergent, to maintain flowability and non-tacky properties, is still a useful product and of satisfactory fl-ow characteristics.

EX~MPLE 7 The procedure described in Example 5 is repeated, with 2% of sodium ~ilicate of Na2O:SiO2 ratio of 1:2.4 being added to the crutcher as a 47.5% solids aqueous solution.
The product made does not gel in the crutcher, in normal manufacturing procedures, but it is desirable to utilize magnesium sulfate and citric acid as processing aids to prevent gelation or freezing whan the holdup time i5 greater than normal. Also, the detergent composition made leaves more residue on washed laundry, which is more noticeabl~
when the colors of such laundry are dark.

The experiment of Example 5 i5 repeated with 5% of hydrous sodium silicate powder ~Bri-tesil) being post~added with the enzyme powder. Such post-added silicate does not appear to adver~ely affect zeolite deposition on washed ''353 laundry significantly and does aid in corrosion prevention with respect to aluminum washing machine parts, and in water soften~
ing and dete.ryent building.

The process of Example 5 is repeated Witil only water, zeolite, bentonite, sodium carbonate, sodium bicarbonate and sodium polyacrylate being present in ~he crutcher mix and in the base beads and with only nonionic de~ergent being post-added thereto. The product resulting is of satisfactory detersive properties but is not commercially acceptable for aes~hetic reasons because of the lack of perfume therein.
Also, it does not clean as well, due to the absence of enz~ne and does not have the bluing and brightening effects that the ultramarine blue and fluorescent material con~ribute to the other formulations.

Claims (27)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Free flowing, spray dried base beads for manufacture of a particulate built synthetic nonionic organic detergent product by application of nonionic detergent thereto, comprising by weight from about 15 to 30% of sodium carbonate, about 10 to 22% of sodium bicarbonate, about 10 to 50% of water softening aluminum silicate, and at least one material selected from about 1 to 20% of bentonite and about 0.05 to 2% of polyacrylate of molecular weight in the range of 1,000 to 5,000.

2. Beads according to claim 1 further comprising up to 18% of sodium silicate.

3. Beads according to claim 2 comprising up to 3% of sodium silicate and 1 to 20% of bentonite.

4. Beads according to claim 3, of a bulk density of 0.6 to 0.9 g./cc. and particle sizes in the range of No.
10 to 100, U.S. Sieve Series, wherein the aluminosilicate is a hydrated water, softening sodium zeolite containing from 15 to 25% by weight thereof of water of hydration and has an exchange capacity for calcium ions which is in the range of 200 to 400 milligram equivalents of calcium carbonate hard-ness per gram of anhydrous zeolite, the sodium silicate is of Na2O:SiO2 ratio in the range of 1:1.4 to 1:3 and the weight ratio of sodium carbonate : sodium bicarbonate is within the range of about 1 to 3.

5. Beads according to claim 4 comprising from 20 to 30% of sodium carbonate, 13 to 22% of sodium bicarbonate, 35 to 45% of hydrated zeolite, 0% of sodium silicate, 5 to 20% of bentonite and 1 to 15% of water, exclusive of the water of hydration of the zeolite, and in which the zeolite is Zeolite A, of ultimate mean particle sizes in the range of 3 to 12 microns, of a calcium ion exchange capacity of 250 to 350 mg; eq./g. and of a hardness depletion rate residual hardness less than 0.01 mg./1. per liter in ten minutes, the 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% concentration in water, and the weight ratio of sodium carbonate : sodium bicarbonate is within the range of 1 to 2.

6. Beads according to claim 5 which are of a bulk density of 0.6 to 0.8 g./cc., comprising 0.05 to 0.5%
of sodium polyacrylate of molecular weight in the range of 1,000 to 5,000 and wherein the bentonite is beneficiated Wyoming bentonite of swelling capacity in the range of 7 to 15 ml./g. and of viscosity in the range of 8 to 30 cp. at 6% concentration in water.

7. Beads according to claim 2 comprising 20 to 40% of water softening aluminum silicate, 4 to 12% of sodium silicate and 1 to 15% of bentonite.

8. Beads according to claim 7, of a bulk density of 0.6 to 0.9 g./cc. and particle sizes in the range of No.
10 to 100, U.S. Sieve Series, wherein the aluminosilicate is a hydrated water softening sodium zeolite containing from 15 to 25% by weight thereof of water of hydration and has an exchange capacity for calcium ions which is in the range of 200 to 400 milligram equivalents of calcium carbonate hard-ness per gram of anhydrous zeolite, the sodium silicate is of Na2O:SiO2 ratio in the range of 1:1.4 to 1:3 and the weight ratio of sodium carbonate : sodium bicarbonate is within the range of about 1 to 3.

9. Beads according to claim 2 comprising from 20 to 25% of sodium carbonate, 13 to 19% of sodium bicarbonate, 30 to 37% of hydrated zeolite, 5 to 8% of sodium silicate, 5 to 8% of bentonite and 4 to 10% of water, exclusive of the water of hydration of the zeolite, and in which the zeolite is Zeolite A, of ultimate mean particle sizes in the range of 3 to 12 microns, of a calcium ion exchange capacity of 250 to 350 mg. eq./g. and of a hardness depletion rate residual hardness less than 0.01 mg./l. in ten minutes, the sodium silicate is of Na2O:SiO2 ratio in the range of 1:2 to 1:2.4, the bentonite is a swelling clay having a swelling capacity, in water, of 3 to 15 ml./gram and a viscosity of 3 to 30 centipoises at 6% concentration in water, and the weight ratio of sodium carbonate : sodium bicarbonate is within the range of 1 to 2.

10. Beads according to claim 9 which are of a bulk density of 0.6 to 0.8 g./cc., comprising from 0.1 to 2%
of sodium polyacrylate of molecular weight in the range of 1,000 to 5,000, and wherein the bentonite is beneficiated Wyoming bentonite of swelling capacity in the range of 7 to 15 ml./g. and of viscosity in the range of 8 to 30 cp.
at 6% concentration in water.

11. Beads according to claim 2 comprising 20 to 40% of water softening calcium silicate, 4 to 18% of sodium silicate and 0.1 to 2% of polyacrylate of molecular weight in the range of 1,000 to 5,000.

12. Beads according to claim 11 of a bulk density of 0.5 to 0.8 g./cc. and particle sizes in the range of No.
10 to 100, U.S. Sieve Series, wherein the aluminum silicate is a hydrated water softening sodium zeolite containing from 15 to 25% by weight thereof of water of hydration and has an exchange capacity for calcium ions which is in the range of 200 to 400 milligram equivalents of calcium carbonate hard-ness per gram of anhydrous zeolite, the sodium silicate is of Na2O:SiO2 ratio in the range of 1:1.4 to 1:3 and the weight ratio of sodium carbonate : sodium bicarbonate is within the range of about 1 to 3.

13. Beads according to claim 12 comprising from 20 to 25% of sodium carbonate, 13 to 19% of sodium bicarbonate, 30 to 37% of hydrated zeolite, 7 to 15% of sodium silicate, 0.5 to 1.5% of sodium polyacrylate and 3 to 10% of water, exclusive of the water of hydration of the zeolite, and in which the zeolite is Zeolite A, of ultimate mean particle sizes in the range of 3 to 12 microns, of a calcium ion exchange capacity of 250 to 350 mg. eq./g. and of a hardness depletion rate residual hardness less than 0.01 mg./l. in ten minutes, the sodium silicate is of Na2O:SiO2 ratio in the range of 1:2 to 1:2.4, the polyacrylate is sodium poly-acrylate of molecular weight in the range of 1,000 to 3,000, and the weight ratio of sodium carbonate : sodium bicarbonate is within the range of 1 to 2.

14. A method of manufacturing base beads of claim 1 which comprises spray drying a crutcher mix containing 40 to 75% of solids, corresponding to those recited in such claim, in an aqueous medium, and during such spray drying decomposing a portion of the sodium bicarbonate present therein -to sodium carbonate.

15. A method according to claim 14 which comprises spray drying a crutcher mix containing 50 to 65% of solids corresponding to those recited in claim 6 in an aqueous medium, and during such spray drying decomposing a portion of the sodium bicarbonate present therein to sodium carbonate and thereby increasing the capacity of the resulting beads for absorbing nonionic detergent in liquid state due to the release of carbon dioxide and the presence of the polyacrylate.

16. A method according to claim 14 which comprises spray drying a crutcher mix containing 50 to 65% of solids corresponding to those recited in claim 10 in an aqueous medium, and during such spray drying decomposing a portion of the sodium bicarbonate present therein to sodium carbonate and increasing the capacity of the resulting beads for absorbing nonionic detergent in liquid state due to the presence of the polyacrylate.

17. A method according to claim 14 which comprises making a crutcher slurry of improved gelation and setting retarding characteristics comprising by weight from 40 to 70% of solids and 60 to 30% of water, of which solids content, on an 100% solids basis, about 10 to 25% is sodium carbonate, 15 to 30% is sodium bicarbonate, with the weight ratio of sodium carbonate : sodium bicarbonate being within the range of 0.5 to 2, 20 to 40% is water softening aluminosilicate, 5 to 18% is sodium silicate and 0.1 to 2% is polyacrylate of molecular weight in the range of 1,000 to 5,000, and spray drying such crutcher mix in a spray drying tower.

18. A detergent composition which comprises beads of claim 1 having absorbed in them a nonionic detergent so that the percentage of such nonionic detergent in the composi-tion is within the range of 8 to 30%

19. A detergent composition according to claim 18 wherein the nonionic detergent is a condensation product of 6 to 12 mols of ethylene oxide and a higher fatty alcohol of 12 to 16 carbon atoms, the proportion of such nonionic detergent in the composition is within the range of 15 to 22% and which detergent composition also comprises 0.5 to 3% of an enzyme.

20. A detergent composition according to claim 18 which comprises beads of claim 6 having absorbed in them a nonionic detergent so that the percentage of such nonionic detergent in the detergent composition is within the range of 8 to 25%.

21. A detergent composition according to claim 18 which comprises beads in accordance with claim 8 having absorbed in them a nonionic detergent so that the percentage of such nonionic detergent in the composition is within the range of 8 to 25%.

22. A detergent composition according to claim 21 wherein the nonionic detergent is a condensation produce of 6 to 12 moles of ethylene oxide and a higher fatty alcohol of 12 to 16 carbon atoms and which detergent composition also comprises from 0.5 to 3% of an enzyme.

23. A detergent composition according to claim 21 which comprises beads of claim 10 having absorbed in them a nonionic detergent so that the percentage of such nonionic detergent in the detergent composition is within the range of 8 to 25%.

24. A detergent composition according to claim 18 comprising by weight from 13 to 28% of sodium carbonate, 8 to 18% of sodium bicarbonate, 15 to 35% of water softening aluminum silicate, 3 to 14% of sodium silicate, 0.1 to 1.6%
of polyacrylate of a molecular weight in the range of 1,000 to 5,000, and 8 to 30% of a nonionic detergent.

25. A detergent composition according to claim 24 of a bulk density of 0.6 to 0.9 g./cc. and particle sizes in the range of No. 10 to 100, U.S. Sieve Series, wherein the aluminum silicate is hydrated Zeolite A containing from 15 to 25% by weight thereof of water of hydration, the sodium silicate is of Na2O:SiO2 ratio in the range of 1:1.4 to 1:3, the polyacrylate is sodium polyacrylate of molecular weight in the range of 1,000 to 3,000, the weight ratio of sodium carbonate : sodium bicarbonate is within the range of 1 to 2, the nonionic detergent is a condensation product of 5 to 12 moles of ethylene oxide and a mole of higher fatty alcohol of 12 to 16 carbon atoms and which composition contains water, exclusive of the water of hydration of the zeolite, and in which composition the percentages of components are within the ranges of 16 to 21% of sodium carbonate, 10 to 15% of sodium bicarbonate, 22 to 32% of hydrated zeolite, 8 to 13% of sodium silicate, 0.5 to 1.5% of sodium poly-acrylate, 3 to 6% of moisture and 10 to 22% of nonionic detergent.

26. A crutcher slurry of improved miscibility and pump-ability, suitable for the manufacture of base beads of claim l by the method of spray drying a crutcher slurry containing 40 to 75% of solids, corresponding to those recited in such claim, in an aqueous medium, and during such spray drying decomposing a portion of the sodium bicarbonate present therein to sodium carbonate, said crutcher slurry comprising by weight from 40 to 70% of solids and 60 to 30% of water, of which solids content, on a 100% solids basis, about 10 to 25% is sodium carbonate, 15 to 30% is sodium bicarbonate, with the weight ratio of sodium bicarbonate : sodium carbonate being within the range of 0.5 to 2, 20 to 40% is water softening aluminum silicate, 4 to 18% is sodium silicate and 0.1 to 2% is polyacrylate of molecular weight in the range of 1,000 to 5,000.

27. A crutcher slurry according to claim 26 which comprises, on an anhydrous basis, 1.5 to 2.5% of magnesium sulfate, 0.2 to 0.5% of sodium citrate, 0.2 to 0.4% of ultramarine blue, 1.5 to 3% of fluorescent brightening agent and 0.5 to 1.5% of sodium polyacrylate of molecular weight in the range of 1,000 to 3,000.