CA1036456A - Detergent composition - Google Patents

Abstract

DETERGENT COMPOSITION

ABSTRACT OF THE DISCLOSURE
A process for the preparation of a deter-gent composition in the form of free flowing beads comprises spray drying an aqueous slurry containing anionic detergent and water-insoluble aluminum silicate molecular sieve and blending the spray dried composition with a liquid or tacky nonionic detergent, and the compositions produced by the process.

Description

1~36~S6 DETERGENT COMPOSITION

An aspect of this invention relates to home washing of clothes, using automatic washing machines and using a wash water containing dispersed therein a finely divided water-insoluble alkali metal aluminum ~ilicate molecular sieve and an anionic detergent, preferably with an a~kali metal silicate and a nonionic detergent, too. It has been found that combinations of a molecular sieve and water-soluble builders, with relatively large amounts of sodium silicate, give especially good results. One particularly suitable added builder salt for use in such compositions is trisodium 2-oxa-1,1,3-propane tricarboxylate, the e~fect of --which, in combination with the molecular sieve and sodium silicate, is found to exceed that of penta-sodlum tripolyphosphate. Thus, a particular preferred composition ~e.g., for use in a washing machine containing 150 ppm hard water at 0.15%
concentration) contains 10% tridecylbenzenesulfonate, 20~ molecular sieve, 15% alkali metal silicate (Me20:SiO2 ratio of 1:2.35), 15% alkali metal

2-oxa-1,1,3-propane tricarboxylate, 2% nonionic detergent, 0.5% sodium carboxymethylcellulose and the balance sodium ~ulfate and water. In other embodiments, where phosphate and NTA are unobjec-tionable, the preferred trisodium 1~P3645~i 2-oxa-1,1,3-propane tricarboxylate (TO~T) is replaced wholly or in part (ë.g., 1/3 or 1/2 thereof) by pentasodium tripolyphosphate ~TPP) or trisodium nitrilotriacetate (NTA), with the latter giving particularly good results.
It has been found that an increase in the amount of anionic detergent permits a corresponding decrease in the amount of sodium silicate.
For instance an increase from 10% to 15% gives a marked improvement even when the sodium silicate proportion is correspondingly reduced from 20% to 15%, with unchanged proportions of molecular sieve (e.g., 30%) and of the other constituents (e.g., 2% nonionic detergent, 0.5% sodium carboxymethyl-cellulose and 35% sodium sulfate).
Instead of the alkylbenzenesulfonate an olefin sulfonate detergent, e.g., of 15 to 18 carbon atoms, or other suitable anionic detergent may be used, preferably as a partial replacement only.
According to the present invention, there is provided a detergent composition in the form of free-10wing hollow beads having a maisture content of 3~ to 15~ by wcight which comprises spray dried beads of a detergent composition corltalning at least about 5% by weight of a water-soluble, synthctic, organ~c~ anionic dotorgent and about 15 to 45% by weight of finely dlvldod, wntor-insoluble sodium or potassium aluminum silicate molecular siovc, having the capacity to remove calcium ions from water, the proportion of said sieve being calculated on an anhydrous basis and being greater than the proportion of anionic detergent, having a post-added liquid or tacky nonionic detergent sorbed thereon, the proportion of sorbed nonionic detergent being at least 1% by weight and the total proportion of nonionic detergent being~less than 2/3 of the weight of said molecular sieve.
In another aspect, the invention provides a process for preparing a detergent composition in the form of free-flowing hollow beads which comprises forming an aqueous slurry of a detergent composition containing at least about 5% by weight of a water-soluble synthetic, organic, anionic detergent and about 15 to ~5% by weight of a finely divided, water-insoluble sodium or potassium aluminum silicate molecular sieve having the capacity to ~ - 2 -.

~ ~3~i6 remove calcium ion from water, the proportion of said sieve being calculated on an anhydrous basis and being greater than the proportion of anionic detergent, and the balance being a water-soluble detergent builder salt selected from the group consisting of inorganic and organic builder salts;
spray drying said aqueous detergent composition to form free flowing hollow beads having a moisture content of 3% to 15% by weight; and then blending said beads with a liquid or tacky nonionic detergent to form free flowing beads, the amount of nonionic detergent blended therewith being at least 1% by weight and the total proportion of said nonionic detergent being less than 2/3 of the weight of said molecular sieve.
In general, in the compositions oftthis invention the proportion of sodium silicate is at least about half the proportion of molecular sieve tbased on dry weight) and at least about equal to or more than the proportion of organic detergent. It is also found that the use of such higher proportions of sodium silicate, in accordance with this invention, gives wash wat~rs in which the - 2a -~ll)364S~
finely divided molecular sieve is more stably suspended,and improves the deflocculation of particulate soils.
It is conventional when using household automatic washing machines of the type employed in the United States to employ detergent compositions at a concentration of about 0.15~ in the wash water. For use in such concentration the propor-tion of sodium silicate in the formulations of this invention is in the range of about 12 to 25~, preferably about 15 to 20% and the proportion of molecular sieve is in the range of about 15 to 35%, preferably about 20 to 30%, while the proportion of anionic detergent is preferably in the range of about 10 to 20%, more preferably about 10 to 15%.
However, the weights of various components may be such that the synthetic organic anionic detergent tincluding soap~) may be at least about 5%, the molecular sieve may be about 15 to 45% (being more than that o the anionic detergent), the silicate content may be almost up to that of the molecular sieve, the TOPT may be 1/2 to twice the silicate ` and the nonionic may be up to 2/3 the molecular sieve weight, while still making a free flowing product.
One particularly good detergent formula-: tion contains about 10% sodium linear alkylbenzene-sulfonate, 2% nonionic detergent, 1% soap, 24%

~L~36456 molecular sieve, 15~ sodium silicate, about 1/2 to 1% sodium carboxymethyl cellulose and the balance sodium sulfate and water (together with small ! amount~ of optical brighteners and conventional minor adjuvants). Another detergent composition of I - superior performance i~ otherwise similar but j contains 20% sodium silicate and 30% molecular sieve. In a preferred form the weight ratio of sodium silicate to molecular sieve (on an anhydrous basis, as usual) is in the range of about 0.5:1 to 0.8:1, more preferably about 3:5 to 3:4. The silicate,preferably sodium silicate, has an Na2O:SiO2 ratio o about 1:2 to 1:3.2, preferably 1:2.0 to 1:2.4, e.g., 1:2.35.
lS The following examples are given to illustrate this invention further~ In this applica-tion all proportions are by weigh~ unless otherwise indiaated.

~.~36456 In the tabulated Examples below, the com-positions are added to the water (e.g., water of 150 ppm hardness having a Ca:Mg ionic ratio of

3:2) used for washing clothes in amount of 1.5 grams of the compo~ition per liter of water. A
suitable washing temperature employed i5, for example, about 50C; and the period for agitated washing before spinning (i.e., before centrifuging to remove the wash water, prior to rinsing) is about 10 minutes. A standard wash load, such as 3.S kilograms, of mixed laundry (cottons, poly-esters and blends) are used and washings are for the usual times, e.g., 15 minutes of a 30 minute lS machine aycle.

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Notes: 1036~56 (1) Sodium linear alkylbenzenesulfonate having an average of about 13 tspecificaily 12.8) carbon a~oms in the alkyl chain. The chain length distri-bution (by weight) is às follows:
No. of carbon 10 11 12 13 14 atoms in chain:
Percentage : 3.2 11.1 15.8 38.4 31.5 j The distribution (by weight) of the position, on the carbon chain, of the aromatic ring is as follows:
Position on 2 3 4 5 6 and 7 carbon chain:
Percentage : 16.8 14.3 17.2 26.1 25.6 (2) Sodium olefin sulfonate made from an olefin mixture containing 78% alpha~olefins, 7-8% internal olefins, 14-15% olefins having a pendent =CH2 group (i.e., having a vinylidene group) and 0.1~ of parafins, which mixture contains 1.7% C12 oleins, 6S% C14 olefin , 33.2~ C16 olefins and 0.1~ C18 olefins. The reaction is carried out in conventional manner: the olefin is sulfonated with S03 highly diluted with alr, using slightly over 1 mol of S03 per mol of olefin, the resulting acid mix is made alkaline with excess aqueous NaO~, thus converting alkenyl sulfonic acids, formed during sulfonation, to the corresponding sodium salts, and the resulting alkaline mixture is heated at elevated ~ temperature (e.g., 170C ) at superatmospheric pressure to convert sultones, formed during the iL03645~;
sulfonation, to the corresponding sodium hydroxy-alkane sulfonates and alkenyl sulfonates.
(3) Type 4A molecular sieve containing 21~
moisture (proportions of molecular sieve in the foregoing examples are on an anhydrous basis, i.e., in Example 1 the proportion of moisture-containing molecular sieve actually added is 38.0%), having a mean particle diameter of 6.4 microns. All the particles are less than ~8.7 microns in diameter, 98~ are less than 14~4 microns, 94% le~s than 11.0 microns, 69% less than 7.6 microns and 15~ less than 4.1 microns. The X-ray diffraction peaks of the molecular sieve are as follows:

~36~5~

er o o CO
o 1~

~o o ~D

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N
,~ ~
~ ~ CO CO
r~ ~r co 1` co u~ o a~
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r~
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,~ o H tJ~ H
H ~C H

In ~36~56

(4) Na2O:SiO2 ratio of ~f 1:2.35, added as an aqueous solution.

(5) Pentasodium tripolyphosphate.

(6) Triso~ium nitrilotriacetate (added as the s monohydrate, but proportions given are on an anhydrous basis).

(7) "Neodol 45-11", reaction product of 11 mols of ethylene oxide and 1 mol of a mixture of C14 and C15 ~traight chain, normal primary alXanols, said mixture having an average of about 14-15 (e.g., 14.5) carbon atoms. (This may be added in the crutcher or, in a preferred embodiment of the invention may be post-sprayed onto the beads made from the rest of the formulation or may be added partly in the crutcher and partly after spray drylng or other formulation of the rest of the composition).
~8) ~Sodium carboxyme~hylcellulose, of conventional detergent grade.
~he foregoi.ng compo~ltions are formed into hollow spheres or beads by spray drying. In preparing a mixture for spray drying one blends an aqueous slurry of the alkylbenzenesulfonate or other detergent with an aqueous sodium silicate, adds optical brighteners, sodium carboxymethyl-* TRADE~IARK

~3645~
cellulose, sodium sulfate, nonionic detergent, soap, and the molecular sieve (containing 18-27~
water, e.g., 20%),all while stirring in a conventional manner in a crutcher. The moisture content of the crutcher mix is about 50~ but in variations o~ the method may be from 35 to 70%. The mixture, at an elevated temperature of 50 to 90C, e.g., 65C,is then sprayed into heated air (e.g., countercurrently in a spray tower into air having a temperature of 100C to 400C, e.g., 230C) under such conditions that the resulting hollow beads have a moisture content of about 3 to 15%, preferably 4 to 10%.
Onto the surfaces o~ the hollow beads made are sprayed an additional 2%, in each case, of the same nonionic detergent in molten ~orm, while the bead~ are tumbled. All the products made, before and after addition of this nonionic, are good heavy duty detergents as tested in home washing machines on mixed laundry, using 150 ppm hardness water, but the compositions containing more of the nonionic are generally better.
The preferred molecular sieves are Type 4A molecular ~ieves. The sodium (and potas-sium) forms of Type A sieves are well known. See, for instance, U.S. patent 2,882,243 which describes them as zeolite A. The water-containing hydrated form of the molecular sieve is preferably the form incorporated into the detergent composition. The 1].

~36~;6 molecular sieves are preferably of fine particle size, such as cubic crystals having mean particle diameters below 8 microns, e.g., 1/2, 1, 2, 4 or 6 microns. The manufacture of such crystals is well known in the art. Preferably the crystals of hydrated zeolite A that are formed in the crystal-lization medium (such as a hydrous amorphous sodium aluminosilicate gel) are used without the high temperature dehydration (calcining, e.g., to 2-3%
water content) that is normally practiced in preparing such crystals for use as catalysts te.g., cracking catalysts); that is in the preferred practice of the invention the molecular sieves are used in completely or almo~t completely undehydrated condition, 9uch as i8 obtained by filtering off the crystals, washing them with wster and drying them in air 90 that their water content is about 20%.
It has Also been found that the efectiveness of a moleoular sieve that has been calcined may be signi~icantly increased by soaking it in water (e.g., deionized water at room temperature) and then drying in air at, say, room temperature or 110C, giving a product having a water content of about 20%. In general, it is preferable to use a molecular sieve whose rate of calcium ion uptake is such that when 375 ppm (anhydrous basis) of the molecular sieve are placed in water at 45C
containing 40 ppm of dissolved calcium ion,while ~(~3~4S6 vigorously stirring, the dissolved calcium ion content of the water is reduced to below about 8 ppm, preferably below 3 ppm, within 5 minutes.
More preferably the rate of calcium ion uptake is such that an appreciable effect is also observed ; within 2 minutes, the dissolvad calcium ion content at that time being preferably less than 12 ppm, most preferably less than 3 ppm.
In the foregoing test for rate uptake of calcium ion, the water is deionized water in which calcium chloride has been dissolved (i.e., 110 ppm of CaC12 to provide 40 ppm of Ca ion). The stirring may be effected in a 250 ml beaker with a glass-encased magnet as the s~irring element (the beaker being placed, for instance~ on a conventional Corning hot plate type of magnetic stirring motor, set ~t moderate speed). Timing is started as soon as the molecular sieve is added to the water. At ; predetermined times ~e.g., 2 minutes and 5 minutes) a sample o~ the water is removed and the dispersed mo~ecular sieve particles in that sample are removed immediately by vacuum filtration (a procedure that takes up to about 10 seconds overall). The filtered water sample can then be analyz~d for its calcium content (as by a standard EDTA titration method).
The compositions may contain sodium carbonate to provide additional alkalinity or as a ! - 13 ~Q36gL5~
filler (in place of sodium sulfate) or as a carrier for liquid, pasty or soft solid ingredients (or for ; any combination of these or other purposes) in such compositions. It is known that detergent composi-tions containing sodium carbonate tend to form insoluble calcium carbonate in the wash water which can lead to undesirable stiffening ("boardiness") of the washed fabrics due to interaction of the hard water and the sodium carbonate. This tendency is greatly inhibited or substantially eliminated in compositions containing the molecular sieve. Such composi~ions,designed for use at concentrations of about 0.15~ in the wash water,may be like those of Examples 1-7 but may also contain 10, 15, 20, 25 or 30~ or more o sodium carbonate (i.e., corres-ponding to a carbonate content of about 80, 130, 170, 210 or 260 ppm or more, in the wash water).
! All, or part of the sodium carbonate of the composi-tion may be pre-blended as a dry powder with the liquid, pasty or waxy non-ionic detergent (such as molten Neodol 45-11) to form free flowing particles which may then be post-added to the free-flowing spray-dried beads of the remainder of the detergent composition but it i9 often preferred to blend (e.g., spray) the same nonionic detergent, in liquid form, with the spray dried or otherwise hollowed beads while tumbling them. Proportions of 2, 4 or 6~ of the nonionic can be post-added to 1~36~56 the spray-dried bead~ made from a detergent crutcher mixture containing sodium carbonate, which produces a composition having good flow characteristics despite its rather high content of nonionic deter-gent. It is found that the formation of insoluble calcium carbonate in solutions containing sodium carbonate is inhibited by the presence of the molecular sieve and it is thus also within the broader scope of thi~ aspect of the invention (relating to the use of sodium carbonate) to reduce the amount of sodium silicate when carbonate is employed. The proportion of sodium carbonate present in the product will generally be 1 eæB than ; the proportion of molecular ~ieve.
In the embodiment of the invention in which sodium carbonate powder i9 pre-blended with the nonionic detergent, after which the mix is blended with the re~t of`the product, the weight ratlo of the nonionic detergent to sodium carbonate may be up to about 1:1, such as about 0.1:1, 0.2:1, 0.3:1, 0.5:1, 0.7:1 and 0.9:1. The ~odium carbonate may be substantlally anhydrous and may be in the form of a fine powder of about 2 to 10 or 20 microns mean particle diameter which may be simply mixed mechanically with the nonionic detergent which coats and/or agglomerates the sodium carbonate particles (e.g., to form agglomerates which are of about the same size as the spray-dried beads).

~364~6 The use of sodium carbonate is illustrated in the following Examples 8-28:

Examples 1-7 are repeated except that the formulations contain 20% sodium carbonate (added in anhdrous form in place of part of the sodium sulfate). The composition~ are spray dried (~rom an aqueous mixture of all the ingredients thereof) to form free flowing hollow beads which may then be blended with the nonionic detergent as described.
The products are good heavy duty detergentSwith free 10wing characteristics.

; Examples 8-14 are repeated except that 19 the additional nonionic detergent is included in the ~rutcher instead of being post-sprayed onto the ~pray~dried bead~. Some of the nonionic plumes ~is lost out the spray tower top) during drying and the products are less effective detergents due to such losses.
.

Examples 1-7 are repeated, with the compo~itions being spray-dried from an aqueous , mixture o all the ingredients thereof to form ree flowing hollow beads but not having nonionic detergent post-blended with them. 6 Parts o - ~364S6 anhydrous ~sodium carbonate powder and 5 parts of the same nonionic detergent are mechanically blended to form a free flowing granular mixture of agglom-erated particles and the res~ilting granules are then added to the spray-dried beads in amounts to bring the nonionic detergent contents of the resultin~ products to about 5%, after which the products may be blended with an additional 2% of the same nonionic detergent. (The word "blending"
includes post-spraying and tumbling).
It has also been found, unexpectedly, that the free flowing spray-dried beads of deter-gent compositions containing the molecular sieves can carry higher loadings of oversprayed nonionic detcrgcnt than can powder blends of detergent components, although normally lower loadings will bc cmployod. This is illus*rated in Example 29 below. Thus 9uch compositions may contain about 15 to ~5%~ (e.g.~ about 20, 30 or 35%) of the molecular siovc togethcr with an anionic detergent, usually present in amo~mt which is at least 5% (such as 10 or 15%) but is generally less than the amount of molecular sieve. The proportion of nonionic detergent in the composition may be low, say 2%, or high (such as the 20% in Example 29, or more) or intermediate (e.g., 3, 4, 5, 8 or 10%); generally it will be less than about two-thirds of the proportion of molecular sieve. It will be appre-ciated that the post-addition of the nonionic 16J36~56 ~, detergent makes it po~sible to carry out the spray drying with little or no nonionic detergent presant (and therefore little or no "pluming" in the exhaust from the spray drying tower). It is also within the broader scope of this aspect of the invention to past-add, similarly, other tacky materials (such as wash-active oily or waxy addi-tives) in place of all or part of the nonionic detergent.

1, 10 EXAMPLE 29 ., .
(a) A detergent composition of the following approximate composition is made by spray drying the named ingredients, from an ac,~ueous ~lurry thereof:
10~ ~odium linear alkylbenzenesulfonate (as in Example 1); 2~ nonionic detergent (Alfonic 1618-65)7 1~ soap (~odium 90ap of 80% tallow atty acids and 20~ coconut oil fatty acids); 33~ molecular sieve o Example 1; 7~ sodium silicate (Na20:SiO2 ratlo of 1:2.4)~ 0.$4 ~odium carboxymethylcellulose;
4g (apparent) water; 0.8~ of a mixture of optical brighteners; and the balance being sodium sulfate.
The sodium silicate is supplied to the mixture, as an aqueous slurry; the molecular sieve is supplied to the mixture in hydrated form (i.e., as a powder containing about 20% moisture). The apparent water content of 4~ is that measured by adding hydrocarbon solvent (Skelly V) and distilling off the water at 116-143C; the total water content is about 8% when ~)36~S~
measured with a DuPon~ moisture analyzer, uRing a dehydrating temperature of 160C or 200C.
The re~ulting hollow spray dried beads are found to have generally spherical form; when viewed with the electron scanning microscope the particles of molecular sieve are seen to be concen-trated internally, i.e., near the internal walls of the beads.
11 Grams of molten nonionic detergent (Neodol 45-11) are poured gradually onto 50 grams of the 3pray dried bead~ at room temperature while stirring the mixture. The resu ting product is a free flowing granular mixture that retains its granular form when a mass of the particles i9 between one' B ingers. (In contrast, when the same amount of molten nonionic detergent is added to conventlonal spray-dried detergent beads containing abouk 33~ pentasodium tripolyphosphate in place o the approximately 32% of molecular sieve, the resultlng produat is caky and forms a coherent lump when pressed between one's fingeri.) The granular product contains (by calculation) about 8% sodium alkylbenzenesulfonate, about 20% nonionic detergent I and about 27~ molecular sieve,and is a good detergent.
`~ 25 A similar effective product is made when the ; corresponding potassium form of the molecular sieve is used instead of part or all of the sodium form.
A similar change is also made in the silicate ; ~36~S~i cation without difficulty.
(b) Example 29(a) is repeated except that the proportion of molecular sieve is decreased to about 25~, the proportion of sodium silicate is increased to about 15%, and the proportion of sodium carboxymethyl cellulos~ is increased to about 1%.
The product resulting from the pouring of 11 grams of molten nonionic detergent on*o 50 gr~ms of spray dried beads i~ ~omewhat tacky or caky and not as free-flowing as desired but when the proportion of added molten nonionic detergent is decreased to 5 grams (to SO grams of spray dried beads) the product is a ree flowing granular detergent composition.
~c) Example 29(a) is repeated except that the proportion of molecular sieve is decreased to about 30%, the proportion o~ alkylbenzene sulfonate i~ increased to about 15~, the proportlon o sodium 8iliaate i~ increased to about 20~ and the propor-tion of sodium carboxymethyl cellulose is increased to about 1%, while the proportion of sodium -~ulfate is correspondingly decreased. A free flowing granular detergent product is obtained.
The bulk specific gravities of the spray-dried beads used in Examples 29(a),29~)and 29(c) are about 0.37, 0.33 and 0.31,respectively.
As is conventional in the art, the 1~36~56 spray-dried detergent compo3itions used in this invention will generally be made up of beads of such size that substantially all ~by weight) passes through a 6 mesh screen (a~l screen sizes given herein are U.S. Standard) and substantially all (by weight) is retained on a 200 mesh screen (i.e., ranging from about 0.75 mm, to about 3.3 mm in particle size). Preferably the particle si~e distribution can range from about all through a 14 mesh screen to about all retained on a 100 mesh screen (i.e., ranging in particle size from 0.14 mm to 1.5 mm). Another particularly useful size distribution is not more than about 30% retained on a 16 mesh screen and not more than about 7~ through a 100 mesh screen. U~ually the major portion of the spray-dried product i9 made up of beads having partiale diameters below 1 mm, preferab~y below 0.9 mm. The bulk specific gravity of the spray-dried product is usually below about 0.8, more generally below about 0.6, preferably below about 0.6 and still more preferably at least about 0.3 and in the range of about 0.3 to 0.4.
The nonionic surfactants having the most desirable detergency properties are usually viscous liquids or unctuous pa~ty or tacky ~olids at room temperature, ~uch as those having melting points below about 40C. and having significant volatility under commercial spray drying conditions. Typical `- 1(1136~56 nonionic detergent~ are polyoxyethylene and poly-oxypropylene derivatives that are usually prepared by the addition or ethylene oxide and/or propylene oxide to compounds having a hydrophobic hydro-carbon chain and containing one or more active hydrogen atoms, such a~ alkylphenols, fatty alcohols, fatty acids, fatty mercaptans, fatty amines, fatty amides and polyols, e.g., fatty alcohols having an

8 to 20, typically 10 to 18 carbon atoms alkyl chain and ethoxylated with an average of about 3 to 20, typically 5 to 15 ethylene oxide units.
Commercially available ethoxamers falling into this category are NEODOL 45-11, which is an ethoxylation product ~having an average of 11 ethylene oxide units) of a 14 to 15 carbon straight chain fatty alcohol (Shell Chemical Company); NEODOL 25-7, a 12 to 15 carbon chaln fatty alcohol ethoxylated with an average o~ about 7 ethylene oxlde units; ALFONIC*
1618-65, which is a 16 to 18 carbon alkanol ethoxy-lated with an avera~e o~ 10 to 11 ethylene oxide units tCont~nental Oil Company); and Pluronlc ~-26, having a 12 to 13 carbon alcohol etherified with ethylene oxide and propylene oxide tBASF-Wyandotte Chemical Company).
2S The reason for the superior ability of the spray-dried beads made with the molecular sieves to carry otherwise tackifying materials such as nonionic surfactants is not clearly understood.

* TRADE MAR~S

~ 22 A~ ~

~364~6 It may be due to the structure of the bead, or to an increased internal surface area owing to the presence of the small insoluble particles of molecular sieve; see the interior of the broken bead illustrated in FIG. 1 (which is a photomicrograph made with a scanning electron microscope, the scale being indicated next to the photomicrograph, of a spray-dried bead prior to the post-addition of nonionic detergent). When viewed with an ordinar~ light mlcroscope the walls of the beads appear to become less opaque after treatment with the nonionic detergent, which indicates that the latter has been sorbed into the bead material. It also appears that the presence of the ~inely divided insoluble solid particles, particularly when they are distributed ~as a porous, bonded aggregate) through much of the interior of the bead, provides beads which are stronger or le~ likely to de~orm under pre~sure and therefore have lesser tendencles to aggregate together or to interfere wlth flow. It i~ there-fore within the broader scope of this aspect of the invention to replace a part of the molecular sieve by other water-insoluble solid particles, prefer-ably of similar sizes, shapes and characteristics, to obtain similar free flowing and effective heavy duty detergents.
As indicated in Examples 1-7, for instance, the anionic detergent may be an alkylbenzenesulfonate -3L~36~
or an olefin sulfonate. In the alkylbenzene-sulfonate the number of carbons in the alkyl group may be, for instance, in the range of about 10 to 16; preferably the alkyl i9 a straight chain radical of an average length of about ll to 13 or 14 carbon atoms. Preferably, the alkylbenzene-sulfonate has a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50~) of 2- (or lower) phenyl isomers;
in other terminology, the benzene ring is prefer-ably attached in large part at the 3 or higher (e.g., 4, 5, 6 or 7) position of the alkyl group and the content of isomers in which the benzene ring i9 attached at the 2 or l position is corres-pondingly low. One suitable type of suoh detergent i8 described in U.S. Patent 3,320,174 to Rubinfeld.
Olefin sulfonate detergents are well known ln the art. Generally they contain long chain alken yl sulfonate~ or long chain hydroxy-alkane sulfonates ~with the OH being on a caxbon atom whlch i8 not directly attached to the carbon atom bearing the -SO3 group). More usually, the olefin sulfonate detergent comprises a mixture of these two types of compounds in varying amounts, often together with long chain disulfonates or sulfate-sulfonates. Such olefin sulfonates are descxibed in many patent~, such a~ U.S. patents No's. 2,061,618; 3,409,637; 3,332,880; 3,420,875;
3,428,654; 3,506,580; British patent No.

_ 24 lQ36~S~;
1,139,158; and in the article by Baumann et al. in Fette-Seifen-Anstrichmittel,Vol. 72,No. 4, pp.
24i-253 (1970). All the above-mentioned disclosures are incorporated herein by reference. As indicated in these patents and the published literature, the olefin ~ulfonates may be made from straight chain alpha-olefins, internal olefins, olefins in which the unsaturation is in a vinylidene side chain (e.g., dimers of alpha-olafins), etc., or more usually, from mixtures of such compounds, with the alpha-olefin normally being the major constituent.
The sulfonation i8 usually carried out with ~ulfur trioxide under low partial pressure, e.g., S03 highly diluted with inert gas such as air, nitrogen or S03 under vacuum. This reaction generally yields an alkenyl sulfonlc acid, often together with a sultone7 the resulting aci~ic material is generally then made alkaline and i9 treated to open the sultone ring to ~orm hydroxyalkane sulfonate and alkenyl sul~onate. The number of carbon atoms in the olefin is u~ually within the range of 10 to ; 35, more commonly 12 to 20, e.g., a mixture principally of C12, C14 and C16 having an average of about 14 carbon atoms or a mixture principally of C14, C16 and C18 having an average of about 16 carbon atoms. The preferred olefin sulfonates are sodium salts but it is within the broader scope of the invention to use other water-soluble salts such -as ammonium or potassium salts thereof.
The anionic detergent may be a paraffin sulfonate, e.g., of 10 to 20 carbon atoms; these may be the primary paraffin sulfonates made by reacting long chain alpha-olefins and bisulfites (e.g., sodium bisulfite) or paraffin sulfonates having the sulfonate groups di3tributed alcng the paraffin chain, such as the products made by reacting a long chain paraffin with sulfur dioxide and oxygen under ultraviolet light, followed by neutralization with NaOH or other suitable base (as in U.S. Patents 2,503,280; 2,507,088; 3,260,741;
3,372,188; and German Patent 735,096).
Other anionic detergents are water-soluble soaps of, or instanca,h~gherfatty acids ; such as lauric, myristic, stearic, oleic, elaidic, iso~tearic, palmitic, undecylenic, tridecylenic, pentadecylenic, 2-lower alkyl higher alkanoic (such as 2-methyl tridecanoic, 2-methyl pentadecanoic or 2-methyl heptadecanoic) or other saturated or unsaturated atty acid of 11 to 20 carbon atoms~
Soaps o dicarboxylic acids may also be used, such as the soaps of dimerized linoleic acid. Soaps o such other higher molecular weight acids such as resin or tall oil acids, e.g., abietic acid, may also be employed. Specific examples of suitable soaps are the sodium soaps of mixture~ of tallow fatty acids and coconut oil fatty acids (e.g., 3~1 and 4:1 ratios). Soaps may also be used in 645~
small amounts as foam-decreasing agents.
Other anionic detergents are sulfates of higher alcohols, such a~ sodium lauryl sulfate, ~odium tallow alcohol sulfate, Turkey Red Oil or other sulfated oils, or sulfates of mono- or diglycerides of fatty acids (e.g., stearic mono-glyceride monosulfate), alkyl poly(ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having 1 to 5 ethenoxy groups per molecule);
lauryl or other higher alkyl glyceryl ether sulfonates; and aromatic poly(ethenoxy) ether sulfates ~uch as the ~ulfates of the condensation produats of ethylene oxide and nonyl phenol (usually having 1 to 20 oxyethylene groups per molecule, preferably 2-12).
The ether sul~ate may also be one having a lower alkoxy ~e.g., methoxy) substitutent on a carbon clo~e to that carrying the sulfate group, such as a monomethyl ether monosulfate of a long chain vicinal glycol (e.g., a mixture of vicinal alkane-diols o~ 16 to 17, 18 or 20 carbon atoms in a ~traight chain).
Other anionic detergents include also the acyl sarcosinates (e.g., sodium lauroyl sarcosinate) the acyl e~ters (e.g., oleic acid ester) of i80-thionates, and acyl N-methyl taurides (e.g., potassium N-methyl lauroyl- or oleyl tauride).
Another type of anionic detergent i9 an alkyl ~ 31~45~;
phenol disulfonate such as one having an alkyl group having some 12 to 25 carbon atoms, preferabl~
a linear alkyl of about 16 to 22 carbon atoms, which may be made by sulfonating the corresponding alkyl phenol to produce a product containing in excess of 1.~, preferably about 1.8 (e.g., 1.8 to 1.9 or l.9S) So3H groups per alkyl phenol molecule.
The disulfonate may be one whose phenolic hydroxyl group is blocked, as by etherification or e~terification. Thus, the ~ of the phenolic OH
may be replaced by an alkyl ~e.g., ethyl) or hydroxyalkoxyalkyl [e.g., a -(C-~2CH20)XH group in which x is one or more, such as 3, 6 or 10, and the resulting alcoholic ~H may be esterified to form a sulateJ.
Most commonly the anionic detergents are employad as ~odium salts but other alkali metal salts, or ammonium or even alkaline earth metal ~c.g., magnesium salts) may be used. Mixtures o ~0 ~arious anionic detergent~, e.g., a mixture o~ a sodium alkylbenzenasulfonate and a sodium ole~in sulfonate, may be employed. Any of the described anionic detergents may be ~ubstituted for the anionics in the Examples to produce useful heavy duty detergents.
The composition preferably also contains a fluorescent brightener in small amount. Such brightenexs are well known. They may be coumarin types, as illustrated in U.S. patents 2,590,485;

~36~56 2,600,375; 2,610,152; 2,647,132; 2,647,133;
2,791,564; and 2,882,186; triazolyl stilbene types, as illustrated in U.S. phtents 2,668,777; 2,684,966;
2,713,057; 2,784,183; 2,784,197; 2,817,665;
2,907,760; 2,927,866; and 2,993,892; stilbene cyanuric types, as illustrated in U.S. patents 2,473,475; 2,526,668; 2~595,030; 2,618,636;
2,658,064; 2,658,065; 2,660,578; 2,666,052;
2,694,064; and 2,840 F 557; acylamino stilbene types, as illu~trated in U.S. patents 2,084,413;
2,468,431; 2,521,665; 2,528,323; 2,581,057;
2,623,064; 2,674,604; and 2,676,982; or miscel-laneous types, 3uch as are shown in U.S. patents 2,911,415 and 3,031,460. The amount of brightener employed may be, for instance, in the range of about 1/20~ to 1%, e.g., 1/10% to 1/2%. A suitable combination of brighteners in¢ludes (a) a naph-thotriazola stilbene sulfonate brightaner, sodium 2-~ul~o-4-t2-naphtho-1,2-triazolyl) stilbene, (b) another ~tilbene brightener, bi~-tanilino diethanol~
amino triazinyl) stilbene disulfonic acid, ~c) another stilbene brightener, ~odium bis-(anilino morpholino triazinyl) stilbene disulfonate and (d) an oxazole brightener, havinq a l-phenyl 2-benzoxazole ethylene structure, 2-styryl naphtha [1, 2 d]-oxazole, in the relative proportions, a:b:c:d, of about 1:1:3:1.2.
Other ingredients which may be included _ 29 1~36~5~
are foam-suppressing agent~; for this purpose soaps, or high molecular weight amide or amine foam suppressors, Yuch as N,N-dilauryl (or dicoco alcohol) amine, may be employed in small amounts, e.g. 1/2 to 8~ of the total composition.
Optionally the compositions of the Examples contain minor proportions (e.g., about 5 to 15%) of ~odium per~orate for its bleaching effects.
Instaad of using a Type 4A molecular ~ieve in the Examples, in which sodium i9 the cation, one may employ a Type 3A having a potassium cation or the molecular sieve may contain both sodium and potassium cations in various relative atomic proportions, e.g., 1:9, 1:1, 9:1, or other cationsmay be sub~tituted (e.g., Li or NH4 ) in whole or part, preferably only in part, e.g., up to 30%. All or part of the Type A sieve may be replaced by another molecular sieve capable of exchangin~ calcium,such as Type X ~e.g., in sodium form). Useful molecular sieves of various types are well known in the art; see, for instance, the book "Zeolite Molecular Sieves" by Donald W. Breck, published in 1973 by Wiley-Interscience. The zeolites that are used in the Examples are prefer-ably in a form which is hydrated and substantially free of water-insoluble binder.
This invention can be used to provide 1~369~i6 hlghly effective substantially phosphate-free high performance heavy duty household laundry detergent compositions which are highly effective against a wide variety of soils for a wide variety of fabrics, including cotton, nylon, polyester (e.g., poly-ethylene terephthalate), etc. They may be used in automatic washing machines of the type (common in the U.S.) in which the wash water i5 centrifugally driven through the clothes (during the "spin"
portion of the washing cycle) without cauaing signi~icant deposition o~ the particles on the clothes, which i~ surprising, aGnsidering the insolubility characteristics of the zeolite molecular sieves. The wash water may be hot (e.g., 50C, 60C or higher) or cool (e.g., 40C, 25C, 20C
or lower). The water may be soft or hard (e.g., having a hardness, expressed as CaCO3,of 50, 100, 150 or 200 ppm).
A~ wa~ indicated above, the bulk specific gravlty o~ the ~pray-dried be~d~ in Example 29 i~
ln the range of about 0.3 to 0.4. The bulk speci-fic gravity of the molecular sieve in that Example is about 0.25, but other useful molecular sieves may be of varying bulk specific gravitie~, e.g., about 0.2 to 0.5, such as about 0.25 to 0.45. The true specific gravity of the molecular sieve-~ is usually about 2, such as within the range of 1.5 to 2.5.

~L~a6~6 In Example 3 the use o trisodium-2-oxa-1,1,3-propane tricarboxylate (a builder sold by Monsanto Chemical~ i3 described. Compositions of this type in variations of the described example and in the otXer ~xample~ ma~ contain, for instance, an amount of trisodium-2-oxa-1,1,3-propane tri-carboxylate which is at least about 1/2 the weight of sodium silicate, preferably not more than about twice the weight of the latter, such as about 15 to 20~ of trisodium-2-oxa-1,1,3-propane tricarboxylate, about 20 to 30~ o~ the molecular sieve and about 10 to 20~ of the sodium silicate, twith the proportion of organic anionic detergent etc., being, for instance, as described on pages 3 and 4, above) when intended or use in the wash water at 0.15%
concentration, for instance. In another aspect of the invention it is ound that built detergent compositions in which the sole or predominant builders are approximately e~ual amounts of the tri90dium-2-oxa-1,1,3-propane tricarboxylate and the sodium silicate (such as about 20~ of each of these two ingredients), without as much molecular sieve, give unexpectedly good fabric-washing results (again, with proportions of the other ingredients being, for instance, as described on pages 3 and 4, above and a~ in ~xamples 2, 5 and 6).

_ 32 3~@~6~S6 As indlcated above, another material whlch may be included in the blend of molecular sieve, sodium silicate and anionic detergent, if otherwise unob~ectionable, is trisodium nitrilotriacetate For instance (as illustrated in Example 4, above) one may employ about 10 or 15 to 20~ of this ingredient in the composition (with the proportions of the other ingredients being as ; described on pages 3 and 4 above, for instance) and . 10 a eood heavy duty detergent i8 produced.
Further, as stated heretofore, it should be understood that this invention broadly relates to detergent compositions in the form of spray dried beads comprising at least 5~ by weight of a water-soluble anionic organic detergent in combination with a detergent builder system which includes a water-insoluble alumlnum silicate molecular sieve in a pro-portion at lea~t e~ual to that of the detergent and havin~ an oily, waxy or tacki~ying material sorbed ~0 onto the beads. While the pre~erred sorbed material is a liquid or pasty nonionic detergent such as primary and secondary ethoxylated alkanols, other suitable oily, waxy and ordinarily tackifylng materials which may be used to enhance the properties of the detergent composl-25 tion include, for example, concentrated aqueous slurries of water-soluble salts of anionic sulfonated or sulfated materials such as high alkyl sulfates, olefin sulfonates -~6~5~;
and alkane sulfonates, and higher alkyl polyethenoxy ether sulfates; cationic quaternary ammonium fabric softeners, C8-C18 acyl alkanolamides, and aqueous or non-aqueous dispersions of halohydrocarbon and non-ionic polyether textile treating agents. Such materials can usually be convenient applied by spray atomization onto a moving bed of the spray-dried beads. After aging, effective washing composi-tions in the form of free-flowing hollow beads are produced.
The invention provides highly effective detergent compositions having ralatively low phosphate contents, e.g., water-soluble phosphate contents well below 20~, preferably below 15~, such as 10% or less, e.g., 5~, and most preferably they are substantially free o~ phosphates. They may also be ~ree of carbonates and I~TA in some preferred embodiments.

Claims (23)

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

1. A process for preparing a detergent composition in the form of free-flowing hollow beads which comprises forming an aqueous slurry of a detergent composition containing at least about 5% by weight of a water-soluble synthetic, organic, anionic detergent and about 15 to 45% by weight of a finely divided, water-insoluble sodium or potassium aluminum silicate molecular sieve having the capacity to remove calcium ion from water, the proportion of said sieve being calculated on an anhydrous basis and being greater than the proportion of anionic detergent, and the balance being a water-soluble detergent builder salt selected from the group consisting of inorganic and organic builder salts; spray drying said aqueous detergent composition to form free flowing hollow beads having a moisture content of 3% to 15% by weight; and then blending said beads with a liquid or tacky nonionic detergent to form free flowing beads, the amount of nonionic deter-gent blended therewith being at least 1% by weight and the total proportion of said nonionic detergent being less than 2/3 of the weight of said molecular sieve.

2. A process according to claim 1 wherein the aqueous detergent composition further includes up to 2% by weight of liquid or tacky nonionic detergent, based upon the weight of the beads.

3. A process according to claim 1 wherein said molecular sieve is a Type 4A sodium aluminum silicate in hydrated form.

4. A process according to claim 1 wherein said aqueous slurry includes in addition a sodium or potassium silicate having an Me2O:SiO2 ratio of about 1:2 to 1:3.2, the proportion of said silicate being 7% to 25% by weight of said free-flowing, spray-dried beads.

5. A process according to claim 4 wherein the silicate is sodium silicate of an Na2O:SiO2 ratio of 1:2 to 1:2.4 and the weight ratio of said silicate to said molecular sieve is about 0.5:1 to 0.8:1.

6. A process according to claim 5 wherein the weight proportions of constituents in the aqueous slurry are such as to result in a product, after drying, which comprises about 10 to 20% of synthetic organic anionic detergent, about 15 to 35% of molecular sieve and about 12 to 25% sodium silicate.

7. A process according to claim 5 wherein the aqueous slurry includes, in addition, trisodium-2-oxa-1,1,3-propane tricarboxylate in an amount of about 1/2 to twice the weight of the sodium silicate.

8. A process according to claim 1 wherein the aqueous slurry includes, in addition, sufficient sodium carbonate so that the product contains from 10 to 30% by weight thereof.

9. A process according to claim 1 wherein the molecular sieve is a potassium aluminum silicate molecular sieve.

10. A process according to claim 1 wherein the detergent composition is free of inorganic phosphate builder salts and carbonates.

11. A process according to claim 1 wherein the nonionic detergent is a condensation product of a C8-C20 alkanol and 3 to 20 moles of ethylene oxide and is sprayed in molten droplet form onto the surfaces of tumbling spray dried detergent composition beads.

12. A detergent composition in the form of free-flowing hollow beads having a moisture content of 3% to 15% by weight which comprises spray dried beads of a detergent composition containing at least about 5% by weight of a water-soluble, synthetic, organic, anionic detergent and about 15 to 45% by weight of finely divided, water-insoluble sodium or potassium aluminum silicate molecular sieve, having the capacity to remove calcium ions from water, the proportion of said sieve being calculated on an anhydrous basis and being greater than the proportion of anionic detergent, having a post-added liquid or tacky nonionic detergent sorbed thereon, the proportion of sorbed nonionic detergent being at least 1% by weight and the total proportion of nonionic detergent being less than 2/3 of the weight of said molecular sieve.

13. A product according to claim 12 wherein said spray-dried beads of detergent composition contain up to 2% by weight of liquid or tacky nonionic organic detergent, based upon the weight of the beads, and the total proportion of nonionic detergent is 3% to 20% by weight of said composition.

14. A product according to claim 12 wherein said molecular sieve is a Type 4A sodium aluminum silicate in hydrated form.

15. A product according to claim 12 wherein said spray dried beads of detergent composition include a sodium silicate of an Na2O:SiO2 ratio of 1:2 to 1:3.2 and the weight ratio of said silicate to said molecular sieve is about 0.5:1 to 0.8:1.

16. A product according to claim 15 wherein the weight proportions of the constituents in the final product comprise about 10 to 20% of synthetic organic anionic detergent, about 15 to 35% of molecular sieve and about 12 to 25% sodium silicate.

17. A product according to claim 15 wherein the final composition includes, in addition, trisodium-2-oxa-1,1,3-propane tricarboxylate in an amount of about 1/2 to twice the weight of the sodium silicate.

18. A product according to claim 12 wherein the molecular sieve is a potassium aluminum silicate molecular sieve.

19. A product according to claim 12 wherein the nonionic detergent is a condensation product of a C8-C20 moles of ethylene oxide and is added by spraying in molten droplet form onto the surfaces of tumbling spray dried beads of a detergent composition.

20. A detergent composition which comprises at least about 5% by weight of a water-soluble, synthetic, organic, anionic detergent, about 15 to 45% by weight of a finely divided, water-insoluble sodium or potassium aluminumsilicate molecular sieve having the capacity to remove calcium ion from water, the proportion of molecular sieve being calculated on the anhydrous basis and being greater than the proportion of anionic detergent, an alkali metal silicate, wherein the alkali metal, Me, is sodium or potassium and the MeO:SiO2 ratio is in the range of about 1:2 to 1:3.2, in a weight ratio to said molecular sieve in the range of about 0.5:1 to 0.8:1 and trisodium-2-oxa-1,1,3-propane tricarboxylate in an amount in the range of about 1/2 to twice the weight of said alkali metal silicate.

21. A detergent composition which comprises at least about 5% by weight of a water-soluble, synthetic, organic, anionic detergent, about 15%
to 45% by weight of potassium aluminum silicate molecular sieve, the proportion of molecular sieve being calculated on an anhydrous basis and being greater than the proportion of anionic detergent, and sodium silicate having an Na2O:SiO2 ratio of about 1:2 to 1:3.2 in a weight ratio to said molecular sieve in the range of about 0.5:1 to 0.8:1.

22. A detergent composition according to claim 21 which additionally comprises trisodium-2-oxa-1,1,3-propane tricarboxylate in an amount about 1/2 to twice the weight of said sodium silicate.

23. A detergent composition according to claim 21 which contains no inorganic phosphate builder salt and no carbonate.