AU688277B2 - Detergent composition and process for its production - Google Patents

Description

OPI DATE 29/03/94 APPLN. ID 49553/93 AOJP DATE 23/06/94 PCT NUMBER PCT/EP93/02340 AUJ9349553 INl tKNA IIUNAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 5 C11D 11/02, 17/06 (ll) International Publication Number: A (43) IntErnationa Publication Date: WO 94/05767 17 March 1994 (17.03.94) (21) International Application Number: (22) International Filing Date: Priority data: 941,995 8 Septem 941,510 8Septem PCT/EP93/02340 28 August 1993 (28.08.93) ber 1992 (08.09.92) ber 1992 (08.09.92) (71) Applicant (for AU BB CA GB IE LK MN MW NZ SD only): UNILEVER PLC [GB/GB]; Unilever House, Blackfriars, London EC4P 4BQ (GB).

(71) Applicant (for all designated States except AU BB CA GB IE LK MN MWNZ SD): UNILEVER NV [NL/NL]; Weena 455, NL-3013 AL Rotterdam (NL).

(72) Inventors: KARPUSIEWICZ, William, Martin 2 Yarmouth Court, Washingtonville, NY 10992 GOLD- MAN, Andra, Joy 1478 W. Terrace Circle, Teaneck, NJ 07666 HSU, Feng-Lung, Gordon 99 Ivy Lane, Tenafly, NJ 07670 IRWIN, Charles, Fraser Dalrymple Street, Randolph, NJ 07869 (US).

(74) Agent: GEARY, Stephen; Unilever pic, Patent Division, Colworth House, Sharnbrook, Bedford MK44 I LQ

(GB).

(81) Designated States: AT, AU, BB, BG, BR, BY, CA, CH, CZ, DF, DK, ES, FI, GB, HU, JP, KP, KR, KZ, LK.

LU, MG, MN, MW, NL, NO, NZ, PL, PT, RO, RU, SD, SE, SK, UA, VN, European patent (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OAPI patent (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE., SN, TD, TG).

Published With international search report.

688277 (54)Title: DETERGENT COMPOSITION AND PROCESS FOR ITS PRODUCTION (57) Abstract Detergent powders of high bulk density, containing anionic and nonionic surfactant and builders are prepared by spraydrying a low moisture content slurry containing liquid active surfactants to suspend inorganic solids including selected builders.

A viscosity adjuster may be added to improve processability.

I--I II I- C6184 -1- DETERGENT COMPOSITION AND PROCESS FOR ITS PRODUCTION Technical Field of the Invention This invention relates generally to a process for the production of detergent powder by spray-drying.

Background Traditional mixed active builder containing slurries utilize water as the carrier system for both the active (e.g.

surfactant) and solids builders such as zeolite, carbonate, and the like). This usually results in high slurry moisture content 40-50%).

Liquid active blends on the other hand allow for water and active together to act as a carrier for the solids. The active has changed its function in the slurry. The active instead of being a "solid additive" which must be suspended in the liquid water carrier has itself become part of the liquid carrier system. This change allows for a reduction in the amount of water needed in the slurry as a carrier, because the active substitutes for part of the water.

In the spray-drying process there are frequently opposing factors; for example, more water present ir a slurry, requires more evaporation, with a resultant ir.rease in costs. If less water is used to save costs, the slurry becomes correspondingly more viscous until a point is reached at which it cannot be pumped and metered. An additional factor, due to market considerations is that the finished product requires higher quantities of surfactant. Spraydrying, for example, increased quantities and certain types of nonionic surfactant lead to pluming from the spray tower.

High temperatures contribute to this pluming. Generally L i, IL C6184 2 other things being equal, spray-drying of a slurry having a lower water content leads to less heat input in the tower than higher water content. It is thus desirable to be able to spray-dry low water content slurries while minimizing the problem of high slurry viscosity. A further advantage is that high density powders may be thus obtained.

U.S Patenu 4,738,793 employs low moisture slurries for spraydrying but this is accompl:shed using nonionic surfactants in the substantial absence of anionic surfactant (less than 2% anionic is taught).

The current art describes the use of high shear mechanical devices to achieve high powder density (>600 g/L) with *1 zeolite layering to control particle size distribution of the final product U.S. 4,869,843. Also described in use of nonionic surfactant sprayed onto base powder with addition of secondary materials to achieve high powder density (>450 U.S. 5,030,379 to Knight et al. Specific preparative methods for low water content compositions are disclosed in U.S. 5,075,041.

EP-A-0270240 describes a spray dried zero-phosphate detergent powder and discloses a zeolite built powder of very high bulk density formed by spray drying a slurry having a defined water content, low or zero levels of electrolyte and polymeric polycarboxate present. Nonionic detergent is optionally present in the slurry in a range of 1 to EP-A-0228011 describes a process for preparing a phosphatereduced detergent composition containing inter alia on anionic surfactant and optionally a nononic detergent. The nonionic is primarliy introduced into the detergent powder by spraying on to particles already formed by a spray drying process. The resulting powder is admixed with another spray dried detergent powder which can contain up to 5wt% nonionic -LI- IIII C6184 3 in such small amounts that pluming and any viscosity problems are said not to be present. The slurry from which the second potentially nonionic-containing powder is spray dried may contain a polymeric carboxylic acid.

The method employed by the art for lowering slurry moisture and avoiding pluming from high temperatures or high nonionic concentrations have not been completely satisfactory.

Definition of the Invention A method of slurry preparation and a slurry composition which exhibits exceptionally low viscosity even at low water content, thus enabling it to be spray-dried to a high [Li surfactant concentration without unacceptable pluming has now been discovered. In addition, it has been found that a spray-dried powder of exceptionally high density can be obtained.

Simple mixtures of water and nonionic surfactant, typically result in a very viscous gel. Gel formation may be avoided in producing a liquid active mixture by using a preferred order of addition: water plus caustic, then nonionic plus the acidic form of the anionic surfactant. Water plus caustic changes the characteristic viscosity curve so that when the nonionic is added an emulsion is formed in place of a gel.

Emulsion viscosity, of course, is much less than gel viscosity. The acid precursor of the anionic may then be added and is preferably neutzalized in situ. This makes the liquid active mixture more viscous, but still avoids the gel state. Once this is done, solids addition of the builder, i.e. zeolite and/or carbonate as well as other builders such as NTA and the like may be carried out.

A 0 Lij I I II I-I I C6184 4 In U.S. Patent No. 4, 923, 636 Blackburn and U.S. Patent No.

4, 826, 632 Blackburn, there are disclosed liquid surfactant compositions that can be sprayed onto spray-dried powders to increase the bulk density thereof. While these 'densified' spray dried powders have not been produced by mechanical densification, the disadvantages of using a spray dried powder as a starting point remain.

A blend of surfactants may be used such as that disclosed in Hsu et al. US Serial Number 07/808,314 (Patent Number 5219495) filed 12/16/91 or 07/816,366 filed 12/31/91. In the blend, in addition to a neutralized or partially neutralized anionic surfactant, nonionic surfactants are included.

LA low moisture content detergent slurry is manufactured Sa.

utilizing liquid active surfactant blends containing anionic and nonionic surfactants. This low moisture slurry is then spray-dried using standard spray-drying techniques yielding, if desired, a concentrated or high density base powder.

Accordingly, the invention provides a process for preparing by spray-drying, washing powders containing anionic active, nonionic active and builder, carbonate and zeolite, for example, crystalline and/or amorphous aluminosilicate including the zeolites disclosed in EP,384,070A and 448,297A.

*25 The builders are used in a proportion of at least about 5 to percent of anionic to 1 to 50 percent of nonionic to 5 to percent of a builder.

The slurry is prepared by forming an aqueous mixture of a nonionic and anionic surfactant to which a builder is and other detergent components may be added to produce the slurry for spray-drying. The aqueous anionic-nonionic mixture comprises water, a nonionic active and an anionic active wherein the anionic is incorporated as:

L

C6184 5 i) the acid form of an anionic surfactant and the mixture further contains a neutralising agent whereby the acid is neutralised in situ to form the anionic surfactant; and/or; ii) an anionic surfactant.

Where the anionic surfactant is incorportaed into the mixture as a surfactant preferably the nonionic and anionic surfac:ant are mixed to form a surfactant blend which is then incorporated into the mixture. Suitably preparation of the slurry in which the surfactants are incorporated as a blend is comprised of: A. preparing under agitation a mixture of water, optionally a viscosity adjuster, optionally sufficient alkali metal hydroxide to result in neutralization of the acidic form of desired adjuvants and a prepared surfactant blend containing anionic and nonionic surfactants thus forming an anionic nonionic active mixture, said blend containing about 10% to anionic surfactant, and 0% to 35% water; B. preferably maintaining the temperature of said mixture below about 93.3 0 C (200 0

F);

2 C. then adding under sufficient agitation to said anionicnonionic mixture, sufficient builder and other detergent adjuncts such as sodium silicate, polymer, and the like to result in said powder containing about 5% to 70% of a builder p selected from the group consisting of zeolite, carbonate and mixtures thereof. Other builders such as sodium citrate may also be added. This combination of ingredients forms a final slurry mixture having a maximum amount of about 35% water, the minimum amount of water being sufficient to achieve appropriate viscosity;

I

C6184 6 D. optionally adding a viscosity adjuster, in an amount of from 0 to 50% of said mixture, at any time during the slurry process to result in a viscosity of the final slurry mixture of about 1000 x 10- 3 to 20,000 x 10 Pa.s (1000 to 20,000 cps) measured at a shear rate of 17 to 18 sec and a temperature of 65.5 to 90.5 0 C (1500 to 195 0

F).

E. then adjusting the temperature, if necessary, of said final mixture to about 57.2 to 90.5 0 C (135-195 0 F) and spraydrying said final mixture to form the base powder; Suitably preparation of the slurry in which the anionic surfactant is incorporated in the acid form is comprised of: "'L3 A. preparing under agitation a mixture of water, optionally 0* a viscosity adjuster and sufficient alkali metal hydroxide to result in neutralization of the acidic form of said anionic active and optionally other anionic additives, citric acid; B. adding under said agitation to said mi i-ure, sufficient nonionic active to prepare said powder, said powder having a range of about 1% to 50% by weight nonionic, thus resulting in a nonionic active mixture; C. adding under agitation, to said nonionic active mixture a sufficient amount of the acidic form of said anionic active to result in a final powder con-aining about 5% to 50% of the salt form of said anionic active, thus forming an anionicnonionic mixture; D. preferably maintaining the temperature of said mixture below 93.3 0 C (200 0

F);

C6184 7 E. then adding under sufficient agitation to said anionicnonionic mixture sufficient builder and other detergent adjuncts such as sodium silicate, polymer, and the like to result in said powder containing about 5% to 70% of a builder selected from the group consisting of zeolite, carbonate and mixtures thereof. Other builders such as sodium citrate may also be used. This combination of ingredients forms a final slurry mixture having a maximum amount of 35% water, the minimum amount of water being sufficient to achieve appropriate viscosity; F. optionally adding a viscosity adjuster, in an amount of from 0 to 50% of said mixture, at any time during the slurlry process to result in a viscosity of the final slurry mixture of about 1000 x 10' to 20,000 x 10 Pa.s (1000 to 20,000 S* cps) measured at a shear rate of 17 to 18 sec and a temperature of 65.5 to 90.5 0 C (1500 to 195 0

F).

G. then adjusting the temperature of said final mixture to about 57.2-90.5 0 C (135-195 0 F) and spray-drying said final mixture; DESCRIPTION OF THE INVENTION ,:25 Preferably the water content will be from 10% to 35% by weight of the slurry, in which case it will be possible to spray-dry the powder to a bulk density above 500 g/liter, desirably from 500 to 900 g/liter. Generally, it will be preferred to reduce the water content to the minimum practical level, although the percentage at which this minimum occurs will vary with the content of the other components of the formulation as explained in more detail below.

s t C6184 8 Viscosity is extremely important since for ease of operation any composition, e.g. a slurry, must be capable of being sprayed at pressures commonly used such as 68947.5 Pa psi) to 6894757 Pa (1000 psi) through nozzle sizes of about 0.1 mm to 11 mm or more at temperatures of about room temperature of about 18.30C (65 0 F) up to about 93.30C (200 0 Such low temperatures avoid excess evaporation.

Typically, the viscosity of such composition is about 1000 x 3 Pa.s (1000 centipoise) to 20,000 x 10' Pa.s to (20,000 centipoise) at a temperature of 65.50C (1500) to 850C (185 0

F)

or even somewhat higher at a shear rate of 17 to 18 sec 1 Compositions having a ratio of anionic surfactant to nonionic surfactant of 1:3 to 3:1 may be employed but 1:2 to 2:1 are 15 of especial interest.

2 Preferably, the composition of slurry should be formulated so that the viscosity of the final slurry is about 7000 x Pa.s (7,000) to 20,000 x 10' Pa.s (20,000 cps), preferably less than 20,000 x 10' Pa.s (20,000 centipoise), more preferably less than 10,000 x 10' Pa.s (10,000 centipoise), measured at a r hear rate of 17 to 18 secs at a temperature of 65.50C (1500) to 850C (185 0 The slurry must be sufficiently fluid to allow thorough mixing of all of the :25 components in the mixer. After mixing is finished, the slurry must remain sufficiently fluid to pump it out of a mixing vessel to a spray tower. As better and more efficient mixers become available processing of more viscous systems becomes easier. Conversely, as pumps are improved, higher viscosity slurried can be pumped. The viscosity must be such that the desired physical mixing and pumping can be done economically and chemical reactions if any, such as neutralization take place readily. The final point prior to spray-drying is the actual atomization of the slurry in the tower spray nozzles. There are many different designs of I- L _1 I CL I spray nozzles well known to those skilled in the art with which to achieve appropriate atomization.

Liquid mixing can be defined as a Reynolds number where NR is defined as follows: S ND 2 p ,t NRe

P

where N is Reynolds Number, N is impeller speed, D is impeller diameter, p is specific gravity and jt is viscosity at a shear rate of N7 sec'.

In order to provide appropriate impeller mixing, the final slurry in the mixer should have a flow with a Reynolds Number of about 1 to 10,000 which is conveniently produced by an appropriate impeller design.

VISCOSTTY ADJUSTERS The viscosity of the slurry thus depends upon many functional parameters. The viscosity to be achieved must be appropriate for the slurry to be mixed, pumped and atomized in a spray tower. The viscosity thus may vary within fairly wide ranges.

The viscosity of the slurry can be adjusted by the addition of S• an organic or inorganic additive in a sufficient amount to S: result in a viscosity in the final slurry of about 1000 x 10 Pa.S (1000 cps) to 20,000 x 10' 3 Pa.S (20,000 cps) at a shear rate of 17 to 18 sec and a temperature of 65.5 0 C (1500) to 85 0 C (185 0 Examples of viscosity adjusters are nonionic surfactants, hydrotropes sodium xylene sulfonate), polyethylene glycol, polypropylene glycol and inorganic salts Na 2 This viscosity adjuster may be introduced I I- C6184 10 into the water at the beginning or optionally during the process or may even be added after the anionic precursor but it is preferably added prior to most of the zeolite or other builder solids to insure proper fluidity. The viscosity adjuster may also be put into any of the additives as a mixture and added in this way.

The amount of viscosity adjuster employed is sufficient to insure slurry fluidity and varied from about. 0.5% of the slurry weight to about 30% of the slurry weLght. It also must be realised that when an anionic sulfated or sulfonated precursor is prepared, a certain amount of free or acidic sulfate will be formed. Due to these impurities in the precursor, some sulfate salt will be present. In normal commercial products, this is usually insufficient to fully fluidize the slurry. 0C course, if excess sulfuric or other acid were added intentionally to the precursor, or if the sulfonation or sulfation reaction forming the precursor were terminated prematurely sufficient sulfate or other anion could be introduced with the precursor and the salt formed in situ to fluidize the slurry without adding excess viscosity adjuster.

Temperature during the processing should be ca?efully :25 controlled. Temperatures of 93.30C (2000F) or more have destabilized the slurry and degraded the components.

NONIONIC

9 It is essential to the successful application of the process of the invention that the slurry should contain a nonionic surfactant. Preferably the nonionic surfactant will be an ethoxylated or ethoxylated propoxylated primary or secondary linear or branched chain alcohol having a carbon chain length in the hydrophobic portion of from 5 to 25, and containing

M

C6184 11 from about 5 to about 35 moles of ethylene/oxide and/or propylene oxide per mole of alcohol. Examples of such materials are ethoxylates the Dobanol and Neodol (Registered Trade Mark) alcohols, sold by Shell Chemicals and the Tergitol (Registered Trade Mark) ethoxylated alcohols sold by Union Carbide Corporation. However, other types of nonionic surfactants can also be used, alkyl phenol ethoxylates for example, including in particular the reaction products of alkylene osices, usually ethylene oxide, with alkyl phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxide per molecule; and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine. Other so-called nonionic surfact-actives that may be used include alkyl polyglycosides, long chain "IS tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.

e The amount of nonionic in the final powder will be about 1 to preferably 5 to 50%, more preferably 10 to

ANIONIC

Anionic surfactants which may be formed from precursors sulfonic acids) are also essential.

Typical anionic surfactants include sodium alkylbenzene sulphonates, sodium alkyl sulphates, sodium alkane sulphonates and sodium alkyl ether sulphates. More particularly, C,-Cs primary and secondary alkyl or alcohol sulfates secondary alkane sulfonates, C olefin sulfonates, C 1 o-C. soaps and the like may be employed, preferably, sodium or potassium alkylbenzene sulfonates or alkyl sulfates are employed. Particularly suitable alkylbenzene sulfonates are sodium alkylbenzene sulfonates. Suitable alkyl sulfates are alkyl C6184 12 sulfates, although other alkyl sulfates and sulfonates outside this carbon chain length range, may also be used.

The acid form of the precursor is neutralized in the mixture with sodium, potassium or ammonium hydroxide.

The amount of anionic in the final powder will be about 5 to preferably about 10 to

BLENDS

In addition to the use of individual actives as discussed above, prepared liquid active blends of nonionic and anionic surfactants may be used. These blends and methods for their preparation and use are disclosed in U.S. Patents 4,637,891; '"li 4,826,632; 4,923,636; 5,045,238; 5,075,041 as well as EP 88,612A and 0,265,203; French patent 2,645,876 and GB Patent 1,169594. These blends may be employed with the instant invention, particularly those disclosed in U.S. patents 4,826,632 and 4,923,636 and US Serial Numbers 07/808,314 (Patent No. 5219495) filed 12/16/91 and US 007/816,366 filed 12/31/91 to Hsu et al. hereby incorporated by reference 9.

herein.

The method of preparation of the blend is important. Simple 2*5 admixture of normally 50% aqueous neutralized alkylbenzene sulphonate paste and liquid nonionic surfactant in the desired proportions will give not a mobile isotropic liquid but a highly viscous gel which is difficult to handle.

Liquid nonionic surfactant may be gradually added to an alkylbenzene sulphonate paste (neutral salt) which will typically have an active matter content of about 50% by weight. The resulting viscous material, containing more than water, is then heated to a sufficiently high temperature for a sufficient period of time for the water content to fall 'C6184 13 below 10% by evaporation. A clear mobile liquid is obtained and this remains clear and mobile when allowed to cool to ambient temperature.

According to a second method, alkylbenzene sulphonic acid may be mixed with nonionic surfactant, and the mixture treated with concentrated aqueous sodium hydroxide or potassium hydroxide to effect partial or complete neutralization.

Mixtures fluid at 200 to 80 0 C and containing about 6 to 7% by weight of water may be produced by this method.

According to a variant of the second method, the alkylbenzene sulphonic acid starting material may be in partially neutralized form.

In a third method, a range of compositions containing anionic surfactant, nonionic surfactant and water in relatively high amounts up to about 35% may be prepared containing sodium or potassium hydroxide in excess of that necessary to neutralize the anionic sulfonic acid if a precursor is used. These compositions are sufficiently mobile at temperatures no higher than about 90 0 C. The blends employed are liquid surfactant compositions mobile at a temperature within the range of about 150 to 90 0 C or if the anionic to nonionic ';26 ratio is appropriate and the type of nonionic is appropriate even down to about 5 0 C. This composition contains preferably; o a sodium or potassium salt of an alkylbenzene sulfonate or alkyl sulfate in an amount not exceeding 80% by weight and preferably 5 to 80% or even 20% to 60% by weight, an ethoxylated nonionic surfactant in an amount not exceeding 80% by weight, preferably 5 to 80% and most preferably 20% to 60% by weight, &TNT o0,

~I

C6184 14 sodium or potassium hydroxide in an amount of about 2% to 15% by weight, depending on the ratio of anionic to nonionic. For very high anionic to nonionic ratios of 2:1 up to 4:1 a greater excess of caustic is preferred whereas for lower ratios of 0.125:1 smaller excess amounts such as 2% are sufficient, and water in an amount of 0%-35% by weight preferably 5% to by weight most preferably about 10% up to about 20% by weight.

Higher water contents, that is, contents greater than about 10%, when included in a composition of anionic and nonionic surfactants typically result in gel formation even with low 'L ~ratios of anionic to nonionic such as 0.125:1. The addition of concentrated aqueous hydroxide solution (50 prevents gel formation and reduces the viscosity of the composition even though water is added to the composition by the introduction of the aqueous hydroxide solution. The ability to increase the water content of such compositions greatly expands the operation window. The reduction of the viscosity Vao facilitates the ease of operation by improving pumpability and the like.

Viscosity of the blend is extremely important since for ease of operation any composition must be capable of being processed. Typically, the viscosity of such compositions is about 50 x 10' Pa.s (50 centipoise) to 5000 x 10 Pa.s (5000 centipoise) at a temperature of 600°C or even somewhat higher.

Compositions having a ration of anionic surfactant to nonionic surfactant of 0.125:1 to 4:1 may be employed but 1:1 to 3:1 are of especial interest.

I -~I C6184 15 In addition, an improvement with regard to the processability properties may be obtained in the blend if 0.5-80% by weight of a C,-C, 2 fatty acid is incorporated in the liquid surfactant composition.

In this case, the blend provides a liquid surfactant composition which is mobile at a temperature within the range of 20 to 80 0 C and which comprises a sodium or potassium salt of an alkylbenzene sulfphonate or alkyl sulphate in an amount preferably not exceeding 70% by weight; an ethoxylated nonionic surfactant in an amount preferably not exceeding by weight; and water in an amount preferably not exceeding 20% by weight, more preferably not exceeding 10% by weight; characterized in that it further comprises 0.5 to 80% Dy i weight of a fatty acid having 8 to 22 carbon atoms.

*0 6o 9 According to yet another aspect of the invention, there is 00: provided a process for the manufacture of the above liquid surfactant composition, by mixing said nonionic surfactant with a concentrated aqueous alkali metal hydroxide solution having about 80% to 98% of the stoichiometric amount of said 6 alkali metal hydroxide necessary to neutralize an acid precursor of said sulphate or sulphonate, to form a nonionic alkali dispersion; mixing said acid precursor with said dispersion form a blend; adjusting the pH to about 7; and then mixing the blend with the fatty acid to form the mobile composition.

The compositions include in addition 0.5-70%, preferably 2- 15%, more preferably 2-7% by weight of a fatty acid having 8 to 22 carbon atoms. It is preferred if the fatty acid possesses 12 to 20 carbon atoms, and more in particular 16 to 18 carbon atoms. A suitable fatty acid is coconut fatty acid.

C6184 16

BUILDERS

Selected builder materials are added to the slurry. The builders are preferably zeolite and/or sodium carbonate.

Other substantially solution materials which have a detergency builder action may be used by including them in the slurry. Of course, these builders may be added by post dosing to the composition produced by the spray-drying step.

Examples of substantially soluble detergency builders are sodium tiproly-, pyro- and orothophosphates, sodium citrate and various organic detergency builders such as sodium nitrilotriacetate, ODS; TMS/TDS homopolymers of acrylic acid and copolymers of acrylic and maleic acids. Substantially insoluble builders are, for example, sodium aluminosilicates 1 including zeolites, crystalline, amorphous, as well as calcite, and the like. Generally detergency builders will be present in amounts of from 5 to 70% by weight of the final product, amounts of from 25 to 40% by weight being more general.

OTHER DETERGENT ADJUVANTS The slurries can also contain a number of optional components *5 S such as lather controllers, anti-redeposition agents such as sodium carboxymethlycellulose, fabric softening agents such as quaternary ammonium salts either alone or in combination with clays, anti-ashing aids, starches, slurry stabiliziers b such as homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid; ethylene and maleic anhydride,

S

and of vinyl methyl ether and maleic anhydride, usually in salt form; antioxidants and fluorescers.

In a final process stage the spray-dried powder produced can be dosed with ingredients that are incompatible with the spray-drying process conditions in the amounts required to s i I C6184 17 produce a finished powder. Components may be incompatible for many reasons, including heat sensitivity, pH sensitivity, degradation in aqueous systems and the like.

The usual heat-sensitive zwitterionic surfactants such as derivatives of al-hiphatic quanternary ammonium phosphonium acid, sulphonium compounds in which one of the aliphatic constituents contains an anionic water solubilizing group may be added. Additional components which may be added in this manner are sodium perborate mono- and tetrahydrates, sodium percarbonates and acid bleach precursors such as tetracetylethylene diamine, tetracetylglycouril and sodium nonyl oxybenzene sulphonate, perfumes, enzymes and composite adjuncts. The process is especially suitable for use where 0 it is intended to add composite adjuncts to the spray-dried .1 powder in a dry-dosing step, since such ad]uncts normally 8* have very high bulk density and tend to separate from lighter I powders. Examples of composite adjuncts are antifoam S granules, for instance, granules based on a starch core having a coating of a mixture of liquid and waxy hydrocarbons; composite colored speckles prepared in any way, containing spray-dried base powder granulated with a colored binder solution; and adjuncts containing calcium carbonate seed crystals such as high surface area calcite (80-90 mg The following examples will more fully illustrate that embodiments of this invention. All parts, percentages and e proportions referred to herein and in the appended claims are t by weight of the total composition unless otherwise stated.

EXAMPLE I The mixer includes a Lightnin' A-320 impeller to promote mixing. 114.3kg (252 lbs.) of water is charged into the mixer and heated to 37.7-48.8 0 C (100-120 0 The agitator is C6184 18 set at 40 RPM. 54.88 Kg (121 lbs.) of 50% caustic solution (enough for the neutralisation reactions of precursor alkylbenzene sulfonic acid and citric acid) is added next while maintaining the agitator at about 0.66 rad s 1 (40 RPM) A temperature rise to 54.4-60 0 C (130-140 0 F) is observed.

At this point 90.7kg (200 lbs.) of nonionic surfactant (in this case, Neodol 25-7, a 7EO nonionic) are pumped into the mixer with the agitation still set at about 0.66 rad s 1 RPM). The temperature is observed to decrease approximately 5.50C (10 0 F) to 48.8-54.40C (120-130 0 Close to the end of or after the nonionic charge the agitator may be increased to about 0.83 rad s" (50 RPM), 88.9 Kg (196 lbs.) of b, alkylbenzene sulfonic acid is then added. As the acid is neutralizes the temperature increases and the mixture turns 0" from a transparen_ emulsion to a brown liquid to a white paste. As the mixture reaches the white paste stage, the slurry mixture becomes significantly thicker. It may be necessary to increase the agitation to about 1 rad s RPM) during the acid addition in order to promote good mixing and quicker neutralisation, a short period of about three 6' *minutes after the end of the acid addition is beneficial in order to help ensure full neutralisation. The temperature

'A

increase from the neutralisation reaction is about 16.6- 22.2 0 C (30-40 0 F) resulting in a slurry temperature of 71.1- 73.80C (160-165 0

F)

After neutralisation 43.09 Kg (95 lbs.) of citric acid (for example, Citrosol' 503, a 50% solution) is charged into the 0 mixer. A second neutralisation reaction takes place and the temperature rises 5.5-11.10C (10-20 0 F) to 79.4-850C (175- 1850F). Increasing the agitation tc about 1.16 rad s RPM) and a two minute hold time is beneficial after the citric acid addition in order to facilitate mixing and completion of the reaction. 26.3 Kg (58 lbs.) of sodium S s R 4 IINow C6184 19 sulfate, a viscosity adjuster, is added at this point. A few minutes may be necessary for complete mixing f the sodium sulfate. No effective temperature change is observed.

0.0725 Kg (0.16 lbs.) of Silicone defoamer is added in order to help remove entrapped air bubbles from the slurry.

Removal of entrapped air results in a denser slurry which in turn will result in a denser spray-dried powder. Prior to the zeolite solids addition, the agitator should be increased to about 1.33 rad (80 RPM).

At this point 199.5 Kg (440 lbs.) of 4A zeolite is charged into the mixer. The addition of room temperature solids decreases the temperature of the slurry to 68.3-73.8 0 C (155- 165 0 As the solids are mixed, the slurry viscosity increases and it may be necessary to increase agitation to about 1.5 rad (90 RPM) during zeolite addition or at the end of zeolite addition prior to sodium carbonate addition.

79.83 Kg (176 lbs.) of sodium carbonate are now charged into the mixer. An increase of 2.77-5.55 0 C (5-10 0 F) to a slurry temperature of 71.1-76.60C (160-170 0 F) is observed as the sodium carbonate hydrates. The slurry appears thinner (i.e.

lower viscosity) at this point. 2.31 Kg (5.1 lbs.) of a fluorescent whitener is added next. No temperature increase is observed. Once the whitener is added, the agitation is 2..:25 increased to about 1.66 rad s (100 RPM) and the slurry is heated to a final temperature of 82.2-850C (180-185 0

A

final hold time of 5 minutes may be employed to ensure Sl complete m'xinc of all ingredients. A calculation of Reynolds Number Ne on the final slurry is as follows: NR ND 2 p N impeller speed D impeller diameter p density (specific gravity) 41

-A

A7'X O I C6184 20 pi viscosity (at Nnr shear rate) N 100 RPM 1.667 revolutions (rev) sec D 23 inches =58.42 cm p =1400 gIL =1.4 kg/L NnT= (1.667 rev) (3.1416 1J 5.2 1 sec rev sec p 36,725 cP at 5.2 1 sec n 3.1416 2[1 1 lVRe=ri 667 27e'1[ 5 8 4 2 CR]2 mr 4 1 II 1~3 .141sec 10 lOMcmI LI lx2O-3m3 rev] *I X 10-3 xa~k9sec 36,725 I]1C 00 C a NR. =6 8 Careful temperature control is important since batches which have been heated above 93.3 0 C (200 0 F) have been observed to o* separate and char the nonionic. The slurry described herein may be made, pumped and circulated through piping without 0*020 physical separation issues provided appropriate temperatures are maintained.

0.

900

WO

C 6184 o *0 0 0 a. 0* -21 TYPICAL VISCOSITY PROFILE DATA FROM A MODEL SLURRY AS IN EXAMPLE I IS AS FOLLOWS: Shear Rate J viscosity (cP)xlO' Pa~s *5.2 36,725 7.615 27,270 (T=(159 0 F)70.5 0

C

11.86 19,170 *17.92 13,800* 27.49 9, 858 42.17 6,997 64.71 5, 045 99.26 3,637 152.6 2,611 *value is typically used for reporting purposes.

*interpcl.ated value.

9*00 000 06 000*0 't C6184 0s

S

a 9990 a 9a 0a9* a a.

*9 00 0 I 22 EXAMPLE II A powder is prepared from the slurry of this invention containing the following ingredients: FINISHED POWDER PREPARED FROM 30% SLURRY MOISTURE CONTENT (In order of Addition) TOWER: IN FINISHED

PRODUCT:

Water 12.60 Sodium Hydroxide, 50% soln Alcohol Ethoxylate, 7EO 12.00* Sodium Alkylbenzene Sulfonate 12.00* (neutralized from the sulfonic acid) Sodium Citrate 4.00 (neutralized from citric acid) Silicone Defoamer 0.01 Zeolite, ihydrous 22.00 SAlcohol Ethoxylate, 11EO 1.00 Sodium Carbonate 14.00 Fluorescent Whitening Agent 0.30 Miscellaneous Solids 0.02 Reserved 22.07 (for post-dose ingredients, colorants, perfumes, extra builders, and the like) \4 4/ 7r C6184 *c Re *o S C

S

*0 C 23 these are the components for the liquid active blend 1:1 Linear alkylbenzene sulfonate (LAS):7EO (Nonionic) to yield 24% active in the finished product.

consumed in neutralization reactions.

EXAMPLE III LOW MOISTURE CONTENT MODEL SLURRY PROCESSING IN ORDER OF ADDITION (725.7 Kg (1600 lbs.), finished product bath size) TEMPERAJRE AFTER RAW ADDITION COMPLETE Kc (LBS) Water 22.2 0 C (72 0 F) 129.7 (285.94) sodium hydroxide 41.1 0 C (106 0 F) 55.6 (122.70) nonionic, 7EO 38.3 0 C (101 0 F) 98.7 (217.60) alkylbenzene 63.3 0 C (146 0 F) 92.3 (203.50) sulfonic acid sodium sulfate 61.1 0 C (142 0 F) 63.9 (141.02) citric acid, 50% 68.3 0 C (155 0 F) 43.2 (95.26) silic(:i. defoamer 65 0 C (149 0 F) 0.0725 (0.16) 4A zeolite 60 0 C (140 0 F) 199.5 (440.00) (may have to add heat during zeolite addition in order to maintain ~67.7 0 C (140 0

F)

sodium carbonate 67.7 0 C (154 0 F) 79.8 (176.00) fluorescer whitener 67.2 0 C (153 0 F) 2.29 (5.05) Heat finished slurry batch to 85-93.3 0 C (185-200 0

F).

This slurry formulation will yield an approximate Slurry Moisture Content (SMC) of 30%. Water losses due to evaporation may result in a lower SMC measurement. Extra water can be added to compensate.

J, I HA 24 LOW MOISTURE CONTENT MODEL SLURRY FINAL FORMULATION iqo.

0 0 0800 *0b 000*00 [RAW J% FINAL PRODUCT Water 12.6 nonionic, 7e0 12,5 linear alkylbenzene sulfonate sodium salt (LAS) 12.5 sodium sulfate 8.814 soceiumr citrate silicone defoamer 0.01 4A zeolite 22.0 sidium carbonate 11.0U fluorescer whitener 0.3 miscellaneous solids 0.2018

POST-DOSED

4A zeolite perfume 0.4 sodium carbonate 10.0 speckles enzymes 0.6742 TOTAL 100.C)00 VTo (76184 25 EXAMPLE IV Slurries were prepared as in Example I but the ingredients were varied.

A. LAS/NI 1:1 Slurry Moisture Content Zeolite Sodium Sulfate 8% In order of Addition *S a.

a a a a.

a a a w a. a a.

a a .*a a a a. a a a a.

a a..

a a b e.

S..

S

S

S

S

S

S

St .t.

S* 9 5 Kg Component Final Active Water Misc. Sulf Total Charge Wt.

WATER 12.6000 100.00 0.00 0.00 0.00 100.0 (329.31) 149.37 Sodium Hydroxide 0.0000 50.00 50.00 0.00 0.00 100.0 (150.91) 68.45 Nonionic 12.5000 100.00 0.00 0.00 0.00 100.0 (200.00) 90.72 Cij--7EO (LAS) 12.5000 96.00 0.00 2.00 2.00 100.0 (195.67) 88.75 Anionic Acid Citric Acid 4.0000 50.00 50.00 0.00 0.00 100.0 (95.26) 43.21 Sodium Sulfate 8.0000 100.00 0.00 0.00 0.00 100.0 (122.33) 55.48 Silicone Defoamer 0.0100 100.00 0.00 0.00 0.00 100.0 (0.16) 0.0725 Zeolite 22.0000 90.40 9.60 0.00 0.00 100.0 (389.38) 176.62 Sodium Carbonate 11.0000 100.00 0.00 0.00 0.00 100.0 (176.00) 79.83 Fluorescer 0.3000 95.0 r 0.00 5.00 0.00 100.0 (5.00) 2.27 HOLE* *16.4855 100.00 0.00 0.00 0.00 100.0 (0.00) 0.00 zeolite from E.P. 384,070A and 448,297A.

C6184 27

V,.

0* COMPOSITION RAW FINAL POWDER jBASE POWDER WATER 12.6000 15.0872 NONIONIC 12.5000 14.967/5 LAS 12.5000 14.9675 SODIUM CITRATE 4.0000 4.7896 SODIUM SULFATE 8.0000 9.5792 SILICONE 0.0100 0.0120 ZEOLITE **22.0000 26.3427 SODIUM CARB3ONATE 11.0000 13.1714 FLUORESCER 0.3000 0.3592 MISC. SOLIDS 0.6045 0.7238 HOLE* 16.4855 TOTAL 100.0000 100.0000 to be post dosed 00 0 0.0 0e* C6184 28 B. LAS /NI 1: 1 Slurry Moisture Zeolite 4A Sodium Sulfate In order of Addition 25% total 4% te V.

V V

V

V.

V V V

V.

V

V

Vase V V

V

V.

9

V..

.a Vt V V V. V a..

a Vt.

C

V V 9 *t 9 09 4 9 9 to: 4 to a. 9. 9 Kg Component Final Active Water Misc. Sulf Total Charge Wt.

WATER 12.6000 100.00 0.00 0.00 0.00 100.0 (251.26) 113.97 Sodium Hydroxide 0.0000 50.00 50.00 0.00 0.00 100.0 (121.14) 54.95 Nonionic 12.5000 100.00 0.00 0.00 0.00 100.0 (200.00) 90.71 C, 2 -7EO Sodium Sulfate 4.0000 100.00 0.00 0.00 0.00 100.0 (58.33) 26.46 (LAS) 12.5000 96.00 0.00 2.00 2.00 100.0 (195.67) 88.75 Anionic Acid Citric Acid 4.0000 50.00 50.00 0.00 0.00 100.0 (95.26) 43.21 Silicone Defoamer 0.0100 100.00 0.00 0.00 0.00 100.0 (0.16) 0.0725 Zeolite 4A 22.0000 80.00 20.00 0.00 0.00 100.0 (440.00) 199.58 Sodium Carbonate 11.0000 100.00 0.00 0.00 0.00 100.0 (176.00) 79.83 Fluorescer 0.3000 95.00 0.00 5.00 0.00 100.0 (5.05) 2.29 HOLE* 20.4855 100.00 0.00 0.00 0.00 100.0 (0.00) 0.00 C6184 30

S

ft. ft ft ft ft ft ft.

ft ft ft ft.. ft ft.

ft ft ft 1c ft...

ft ft ft ft ft.

ft. ft.

ft ft ft *oft ft. ft.

ft...

ft ft. ft COMPOSITION RAW FINAL POWDER BASE POWDER WATER 12.6000 15.8462 NONIONIC 12.5000 15.7204 LAS 12.5000 15.7204 SODIUM CITRATE 4.0000 5.0305 SODIUM SULFATE 4.0000 5.0305 SILICONE 0.0100 0.0126 ZEOLITE 4A 22.0000 27.6679 SODIUM CARBONATE 11.0000 13.8340 FLUORESCER 0.3000 0.3773 MISC. SOLIDS 0.6045 0.7602 HOLE* 20.4855 TOTAL 100.0000 100.0000 to be post dosed ft ft ft ftftft ft ft C6184 31 C. LAS/NI 1: 1 Slurry Moisture Zeolite 4A Sodium Sulfate in order of Addition 35% total 4% 70 0 0 0e 0 0 0 00 0 0 0000 0000 *0.0 0* 0 0 004 0000 0 0e 00 0 00 0 0 *00 *0 000 0 a4) 6..

6* 6

S

6 6 S .6* S S 6 S 6 C *SS 66 C 6 *6 6 *eS 6*6 See a C C .6 6 6S6 *S C C C C S 6 S. 5 C 5 1 1 ji Kg Component Final Active Water misc. Suif Total Charge Wt.

WATER 12.6000 100.00 0.00 0.00 0.00 100.0 (187.81) 85.12 Sodium Hydroxide 0.0000 50.00 50.00 0.00 I0.00 100., (121.14) 54.95 Nonionic 17.5000 100.00 0.00 0.00 0.00 100.0 (280.00) 127.06 C,2-,,1-7EOII (LAS) 17.5000 96.00 0.00 2.00 2.00 100.0 (273.94) 124.26 Anionic Acid Citric Acid 4.0000 50.00 50.00 0.00 0.00 100.0 (95.26) 43.35 Sodium Sulfate 4.0000 100.00 0.00 0.00 0.00 100.0 (56.06) 25.43 Silicone Defoamer 0.0100 100.00 0.00 0.00 0.00 100.0 (0.16) 0.0725 Zeolite 4A 22.0000 80.00 20.00 0.00 0.00 100.0 (440.00) 199.58 Sodium Carbonate 11.0000 100.00 0.00 0.00 0.00 100.0 (176.00) 79.83 Fluorescer 0.3000 95.00 0.00 5.00 0.00 100.0 (5.05) 2.29 HOLE* 10.3244 1100.00 10.00 10.00 0.00 100.0 (0.00) 0.00 C6184 33

S

4. 04 4 4 4 we 4 4 4* 444C 44 C4 C 4444 *4*p 4* 4 4 4** *4 44 4444 4 44* COMPOSITION RAW FINAL POWDER BASE POWDER WATER 12.6000 14.0506 NONIONIC 17.5000 19.5148 LAS 17.5000 19.5148 SODIUM CITRATE 4.0000 4.4605 SODIUM SULFATE 4.0000 4.4605 SILICONE 0.0100 0.0112 ZEOLITE 4A 22.0000 24.5329 SODIUM CARBONATE 11.0000 12.2664 FLUORESCER 0.3000 0.3345 MISC. SOLIDS 0.7656 0.8537 HOLE* 10.3244 TOTAL 100.0000 100.0000 to be post dosed .4 4 .4* 4 4.444.

C6184 34 D. LAS /NI 1: 1 Slurry Moisture Zeolite 4A Sodium Sulfate In order of Addition 35% total 8% ge

G

We

C

S

C.

S

0bS S

C.

CS C

SC

*SC

S. CS C S *5 C *WC C

C

C

CS.

C C a..

S

9 S a *99 a St.

9 0 4 5 9@ 4 em. ce a a a a ap S *aa sa.

S 9 9 0 59 49 959 99 5 5 6 a a a *9 a 'a a Kg Component Final Active Water Misc. Sulf Total Charge Wt.

WATER 10.0000 100.00 0.00 0.00 0.00 100.0 (209.14) 94.86 Sodium Hydroxide 0.0000 50.00 50.00 0.00 0.00 100.0 (143.40) 65.05 Nonionic 17.5000 100.00 0.00 0.00 0.00 100.0 (280.00) 127.01 Cj 1 1 -7EO (LAS) 17.5000 96.00 0.00 2.*0 0 2.00 100.0 (273.94) 124.26 Anionic Acid Citric Acid 4.0000 50.00 50.00 0.00 0.00 100.0 (95.26) 43.21 Sodi-um Sulfate 8.0000 100.00 0.00 0.00 0.00 100.0 1(120.06) 54.46 Silicone Defoamer 0.0100 100.00 0.00 0.00 0 .00 100.0 (0.16) 0.0725 Zeolite 4A 22.0000 80.00 20.00 0.00 0.00 100.0 (440.00) 199.58 Sodium Carbonate 11.0000 100.00 0.00 0.00 0.00 100.0 (176.00) 79.83 Fluorescer 0.3000 95.00 0.00 5.00 0.00 100.0 (5.05) 2.29 HOLE* 8.9244 100.00 10.00 0.00 10.00 1100.0 (0.00) 0.00 C6184 36 0g.

0 0

I

00 0 4 000 7 0 *0 a 'icr 000* 0* .4 B 0040 0l~ IS COMPOSITION RAW !FINAL POWDER BASE POWDER WATER 1(>0000 10.9799 NONIONIC 17.5000 19.2148 LAS 17.5000 19.2148 SODIUM CITRATE 4.0000 4.3920 SODIUM SULFATE 4.0000 8.7839 SILICONE 0.0100 0.0110 ZEOLITE 4A 22.0000 24.1558 SODIUM CARBONATE 11.0000 12.0779 FLUORESCER 0.3000 0.3294 MISC. SOLIDS 0.7656 0.8406 HOLE* 8.9244 TOTAL 100.0000 100. 0000 to be post dosed C6184 37 E. LAS/NI 1:1 Slurry Moisture ZeDlite 4A Sodium Sulfate 49, In order of Addition a is 4 0- Y 00.

0e r 9 0 0 00 0* 006 .S S 00 0 0 me..

0e0 00 0 000 000 0 0 99 00 0 S 0 0 00800 [lb.j Kg Component Final jActive jWater jMisc. jSulf [Total Charge Wt.

WATER 12.6000 100.00 0.00 0.00 0.00 100.0 (97.52) 441.23 Sodium Hydroxide 0.0000 50.00 50.00 0.00 0.00 100.0 (154.53) 70.09 Nonionic 20.0000 100.00 0.00 0.00 0.00 100.0 (313A08) 142.01

C,

1 L-7EO (LAS) 20.0000 96.00 0.00 2.00 2.00 100.0 (313.' 142.01 Anionic AcidI Citric Acid 4.0000 50.00 50.00 0.00 0.00 100.0 (95.26) 43.21 Sodium Sulfate 4.0000 100.00 0.00 0.00 0.00 100.0 (54.93) 24.92 Silicone Defoamer 0.0100 100.00 0.00 0.00 0.00 100.0 (0.16) 0.0725 Zeolite 4A 22.0000 80.00 20.00 0.00 0.00 100.0 (440.00) 199.58 Sodium Carbonate 11.0000 100.00 0.00 0.00 0.00 100.0 (176.00) 79.83 Fluorescer 0.3000 95.00 0.00 5.00 0.00 100.0 (5.05) 2.29 HOLE* 5.2439 100.00 0.00 0.00 0.00 100.0 (0.00) 0.00 C6184 39 51*.

*00 COMPOSITION RAW FINAL POWDER BASE POWDER WATER 12.6000 13.2973 NONIONIC 20.0000 21.1068 LAS 20.0000 21.1068 SODIUM CITRATE 4.0000 4.2214 SODIUM SULFATE 4.0000 4.2214 SILICONE 0.0100 0.0106 ZEOLITE 4A 22.0000 23.2175 SODIUM CARBONATE 11.0000 11.6088 FLUORESCER 0.3000 0.3166 MISC. SOLIDS 0.8461 0.8929 HOLE* 5.2439 TOTAL 100.0000 100.0000 to be post dosed 1814 40 F. LAS/NI 1: 1 Slurry Moisture Content Zeolite 4A Sodium Xylene Sulfonate In order of Addition 25% total 1 S. 9 99 9 9 9 99 9 9 9 9 9 9 9 *99 9999 9 9 99 9 ~999 S~~b .9 9 S *99 999999 9 0 a a..

a a. a a. a a..

a a a a. a a a. a .*a a a

S

a a lb. I Kg Component Final Active_ Wtr misc. Sulf Total Charge Wt.

WATER 12.6000 100.00 0.00 0.00 0.00 100.0 (232.04) 105.25 Sodium Hydroxide 0.0000 50.00 50.00 0.00 0.00 100.0 (118.91) 53.94 Nonionic 12.0000 100.00 0.00 0.00 0.00 100.0 (192.00) 87.09 Cl:,-7 EQ (LAS) 12.0000 96.00 0.00 2.00 2.00 100.0 (187.85) 85.21 Anionic Acid Citric Acid 4.0000 50.00 50.00 0.00 0.00 100.0 (95.23) 43.20 Sodium Xylene 1.0000 40.00 60.00 0.00 0.00 100.0 (40.00) 18.14 Sulfonate Silicone 0.0100 100.00 0.00 0.00 0.00 100.0 (0.16) 0.7025 Zeolite 4A 22.0000 80.00 20.00 0.00 0.00 100.0 (440.00) 199.58 Nonionic 1.0000 100.00 0-00 0.00 0.00 100.0 (16.00) 7.26 C. l1Eo Sodium Carbonate 14.0000 100.00 0.00 0.00 0.00 100.0 (224.00) 101.60 Fluorescer 0.3000 95.00 0.00 5.00 0.00 100.0 (5.05) 2.29 HOLE* 21.0742 100.00 0.00 0.00 10.00 100.0 (0.00) 0.00 184 42 's ea 0* 000 0 9..

00 *0 .:*Of RAW ITemp. Observations Pre-Addition Water (97.8 0 F) 36.5 0 C Caustic (97.6 0 F) 36.4 0 C cloudy Neodol 25-7 (112.1 0 F) 44.5 0 C more cloudy (LAS) Acid (109.7 0 F) 43.23C like mayonnaise, fluffy Sodium Citrate (148.8 0 F) 64.9 0 C slightly thinner, still fluffy, like mayonnaise Sodium Xylene (156 0 F) 68.91)C creamier Sulfonate Silicone (145 0 F) 62.8 0 C no change Zeolite 4A (145 0 F) 62.8 0 C thick, very slightly moving around the A-320 impeller Nonionic (125 0 F) 51.7 0 C Heat up, smooth,

C

1 2 1 5 -7E0 slightly mixing Sodium Carbonate (140 0 F) 60 0 C thick but mixes in, slightly moving Fluorescer (154.7 0 F) 68.2 0 C lost moisture, not mixing as well as when sodium carbonate was added, looks thick 26.7% measured moisture C~6 L84 43 0* 0 :0,

COMPOSITION%

*RAW ]FINAL POWDER BASE POWDER WATER 12.6000 15.9644 ANIONIC ACID 12.0000 15.2042 LAS 12.0000 15.2042 SODIUM CITRATE 4.0000 5.0681 SODIUM XYLENE 1.0000 1.2670

SULFATE

SILICONE 0.0100 0.0127 ZEOLITE 4A 22.0000 27.8743 NONIONIC 1.0000 1.2670 SODA ASH 14.0000 17.7382 FLUORESCER 0.3000 0.3801 MISC. SOLIDS 0.0158 0.3801 HOLE* 21.0742 TOTAL 100.0000 100.0000 to be post dosed

LQ

'j (26184 44 G. LAS/NT 1:1 25% total (premanufactured and neutralized blend) Slurry Moisture Content Zeolite 4A Sodium Sulfate 4% In order of Addition a. 4* a a a a.

a a a a.

a a a a a. a..

a eat a. at Wa a. a 0* 6 0 0 004 0 a a..

a a a a 0 9 0 a 0 000 a0* a S 0 *4 00 *00 *0 0 a 0 9 0 S 0 00 0 Fnl Atv% [lb.]I Kg Component Active IWater Misc. Suif Total Charge Wt.

WATER 12.6000 100.00 0.00 0.00 0.00 100.0 (252.93) 114.73 BLEND 25.0000 92.00 8.00 0.00 0.00 100.0 (434.78) 197.21 Sodium Hydroxide 0.0000 50.00 50.00 0.00 0.00 100.0 (65.49) 29.71 Citric Acid 4.0000 50.00 50.00 0.00 0.00 100.0 (95.26) 43.21 Sodium Sulfate 4.0000 100.00 0.00 0.00 0.00 100.0 (64.00) 29.03 Silicone 0.0100 100.00 0.00 0.00 0.00 100.0 (0.16) 0.0725 Zeolite 4A 22.0000 80.00 20.00 0.00 0.00 100.0 (440.00) 199.58 Sodium Carbonate 11.0000 100.00 0.00 0.00 0.00 100.0 (176.00) 79.83 Fluorescer 0.3000 95.00 0.00 5.00 0.00 100.0 (5.05) 2.29 HOLE* 20.8882 100.00 0.00 0.00 0.00 100.0 (0.00) 0.00 *to be post dosed.

*BLEND 12.5% Nonionic 7E0); LAS 12.5% neutralized C6184 46 4* p p

S*

p p p p p p pp app.

pep.

'p p pp.* p p .p COMPOSITION %6 RAW J FINAL POWDER ]BASE POWDER WATER 12.6000 15.9268 BLEND 25.0000 31.6008 SODIUM CITRATE 4.0000 5.0561 SODIUM SULFATE 4.0000 5.0561 SILICONE J.0100 0.0126 ZEOLITE 22.0000 27.8087 TINOPAL FLUORESCER 0.3000 0.3792 MISC. SOLIDS 0.2018 0.2551 HOLE* 20.8882 TOTAL 100.0000 100.0000 to be post dosed ('6184 47 The compositions of Example I, II, III and IV A through F all use separate mixing of the anionic and nonionic actives.

Example IVG is a prepared neutralized blend. In Example I, II, III and IV A through F, the surfactant mixtures were prepared as taught herein. Premanufactured or prepared blends either neutralized or not could be employed in place of the individual addition.

The blends may be prepared as follows: 00 00 0 Oe 0 0 *00 *000,

LAS:

NI:

Sodium Salt of Alkylbenzene su.fonic acid (Stephan trademark Bio-Soft S-100) Nonionic surfactant (C-C,I alcohol ethoxylates), Shell trademark Neodol 25-7 Nonionic surfactant alcohol ethoxylates), Shell trademark Neodol 25-3 liquid phase N13EO: gel formation 0 s 4 o~C I _1 II C6184 48 EXAMPLES V-VII a a p* S a *r a 5 *9* S. SW 55 S. The neutralized mobile liquid surfactant mixture listed in Example V is prepared by mixing the nonionic surfactant with the indicated amount of concentrated aqueous sodium hydroxide solution (50 and subsequently mixing with alkylbenzene sulfonic acid, Stepan Bi--Soft S-100. Examples V-VII indicate that a higher NaOH content maintains the liquid state for a higher level of water present in the composition.

The percentages reported in the following Table are based on the final total content of materials.

Example V VI VII by weight) LAS 43.0 35.3 27.5 NI 43.6 35.8 27.8 Water 10.4 24.6 33.0 NaOH (100%) Excess 3.0 4.3 11.7 Phase L L L at room temperature EXAMPLES VIII-X The following liquid surfactant mixtures are prepared by mixing the nonionic surfactant with concentrated aqueous sodium hydroxide solution (50 in an amount stoichiometric to the alkylbenzene sulfonic acid plus the excess quantity of NaOH solution. This mixture is then mixed with the alkylbenzene sulfonic acid. The viscosity is I I I ('6184 49 measured by a Contraves Rheomat model 108E at room temperature. Examples VIII-X demonstrate the effect of the excess of sodium hydroxide in reducing the viscosity of the surfactant compositions.

a, Go *r a 10' a

S

9* *e a o a.r 00 0 *94.

*0*G *0 a 0.a 0900 a 0 Example VIII IX X by weight) LAS 57.1 54.5 52.1 NI 28.6 27.1 25.9 Water 12.1 13.8 15.4 NaOH (100%) Exceed 2.4 4.6 6.6 Shear Rate, 1/sec 9.85 9.85 9.85 viscosity, cP 4120 532 537 EXAMPLES XI-XV a a..

The following mobile liquid surfactant mixtures are prepared by mixing the nonionic surfactant with concentrated aqueous sodium hydroxide solution (50% w/v) in an amount which is slightly less than stoichiometric to the alkylbenzene sulphonic acid, adding the alkyl benzene sulphonic acid and then a small amount of a 50% sodium hydroxide solution to bring the pH to a value of about 8. Due to the exothermic neutralization reaction, the temperature is raised to about 80 0

C.

Finally, the indicated amount of the fatty acid are added to the mixture.

-I

C'6184 50 Example XI XII XIII XIV XV by weight) Nonionic.3EO 21.14 20.50 19.86 19.23 18.60 Nonionic.7EO 21.15 20.51 19.87 19.24 18.61 NaOH 11.18 10.84 10.50 10.17 9.84 ABS (acid) 45.93 44.55 43.16 41.80 40.52 NaOH 0.60 0.58 0.56 0.54 0.53

C

16

-C,

1 Fatty Acid 0.0 3.02 6.05 9.02 12.00 *4 4* 4 9.

4 4 0O o. 0 4*94 4 4 44 4 S ~4* The pH of the mixtures of Examples 7 at a temperature of about 80 0

C.

XII-XV was between 5.5 and :0.

.0 90 It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in the light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and the scope of the appended claims.

4 0* Scei

Claims (9)

1. A process for preparing by spray-drying, washing powders comprising 5 to 50% anionic active, 1 to 50% nrnionic active and 5 to 70% of a builder selected from the group consisting of zeolite, sodium carbonate and mixtures thereof, comprising preparing under agitation a anionic-nonionic active mixture containing water, a nonionic active, an anionic active and optionally a viscosity adjuster wherein the anionic active is incorporated as: i) the acid form of an anionic surfactant and the mixture further contains a neutralising agent whereby the S* anionic surfactant is formed in situ neutralisation of the said acid form; and/or 0e ii) an anionic surfactant; ngg to said anionic-nonionic active mixture a builder and optionally other detergent adjuvants to form a final slurry ,Ca. mixture having a water content not in excess of about 35% by weight, a viscosity of 1000 x 10 to 20,000 x 10' Pa.s (1000 to 20000 cps) measured at a shear rate of 17 to 18 sec' and a temperature of 57.2 to 90.5 0 C (1350 to 195 0 F) and spray- drying the said final mixture. 9

2. A process according to claim 1 comprising: 9 A. preparing under agitation a mixture of water, optionally a viscosity adjuster and at least sufficient alkali metal hydroxide to result in neutralisation of the acidic form of said anionic active; II I C6184 52 B. adding under said agitation to said mixture, sufficient nonionic active to prepare said powder, thus resulting in a nonionic active mixture; C. adding under said agitation, to said nonionic active mixtr s a sufficient amount of the acidic form of said anionic active to result in said powder, thus forming an anionic-nonionic active mixture; D. then adding to said anionic-nonionic active mixture under sufficient agitation sufficient builder and other detergent adjuvants to result in said final powder, thus forming a final slurry mixture, said final mixture having a maximum amount of 35% water; E. optionally adding a viscosity adjuster, in an amount of from 0 to 50% of said mixture, at any time during the slurry process to result in a viscosity of the final 2.0 slurry mixture of 1000 x 10 to 20,000 x 10 3 Pa.s (1000 to 20,000 cps) measured at a shear rate of 17 to 18 sec' and a temperature of 65.5 to 90.5 0 C (1500 to 195 0 F); F. then adjusting, if necessary, the temperature of said final mixture to 57.2 to 90.5 0 C (135 0 F to 195 0 F) and spray-drying said final mixture.

3. A process according to claim 1 comprising: A. preparing under agitation a mixture of water, optionally a viscosity adjuster, optionally sufficient VT _I I I C6184 3 alkali metal hydroxide to result in neutralisation of the acidic form of desired adjuvants and a prepared surfactant blend containing anionic and nonionic surfactants thus forming an anionic-nonionic active mixture, said blend containing 10% to 80% anionic surfactant, 10% to 80% nonionic surfactc it and 0% to water; B. maintaining the temperature of said anionic-nonionic mixture below about 93.3 0 C (200 0 F); C. then adding to said anionic-nonionic active mixture under sufficient agitation sufficient builder and other detergent adjuvants to result in said final powder, thus forming a final slurry mixture, said final mixture having maximum amount-of 35% water; D. optionally adding a viscosity adjuster, in an amount of S! from 0 to 50% of said mixture, at any time during the 2 slurry process to result in a viscosity of the final slurry mixture of 1000 x 10' to 20,000 x 10 3 Pa.s (1000 to 20,000 cps) measured at a shear rate of 17 to 18 sec I and a temperature of 65.5 to 90.5 0 C (1500 to 195 0 F); E. then adjusting, if necessary, the temperature of said final mixture to 57.2 to 90.5 0 C (135 0 F to 195 0 F) and S' spray-drying said final mixture.

4. A process according to any preceding claim wherein the temperature is maintained below 93.3 0 C (200 0 F). I C6184 A process according to any preceding claim having an anionic to nonionic ratio of about 1:3 to 3:1.

6. A process according to any preceding claim wherein said final slurry mixture has a water content of 10% to about

7. A process according to any preceding claim wherein sufficient agitation is achieved with an impeller wherein said final slurry has a flow with a Reynolds number of 1 to 10,000 in the mixer.

8. A process according to claim 2 in which steps A, B and C may be performed in any order.

9. A slurry as defined in claim 2, step E or claim 3 step D. DATED Signed forl a inao behalf of UNILEVER PLC UnleverAstralia Limited O B. F. JONES, 'mp Secretary.) ee I INTERNATIONAL SEARCH REPORT Inter ml Applca on No PCT/EP 93/02340 A. CLASSIFICATION OF SUBJECT MATTER IPC 5 C11D11/02 C11D17/06 According to Internatonal Patent Classficaton (IPC) or to both national classfication and IPC B. FIELDS SEARCHED Minimum documentation searched (dassification system followed by classification symbols) IPC 5 C11D Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practical, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category Ctation of document, with indication, where appropnate, of the relevant passages Relevant to claim No. A EP,A,O 265 203 (UNILEVER) 27 April 1988 1-10 see page 3, line 3 line 47; claims 4-7; examples US,A,4 923 630 cited in the application A EP,A,O 061 296 (UNILEVER) 29 September 1-10 1982 see example US,A,4 637 891 cited in the application A FR,A,2 568 584 (KAO CORP.) 7 February 1986 1-10 see the whole document A EP,A,0 259 741 (HENKEL) 16 March 1988 1-10 see page 3, line 9 line 32; claims Further documents are listed in the continuation of box C. Patent family members are listed in annex. Speial categories of ated documents: "T later document published after t the ternatonal filing date A document defining the gneral state of the art which is not ted undtand the pnncple or theory undcryng the considered to be of particular relevance invention earlier document but published on or after the international "X document of partcular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventve step when the document is taken alone which is ated to establish the publication date of another "Y document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referrng to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published pnor to the international filing date but m the art. later than the pnority date claimed document member of the same patent family Date of the actual completion of the International search Date of mailing of the mtemational search report

14. 12. 93 23 November 1993 Name and mailing address of the ISA Authorized officer European Patent Office, P.B. 5818 Patentlaan 2 NL 2280 HV Rilswilk Tel. (+31-70) 340-2040, Tx. 31 651 epo n GRITTERN A Fax 3170) 340-3016 GI N, A Form PCT/ISAJ10 (lecond lhet) (July 1992) page 1 of 2 INTERNATIONAL SEARCH REPORT Intct iOail Application No PCT/EP 93/02340 C.(Continuauon) DOCUMENT'S CONSIDERED TO BE RELEVANT Category jCitation of dloctimenl, with tidication, where appropriate, of the rclevant pazaages JRelevant to claim No. EP,A,0 270 240 (UNILEVER) 8 June 1988 see claims; examples EP,A,0 228 011 (HENKEL) 8 July 1987 see page 3, line 39 page 4, line examples 1-10 1-10 I I_ I Form PCT/15A1210 (coninuation of iecond Shoot) (JuY 1992) page 2 of 2 INTERNATIONAL SEARCH REPORT Intel in~ Applewtof No intornuuon on pAtent family mabr PCT/EP 93/02340 Patent document Publication IPatent family Publication cited in search report dax-e mcmbcr(s) Idate EP-A-0265203 27-04-88 AU-B- 601228 06-09-90 AU-A- 7978687 21-04-88 CA-A- 1302195 02-06-92 JP-A- 63110292 14-05-88 US-A- 4826632 02-05-89 US-A- 4923636 08-05-90 US-A-4923630 08-05-90 US-A- 4867951 19-09-89 EP-A-0061296 29-09-82 AT-T- 10010 15-11-84 CA-A- 1182372 12-02-85 US-A- 4637891 20-01-87 US-A-4637891 20-01-87 AT-T- 10010 15-11-84 CA-A- 1182372 12-02-85 EP-A,B 0061296 29-09-82 FR-A-2568584 07-02-86 JP-A- 61042598 01-03-86 JP-A- 61066798 05-04-86 0E-A- 3528190 13-02-86 GB-A,B 2166452 08-05-86 EP-A-0259741 16-03-88 IJE-A- 3630533 10-03-88 CA-A- 1298163 31-03-92 JP-A- 63069893 29-03-88 US-A- 4820448 11-04-89 EP-A-0270240 08-06-88 AU-B- 602932 01-11-90 AU-A- 8041687 05-05-88 CA-A- 1303938 23-06-92 JP-A- 63122797 26-05-88 EP-A-0228011 08-07-87 DE-A- 3545947 02-07-87 JP-A- 62158800 14-07-87 US-A- 4849125 18-07-89 Form PCT/ISA/210 (patent family anexa) (July 1992)