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Publication numberUS3868336 A
Publication typeGrant
Publication date25 Feb 1975
Filing date6 Aug 1973
Priority date11 Mar 1971
Also published asCA962158A1
Publication numberUS 3868336 A, US 3868336A, US-A-3868336, US3868336 A, US3868336A
InventorsFerreri Paul, Mazzola Louis R
Original AssigneeLever Brothers Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for improving flowability of detergents
US 3868336 A
The caking and flow-inhibiting properties imparted by the external incorporation of an oily detergent improver on the particles of a heat-dried detergent composition, are inhibited by a porous or finely divided flow-promoting agent, also applied externally.
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Description  (OCR text may contain errors)

United States Patent Mazzola et al.

PROCESS FOR IMPROVING FLOWABILITY OF DETERGENTS Inventors: Louis R. Mazzola, Mahwah; Paul Ferreri, Allendale, both of NJ.

Lever Brothers Company, New York, N.Y.

Filed: Aug. 6, 1973 Appl. No.: 385,785

Related U.S. Application Data Continuation of Ser. No. 123,313, March 11, 1971, abandoned.


U.S. Cl 252/527, 252/135, 252/139, 252/140, 252/159, 252/DlG. 2, 252/DlG. 11, 252/D1G. 15

Int. Cl Clld 3/066 Field of Search 252/527, 140, 546, 155, 252/112, 382, 383

References Cited UNITED STATES PATENTS 4/1952 Durgin 252/140 FOREIGN PATENTS OR APPLICATIONS 698,560 11/1964 Canada 252/139 Primary Examiner-Leland A. Sebastian Attorney, Agent, or FirmLever Brothers Company [57] ABSTRACT The caking and flow-inhibiting properties imparted by the external incorporation of an oily detergent improver on the particles of a heat-dried detergent composition, are inhibited by a porous or finely divided flow-promoting agent, also applied externally.

7 Claims, 3 Drawing Figures PROCESS FOR IMPROVING FLOWABILITY OF DETERGENTS This is a continuation, of application Ser. No. 123.313. filed Mar. ll, l97l, now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is concerned with Howpromoting agents, for the purpose of lessening. or eliminating caking. stickiness. and oiling out. such as would be encountered when an oily liquid detergency improver is applied to the particles of a particulate detergent composition in the absence of the flow-promoting agent.

Specific types of detergent compositions and oily liquid detergency improvers to which the present invention is applicable are exemplified in copending applications Ser. Nos. 721.084 filed Apr. I2, 1968 now abandoned. and 45.239 filed June 10. 1970 now abandoned, both assigned to the same assignee as the present application.

The conventional detergent composition having therein an anionic or nonionic detergent and a polyphosphate imparts a level of detergency within ranges regarded usual in the art. The detergency has been improved beyond the accepted levels. as disclosed in the aforementioned applications. by the addition of one or more detergency improvers, comprising the ethylene oxide adducts of C,.C substantially unbranehed alkanols having a deficiency of ethylene oxide as compared with the ethylene oxide content of adducts having detergent properties. Other detergency improvers are also effective, as described hereinafter.

Without the use ofa flow-promoting agent. caking of the detergent composition containing the detergency improvers of the invention, along with stickiness of the detergent product in the carton and oiling out. or seepage of the oily detergency improver from the packed product into the carton material has been a problem. No oiling-out or flow problems have been encountered with nonionic detergent compositions of the type disclosed in the present application in the absence ofa detergency improver of this invention, probably because of the greater hydrophilic properties imparted by the higher ethylene oxide content of the nonionic detergents as compared with the more hydrophobic or oily properties characteristic of the detergency improvers having comparatively low ethylene oxide contents.

2. The Prior Art The caking of detergent or other compositions, or the interference with free-flowing properties by the presence of water or oily substance has always presented a problem, and this problem has received considerable attention in the art, as shown in the summary which follows.

US. Pat. No. 2.594.257 discloses the use of attapulgite. kieselguhr. and bentonite in a nonionic detergentpolyphosphate composition to render the composition non-oily and free flowing. This patent teaches that a condensate of a tertiary alkyl mercapatan and 5 to 40 moles ethylene oxide per mole of mercaptan in a detergent composition readily strikes through the paper package in which the product is wrapped, and that this is prevented by the incorporation of attapulgite into the product.

The nonionic condensate to which this patent is applicable. namely a condensate of a tertiary alkyl mercaptan and 5 to 40 moles ethylene oxide. is a detergent and contains more than the 5l/r maximum ethylene oxide content permissible in applicants detergency improvers, and compositions containing this nonionic are improved as to oiling out and free-flowing characteristics by attapulgite. In contrast. applicants nonionics are detergency improvcrs having relatively short ethylene oxide chains. that is, not over about 5 lil ethylene oxide by weight. and compositions containing these nonionics are inadequately improved as to flow properties by attapulgite.

The coating of detergent particles with a liquid. water-insoluble detergency improver is known. and disclosed in U.S. Pat. No. 2.768.095. This patent discloses the use of a fluidized bed technique for carrying out the coating process. but the patentee gives no indication that a problem exists regarding stickiness or adverse effect of the detergency improver on flow properties. and consequently there is no disclosure in the patent of the use of a flow-promoting agent.

US. Pat. No. 3.l37.630 describes a process wherein finely divided silicas. rice starch. etc. are added for anti agglomerating purposes to a congealing liquid such as hexane. xylene. etc. followed by droplets of gelatin solution. The mixture thus formed is further processed to make a dry. solid, gelatin particle product. The oily ingredient (cg. hexane) does not remain in the product. and the silica or other anti-agglomerating agent are employed as a suspension in the oily ingredient con taining aqueous droplets of gelatin solution. and in these respects the present invention is distinguished from the disclosure of this patent.

US. Pat. Nos. 3.494.874 and 3.494.875 disclose porous silicas described as suitable for absorption and adsorption. However the pore volumes of these silicas are far below the minimum of 2 ml. per gram required by the present invention.

US. Pat. No. 2.730.507 discloses a process wherein there is added to the particles of a particulated or flaked soap product. a powdered alkaline orthophosphate and carbonate followed by oleic. or the like. acid (an oily material). The problem described in this patent is one of dusting, which was solved by the in situ formation ofa soap on each ofthe particles. the problem and its solution being irrelevant to the present case.

S. A. Mitchell, The Surface Properties of Amor phous Silicas. Chem. and Ind. pp. 924-933 (1966). discusses the physico-chemical properties of porous silicas having pore volumes as high as 4 ml. per gram.

As shown in the foregoing summary. the art prior to the instant invention. other than the aforementioned copending applications. had not progressed to the point of externally applying a detergency improver to the particles of a spray-dried detergent. or of recognizing or solving the eaking problem associated with the use of the aforementioned oily detergency improver.

SUMMARY OF THE INVENTION It has now been discovered that the undesirable characteristics of caking. stickiness. and oiling out imparted by the oily detergency improvers of this invention can be greatly lessened or eliminated by the addition to the product of a flow-promoting agent. as described hereinafter.

it is therefore an object of the present invention to provide a substantially non-caking particulate composition having good flowability. and containing an oily substance on the particles thereof.

It is another object of the invention to provide a substantially non-caking and free-flowing particulate detergent composition having an oily detergency improver on the surface of the particles thereof.

it is a further object of the invention to provide a detergent composition in particulate from having present therein an externally applied oily detergency improver. and a flow-promoting agent to counteract the caking and tackiness imparted by the oily detergency improver.

It is still another object of the invention to provide a process for making a particulate detergent composition having improved detergency comprising admixing with the particles of detergent composition a finely divided flow-promoting agent and an oily detergency improver.

These and other objects of the invention will become apparent the description proceeds.

No criticality has been observed with respect to any particular detergent species or detergent builder. and the utility of the present invention does not depend upon the presence of any specific detergent or builder system. Accordingly the present invention in its broad est aspect relates to a composition having detergent properties. containing a detergent. an oily detergency improver. and a flow-promoting agent.

In a further aspect of the invention there is provided a particulated detergent composition comprising an an ionic detergent. having admixed therewith subsequent to preparation a flow-promoting agent and an oily liquid detergency improver.

In another aspect of the invention there is provided a substantially free-flowing particulate detergent composition having three essential components. namely l particles of a detergent base composition containing an anionic or nonionic detergent. said detergent base composition being present in a proportion sufficient to provide about 0.5% to about 35% by weight. whole composition basis. of said anionic or nonanionic detergent. (2) particles of a flowpromoting agent present in the proportion of about 0.5% to about l7r by weight. whole composition basis. and sufficient to improve the flow characteristics of said detergent composition to the extent of at least a 50 percent pour. and (3) a detergency improver comprising a nonaqueous oily liquid substance. present in the proportion of about 1% to about 35% by weight. whole composition basis. and sufficient to improve the detergency characteristics of the detergent.

When the anionic detergent is a soap. the proportion thereof may be as high as about 80%. The balance of the composition may comprise water. detergent builders. and the well-known detergent adjuvants disclosed hereinafter as being conventionally employed.

in a more narrow embodiment of the invention there is provided a detergent composition suitable for use in automatic dishwashers. A composition of this type contains a very low proportion of organic detergent. for ex ample 0.5% or less of an anionic detergent, suitably dis odium-4-dodecyl-2,4'-oxydibenzenesulfonate. or about 0.5% to 3% of a nonionic detergent.

The invention also provides a processs for improving the flowability of a particulate composition having detergent properties in an aqueous medium. and containing an oily detergency improver which normally adversely affects the flow properties of said composition. and which normally tends to be desorbed from said composition and to stain a container holding said composition. comprising after-treating said composition with a particulate flow promoting agent selected from the group of siliceous substances the particles of which have a pore volume of at least 2 milliliters per gram. and non-siliceous substances as more fully described hereinafter. The particles of the flow-promoting agent are external to the particles of the composition having detergent properties.

The particulated detergent composition may be prepared immediately prior to the addition of the flowpromoting agent or may be prepared in advance. The composition need not contain a detergent builder. al though the presence of a detergent builder is preferable. Accordingly the process also comprises preparing an intimately mixed particulate detergent composition comprising an anioic or nonionic detergent. and one or more detergent builders of the types described hereinafter. then blending with said detergent composition a flow-promoting agent selected from the types described hereinafter. The admixture of the flow promoting agent renders the mixture olephilic. thereby accepting the subsequent addition of a non-aqueous oily detergency improver.

In another aspect. the process of the invention comprises blending with a previously prepared spraydried detergent composition having present therein an anionic or nonionic detergent. with one or more detergent builders such as those hereinafter described. a particulate flow'promoting agent thereby rendering the mixture oleophilic. then blending with said mixture a detergency improver comprising an oily liquid substance.

The invention also embodies a process wherein a particulate detergent composition is fed either batchwise or continuously into a substantially horizontal revolving drum. a particulate flow-promoting agent admixed therewith while the contents of the drum are tumbling. and subsequently an oily liquid detergency improver sprayed onto the tumbling mixture.

The present invention is applicable to any detergent composition containing an anionic or nonionic detergent as the active detergent component. The detergent compositions usually contain the well-known inorganic and/or organic builder salts. examples of which include tetrasodium and tetrapotassium pyrophosphate. pent-a sodium and pentapotassium tripolyphosphate. sodium or potassium carbonate. sodium or potassium silicates having an SiO :Na O ratio of about 1:1 to about 3.221. hydrated or anhydrous borax. sodium or potassium sesquicarbonate. the sodium or potassium aminopolycarboxylates. such as nitrilotriacetates. N-( 2- hydroxyethyl)-nitrolodiacetates. ethylenediamine tetraacetates. hydroxyethylenediamine tetraacetates. diethylenetriamino pentaacetates, dihydroxyethyl glycine. phytates. polyphosphonates such as sodium or potassium ethanel -hydroxyl l -diphosphonate. etc.

Also useful are other organic detergent builders such as the sodium or potassium oxydisuccinates. sodium or potassium oxydiacetates. carboxymethyloxysuceinates. hydrofuran tetracarboxylates. ester-linked carboxylate derivatives of polysaccharides. such as the sodium and potassium starch maleates. cellulose phthalates. glycogen succinates. semi-cellulose diglycolates. starch. oxidized heteropolymeric polysaccharides, etc.

Other materials which may be present in the detergent compositions of the invention in minor amounts are those conventionally employed therein. Typical examples include the well-known soil suspending agents, corrosion inhibitors, dyes, perfumes, fillers, optical brighteners, enzymes. suds boosters, suds depressants, germicides, anti-tarnishing agents, and the like. The balance of the detergent compositions may be water.

Examples of anionic detergents useful in accordance with the invention are the higher alkyl mononuclear aromatic alkali-metal sulfonates, such as alkylbenzenesulfonates having about 9 to about 18 carbon atoms in the alkyl group wherein the alkyl group is derived from polypropylene as described by Lewis in US. Pat. No. 2,477,382, or wherein the alkyl group is derived from kerosene, as described by Flett in US. Pat. No. 2,390,295, and Rubinfield in US. Pat. No. 3,320,l74, or wherein the alkyl group is a striaght chain and the benzene nucleus is randomly positioned along the alkyl chain, as described in Baumgartner US. Pat. Nos. 2,723,240, and 2,712,530, and in US. Pat. No. 2,972,583, or wherein the alkyl group is a hexene dimer or trimer as in McEwan US. Pat. No. 3,370,100, or wherein the alkyl group is derived from alphaolefins, as in Swenson US. Pat. No. 3,214,462,

Also there may be employed primary and secondary alkyl sulfates, ie., RO-SO -compounds wherein R represents an alkyl group having from to 20 carbon atoms such as sodium, potassium and magnesium lauryl sulfate, stearyl sulfate, coconut alkyl sulfate and tallow alkyl sulfate; N-long chain acyl N-alkyl taurates and the salts thereof wherein the long chain is from 8 to 20 carbon atoms such as sodium oleoyl methyl taurate, so-,

dium palmitoyl methyl taurate, sodium lauroyl methyl taurate and the corresponding acyl ethyl taurates; long chain alkyl-oxyethylene sulfates wherein the long chain is from 8 to 20 carbon atoms such as sodium or potassium laurylpolyoxyethylene sulfate, sodium lauryloxyethylene sulfate and sodium cetylpolyoxyethylene sulfate; long chain alkyl aryl oxyethylene sulfates wherein the long chain is from 8 to 20 carbon atoms such as ammonium sodium or potassium nonyloctyland tridecylphenoxy monoand polyoxyethylene sulfates; long chain acylisethionates wherein the long chain is from 8 to 20 carbon atoms such as sodium or potassium lauroylstearoyl isethionate; alkaneor alkanesulfonates containing 8 to 20 carbon atoms in the alkane or alkene group such as sodium, potassium or triethanolamine octane-, decane-, tetradecane-, octadecanesulfonate and octene-, decene-, tetradeceneand octadecenesulfonate; alkoxyhydroxyalkanesulfonates wherein the long chain is 8 to 22 carbon atoms such as lauryloxyhydroxypropanesulfonate, stearyloxyhydroxyethanesulfonate and tallowoxyhydroxypropanesulfonate; and fatty acid monoglyceride sulfates wherein the long chain is 8 to 22 carbon atoms such as lauric-, myristic-, palmitic and stearic monoglyceride sulfates; alphasulfo soap, such as the disodium salt of alpha-sulfo fatty acids wherein the fatty acids are derived from tallow, the sulfosuccinates, such as dioctyl sulfosuccinate, sodium salt, the Z-hydroxyalkyl methyl taurines, such as 2-hydroxytetradecyl methyl taurine, the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, such as the sodium salt of sulfated coconut oil monoglyceride, and compounds known as "Medialans, which are amido carboxylic acids formed by condensing fatty acids of C -C chain 6 length with sarcosine, CH NH CH COOH. Generally the alkali metal and basic nitrogen radical salts are employed.

The well-known soaps may be employed. Operable soaps within the present invention are the sodium and potassium salts of acyclic monocarboxylic acids having chain lengths of about 8 to about 22 carbon atoms. Par ticularly useful are the salts of unsubstituted fatty acids derived from natural triglycerides, such as tallow, palm oil, cottonseed oil, olive oil, lard, rapeseed oil. etc, and the so-called high-lauric oils," generally exemplified by the tropical nut oils of the coconut oil class, includ ing in addition to coconut oil, palm kernel oil, babassu oil, ouri curi oil, tucum oil, cohune nut oil. and murumuru oil, and for present purposes, ucuhuba hutter, a triglyceride high in myristic acid esters. A partic ularly useful soap is one prepared from a mixture of about 807! tallow and about 20% coconut oil,

Other suitable anionic synthetic detergents for use in the present invention can be found in the literature, such as Surface Active Agents and Detergents" by Schwartz, Perry and Berch published by lnterscicnce Publishers, the disclosures of which are incorporated by reference herein.

Among the nonionic detergent materials that can be emloyed in the detergent compositions of the invention are the Pluronics (trademark ofthe Wyandotte Chemicals Corp), formed by condensing propylene oxide with propylene glycol to a molecular weight of about 6002,500 to form a base followed by condensing ethylene oxide to this base to the extent of about 30 to about 909 1, total molecular basis. US. Pat. Nos. 2,674,619 and 2,677,700 describe operable nonionic compounds; compounds formed by the simultaneous polymerization of propylene oxide and ethylene oxide. and containing randomly positioned oxypropylene and oxyethylene groups, and having over 309? ethylene oxide by weight. These and related compounds are described in US. Pat. Nos. 2,979,528; 3,036,l l8; 3,022,335; 3,036,l30, and 3,048,548. alkyl phenols having 6l2 carbon atoms in the alkyl portion, (straight or branched) ethoxylated with 625 molar proportions of ethylene oxide, ethoxylates of fatty alcohols having 8-[8 carbon atoms per mole and 5 to 30 molar proportions of oxyethylene groups, and having at least 52% by weight of ethylene oxide.

Examples of specific nonionic detergent compounds are: branched-chain nonyl phenol condensed with 8l4 molar proportions of ethylene oxide, a mixed -C secondary alcohol (Tergitol l5-S) condensed with 9-l4 molar proportions of ethylene oxide. a mixed (T -C alcohol made by the Oxo process (Neodol 45) condensed with 9-l2 moles ethylene oxide, or a mixture of 65% C and 35% C synthetic straight chain primary alcohols condensed with 9-15 molar proportions of ethylene oxide.

The detergency improving agents ofthe invention are organic substances having substantially no detergent power, and are selected from the group consisting of:

a. condensates of ethylene oxide and monohydric primary or secondary alkanols having about 8 to about 16 carbon atoms, the proportion of ethylene oxide being about 10% to about 5 l%, preferably from about 37% to about 51%, by weight.

The alkanols are substantially unbranched, and may normally have from 0% to about 25%357r by weight of short-chain branching, e.g.. methyl, ethyl, and/or propyl groups. usually on the 2-carbon of the alkanol.

b. polymers of propylene oxide having a molecular weight of about 1,500 to 1,800. These compounds have substantially no ethylene oxide, and are referred to as the polyoxypropylene hydrophobic base to which ethylene oxide is added in the manufacture of Pluronies, a trademark of Wyandotte Chemicals Corporation.

c. ethylene oxide condensates of the hydrophobic base described in (b). said condensates having from about to about ethylene oxide in the molecule by weight. These compounds are available from the Wyandotte Chemicals Corporation under the trademark Pluronics.

d. non-polyoxyalkylene substances such as: diphenyl ether; diethylbenzene; tetrahydronaphthalene; dodecylbenzene; benzene; toluene; xylene; isopropylbenzene', dialkyl phthalates wherein the alkyl group ranges in chain length from C, to C for example dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate. dibutyl phthalate. diisobutyl phthalate, butyl benzyl phthalate, methyl nonyl phthalate'. monoand dialkyl ethers of glycols, such as the monoand dimethyl, ethyl, propyl, butyl, pentyl. hexyl. dodecyl, etc. ethers of ethylene, diethylene, propylene, butyiene. hexylenc, etc. glycols.

The detergency improver is used in an amount sufficient to increase the detergency or cleansing power of the detergent compound, which amount will vary with the nature of the detergent compound and the detcrgency improver. However, the weight ratio of the detergent compound to the detergency improver gener ally ranges from about 20:1 to about 1:4 and more usually from about 5:1 to about 1:1. The detergent compositions generally contain from about 0.59? to about 3571 by weight. preferably about 5)? to about 2557? by weight of the detergent compound. and from about 1% to about 35%, preferably about 291 to about 200 and most suitably about 5% by weight of the detergency improver.

Representative specific ethylene oxide condensates useful as detergency improvers are the ethylene oxide condensates of a polyoxypropylene hydrophobic base having a molecular weight from about 1,500 to about 1,800. said condensates having an ethylene oxide content of about 20% to about 30% by weight, and the ethylene oxide condensates of the primary or secondary substantially unbranched octanols, nonanols. deconols, undecanols, dodecanols, tridecanols, tetradecanols and pentadecanols having an average ethylene oxide content ranging from about 1071 to about 51% by weight. Further examples thereof include the commercially available ethylene oxide adduct ofC -C,;, "oxo alcohol with about Z-methyl branching and having an average ethylene oxide content of 37% by weight. the ethylene oxide adduct of C -C, "oxo" alcohol with about 25% 2-methyl branching and having an average ethylene oxide content of 50% by weight. the ethylene oxide adduct of C C, secondary straight chain alco hol having an average ethylene oxide content of 5171 by weight, and the ethylene oxide adduct of Cy-Cu; (1/1) primary straight chain alcohol having an average ethylene oxide content of 48% by weight.

Particularly preferred are compositions wherein the oily liquid detergency improver is a member selected from the group consisting of dibutyl phthalate, the ethylene oxide adduct of C -C oxo alcohol with about 25% 2-methyl branching and an average ethylene oxide LII content ofabout 37% by weight, and a polyoxyethylene derivative of a reaction product of propylene glycol and propylene oxide having a molecular weight of about 1,500 to 1,800, said ethylene oxide adduct having about 207r to about 3071 ethylene oxide adduct by weight.

The detergency improvers belonging to the class of ethylene oxide condensates resemble in molecular structure the nonionic detergent ethylene oxide condensates. The distinguishing chemical feature is the ethylene oxide content. The detergency improvers of this class have an ethylene oxide content of up to about 519? by weight of the entire molecule. while the nonionic detergents as defined for purposes of the invention have, except for the Pluronics as hereinbefore dc scribed, over 51% by weight ofethylene oxide. The detergency improvers are generally water-insoluble or are only sparingly soluble, and are oily in nature. On the other hand, the detergent ethylene oxide condensates are generally soluble in water and may be incorporated in a detergent crutcher slurry and spray dried with the other ingredients without having an oily effect.

As an illustration of the improvement in detergency effected by the incorporation ofthe oily detergency improver, reference is made in the following data, incorporated herein as presented in the aforementioned copending application Ser. No. 721,084 now abandoned.

Examples of the detergent compositions of the inven tion as formulated prior to the addition of the flowimproving agent and the detergency improver are set forth below as illustrative, but not limitative of such compositions. These detergent formulations are prepared by blending together the recited components and are then tested for detergency or cleansing ability in the Terg O-Tometer test wherein the washing conditions were as follows: VCD (vacuum cleaner dust) cloth (65% Dacron 350? cotton); F; ppm (Z/l Ca /Mg'**1;0.27r concentration of total formulations in washing solution; pH 9.7. For a description of the Terg O-Tometer see Sanders and Lambert, J.A O.C.S, 127 May 1950. pages 153-159. The average reflectance of the washed cloths reported in the tables hereinafter is measured with a Gardner Automatic Color Difference Meter. Model AC-3. ln this test procedure, as used herein, an increase in reflectance readings between the control formulation and the test formulations of more than about 2.6 units is considered to establish significant detergency improvement. since such an increase in whiteness or brightness is readily observable to the naked eye.

The Control Formula A, used in Examples 1-10 be low, contains a water-soluble mixed nonionic-anionic detergent active system and is as follows;

Control Formula A EXAMPLES l6 A comparison of the detergency of Control Formula A with that of Control Formula A modified by replacing sodium sulfate content with 5% of various ethylene oxide-alchol adducts is given below in Table I.

TABLE l Average Reflectance of Washed Cloths (duplicate Example No. runs] Formulation Control Formula A Control Formula A containing the ethylene oxide adduct of C C, oxo" alcohol with approxi mately 2-methyl branching and having an average ethylene oxide content of 64% by weight roi- 5 Control Formula A containing the ethylene oxide adduct of -C secondary straight chain alcohol and having an average ethylene oxide content of 529; by weight 6 Control Formula A containing the ethylene oxide adduct of "oxo" alcohol with about 25% 2-methyl branching and having an average ethylene oxide content ol- 37"? by weight Example 1 above is a control formulation. since it does not contain any of the detergency improvcrs of the invention. Examples 2 and 3 are comparative formulations. Although these two formulations contain ethylene oxide adducts ofC C alcohols, such adducts are outside of the scope of the detergency improvers of the present invention because the ethylene oxide content thereof is greater than about 51% by weight. The average reflectance readings obtained for comparative Examples 2 and 3 differ from that obtained for Control Example 1 by only 1.7 and 2.3 units respectively and hence there is not significant improvement in detergency. However, Examples 4-6 contain various detergency improvers ofthe invention and have increases in reflectance readings compared with Control Example 1 of 4.2, 4.3 and 9.1 units respectively. Such increases in reflectance clearly establish the detergency improving properties of the ethylene oxide-alcohol addncts used in Examples 46 of the invention.

EXAMPLES 7l() In these examples Control Formula A is altered by substituting varying amounts of a representative detcrgency improver of the invention for the same amounts ofthe sodium sulfate component of Control Formula A in order to illustrate the variation in detergency improvcment obtained by varying the amount of detergency improver present. The results are set forth in Table II below.

TABLE ll Average Reflectance of Washed ('loths (duplicate Example No runs] Formulation Control Formula A Control Formula A containing 19 of the ethylene oxide adduct of C -C "oxo" alcohol with approximately 25% Z-metbyl branching and having an average ethylene oxide content of 37'; by weight 9 Control Formula A containing 3% 53b of the ethylene oxide adduct of -c "oxo" alcohol with about 25i Zanethyl branching and liming an average ethylene o\itlc content ol 37"? by weight It] (ontrol Formula A containing 5';

olthe ethylene oxide adducl of C C oxo" alcohol \uth about 2? Z-methyl branching and ha\i|ig an average ethylene oxide content of 379; by weight In Table ll above, Example 7 is a control example while Examples 8]O are illustrative of the detergent compositions in which a flow-promoting agent of the instant invention is advantageous. ln Examples 8-10 the amount of detcrgcncy improver added is 1%. 3? and 571 by weight ofthe formulation so that the weight ratio of detergent compounds to detergcncy improver is 16.6:l. 55:1 and 3.3:] respectively while the in crease in reflectance is a significant 2.8. 7.9. and 10.3 units respectively. The data in Table II, therefore. indicate that the detergency of the detergent composition is increased as the amount of detergency improver is increased relative to the detergent compounds present.

The flow-promoting agents are substances useful within the invention to counteract the caking. stickiness, and oiling out characteristics imparted by the presence of the oily liquid detergency improver. and are selected to be chemically inert to the oily dctergency improver.

Many of the flow-promoting agents of the present invention are of a siliceous nature. and some nonsiliceous compounds are effectivev Among the siliceous compounds are certain silicas having physical characteristics described hereinafter. As examples ofoperable silicas there may be mentioned silica aerogels and xcrogels sold under the trademarks Syloid 244 (acrogel *Syloid 63 and Syloid 65 (xerogels) by the Davison Chemical Division of W. R. Grace and Co., (Cabosil (a trademark of Godfrey L. Cabot, lnc.). Hi-Sil 233. (a trademark of the Pittsburg Plate Glass Co). Aerogcl 500 (a trademark of the J. M. Huber Corp). and Zeothix 90 (a trademark of the J. M. Huber Corp); hydrated silicas such as Zcosyl l!) and Zeofree 80 (both trademarks of the J. M. Huber Corp. and mctallosilieon compounds such as Zeolcx 7A and lcolex 23A (both hydrated sodium silico aluminates. and both trademarks of the .l. M. Huber Corp). Nopak C (calcium alumino silicate. and a trademark of the .l. M. Huber Corp.). Britc-Sorb (a synthetic magnesium silicate. and a trademark of the Amerace-Esna Corp). and Dicalitc 416. a trademark of Grefco. lnc.. described as a fused sodium potassium aluminum silicate geologically defined as an amorphous siliceous material of volcanic origin known as Perlitc.

To be acceptable flow-promoting agents. the siliceous-type flow-promoting agents must have a pore volume of at least 2 ml. per gram. preferably about 2.5 to 4 ml. per gram. Pore volume is the term applied to the volume of the intraparticulatc void space within the particles. The pore volume of some representative siliccous materials are shown in Table III below. It will be noted that attapulgite. known in the art as an oilabsorbent. is considerably inferior to the siliceous ma terials of the present invention.

'a silica aerogel. Sylold Z44 a trademark of the Daiisoii Chemical l)l\l\ltll'\ of W R Grace and (o *a hydrated silica haung a mean particle diameter ol about Zeofree till is a trademark of the] M Huber (orp 'a fused potassium aluminum silicate. lhcalite 41h is a trademark o! tilet'co. Inc

II millimierons.

"a complex hydrated magne ium aluminum silicate A variety of particulate non-siliceous substances, most of which are known in the art as detergent adjuncts, are suitable flow-promoting agents. These may be generally described as water-soluble anti-conglutinant deter gent adjuncts in fine particulate form having a particle size not substantially larger than ZOO-mesh.

The non-siliceous water-soluble anti conglutinant de tergent adjunct may be any water-soluble compound which has utility in detergent compositions and is com patible therewith. To be suitable the adjunct must not alter the pH. or change the foaming or detergent characteristics undesirably. and must be obtainable in particulate form not substantially larger than ZOO-mesh. and itself must not promote eaking or adherence of the product.

Accordingly the non-siliceous water-soluble anticonglutinant detergent adjuncts useful in the present invention comprise condensed phosphate. orthophosphate-. polymeric antiredeposition and suspending. polymeric builder-. and neutral and alkaline monomeric detergent adjuncts.

Among the specific compounds within the abovementioned classes. those in the lists below are representative. It will be understood that acid salts. cations other than sodium. and hydrates. where applicable. may be substituted for the compounds listed. provided that the substitutes are subject to the limitations. and have the properties, set forth hereinabove. Condensed, or calcium-sequestering. phosphates sodium tripolyphosphate tetrasodium pyrophosphate 12 Condensed. or calcium-sequestering. phosphates (Coir tinued) sodium trimctaphosphatc NaPQ. w Kurrols salt hcxasodium tetraphosphate lNaP();.),. hexasodiunt hexametaphosphate ()rthophosphatcs Na HPO,

Na HPO NaH PO. mixtures Polymeric anti-rcdcposition and suspending adjuncts polyvinyl alcohol sodium carboxyntethylcellulosc water soluble salts of interpolymers of methyl vinyl ether and maleic anhydride as described in U.S. Pat. No. 2.702.277

polymeric condensates of ethylene and maleic anhydride. The useful polymers of this class are polyarr hydridcs. both linear and cross'linked. The linear polymers are copolymers made up of units having the structure wherein n is a number from about 3.000 to about 10.000. and having molecular weights from about 380.000 to about 1.250.000. and specific viscositics from about 0.6 to about 2. l. as determined on a l percent solution of the resin in dimethyl formamide at 25C. The suitable cross-linked polymers are in general those prepared by cross-linking the aforementioned lin ear copolymers and have viscosities ranging from about 12.000 to about lb().000 cps as measured on a 1? aqueous solution of hydrolyzed anhydride adjusted to pH 9 with NH oH. at 25C. using a Brookfield Viscometer. No. 6 spindle at 5 rpm. The aforementioned linear and cross-linked copolymers of ethylene and maleic anhydride are considered to be water-soluble for purposes of the present definition. since. although the anhydride form is water-insoluble. it may be solubilized by first hydrolyzing with the aqueous solvent. A dcscription of the ethylene-maleic anhydride copolymers useful in the present invention may be found in Product Information Bulletin No. 1066, published by the Monsanto Chemical Co. Polymeric detergent builders starch. such as corn starch. potato starch. amioca starch. tapioca starch. sago starch. wheat starch. rice starch. and taro root starch oxidized starch or oxidized cellulose wherein at least 20% of the original anhydroglucose units have been ring-cleaved by oxidation to form units each having two carboxyl groups as disclosed in U.S. Pat. No. 2.894,.945. and in copending application Ser. No. 17.893. assigned to the instant assignee sodium carboxymethyl oxysuccinate pentahydrate disodium oxydisuccinate disodium oxydiacetate Neutral or alkaline monomeric salts Na,50. NaCl -Continued Neutral or alkaline monomeric salts lNla B O NaBO Na ClI) NuHCO sodium benzenesulfonate sodium toluenesulfonate sodium xylcnesulfonate sodium eumencsulfonate sodium citrate MgSO,

sodium stearate Particularly effective and desirable flow-promoting agents are sodium tripolyphosphate, tetrasodium pyrophosphate, sodium perborate, polyvinyl alcohol, sodium carboxymethylcellulose, sodium oxydiacetate and sodium carboxymethyloxysuccinate pentahydrate.

The proportions of flow-promoting agents useful in the present invention will vary for different detergency m-provers and with the specific flow-promoting agents used to insure that sufficient is used to impart satisfactory flow properties. Usually about 2% to about 8% of the flow-promoting agent is satisfactory, although the proportions may vary from about 0.5% to about l7r. In general the higher the proportion of detergency im prover used, the more flow-promoting agent is requires. From about 04 part to about 10 parts, and preferably from about 0.5 part to about l part by weight of flow-promoting agent for each part by weight of detergency improver is satisfactory.

The beneficial effects of the flow-promoting agents of the invention are manifested in the improved pouring characteristics of the detergent powder containing a flow-promoting agent as compared with the same detergent powder in which the agent is absent The minimum proportion of the flow-promoting agents varies depending upon the particular flowpromoting agent and the detergency improver used. The suitability of a substance as a flowlpromoting agent and the proportions thereof may readily be determined by simply preparing a product as described herein and determining whether the product has a percent pour of at least 50%.

The How or pouring characteristics are determined as follows:

A powder to be tested is placed in a detergent carton measuring 2% inches X 8 7/l6 inches to a level I inch from the top of the carton. The weight of the powder in the box is determined and the open box is then tilted on its narrow edge through an angle, 100 from the vertical. The percentage by weight of powder which flows from the carton undisturbed is determined. This figure is the percent pour. Powders having flow characteristics such that the percent pour is at least about 50% are considered satisfactory.

In the process of preparing the composition of the present invention a particulate detergent composition is prepared in any desired fashion. It may be spray dried, drum dried, spray cooled. drum cooled, agglomerated. dry blended, or prepared in any manner to provide a particulate composition having detergent properties. The particles thereof are placed in a rotating drum, twin-shell blender, fluidizer, or other desired mixing device. While the particles of detergent composition are tumbling or are otherwise in motion, the oily detergency improver and the flow-promoting agent are added in any suitable manner, for example by spraying from one or more spray nozzles onto a tumbling bed of detergent particles in a rotating drum. The finely divided flow-promoting agent may be added in any de sired manner, by dusting. by adding all the agent at one time in a batch process, preferably by applying as a dust to the detergent particles. It is preferred as an order of addition to add the finely divided flow-promoting agent to the detergent particles, and to mix thoroughly to ob tain uniform distribution prior to adding the oily deter gency improver, although if desired, the oily detergency improver may be added first. or may be first mixed with the flow-promoting agent, and the mixture added to the detergent particles; or the detergent particles may be static while the detergency improver and flow-promoting agent are added. followed by thorough mixing.

Normally the detergency improver is added under non-aqueous conditions, that is, water is not added to the detergent particles along with the oily detergency improver.

When the detergent base is prepared by dry blending the components, the dry blend may contain a detergent-building amount of tripolyphosphate or other builder such as for example sodium carbonate. monosodium oxydisuccinatc. sodium carboxymethyl oxysuc cinate pentahydrate. the flow-promoting agent subsequently added may also be one of these same builder substances. However the builder substance employed in detergent-building amounts will have relatively large particles, usually of the order of about 60-mcsh or larger, to avoid fines" in the product and will not possess an important characteristic of a flow-promoting agent of the invention, namely a particle size not sub stantially larger than about ZOO-mesh. and will not function as a flow-promoting agent. The flow promoting agent may be added at any time during the mixing of the components in the specific instance of a dry-blending operation. However when incorporated into a particulate detergent base, the addition must be in the nature of an after-treatment if the flow promoting properties of the agent are to be utilized.

The term oleophilic" as used herein refers to the property of absorbency with respect to the transfer of oily liquids from the free state into the pores of, or to the surface of, the flow-promoting agent.

The term "oily" refers to the hydrophobic character of the liquid detergency improvers used within the present inventionv The substances described herein as oily" are in general insoluble or only sparingly soluble in water, and behave as an oil when applied to the sur faces of particles of a detergent composition, adversely affecting the flow properties of the particles,

The term finely divided" refers to particle size, in particular to the particle size of the flow-promoting agents which in accordance with the present invention, may be within the range of about 0.0] micron to about 74 microns (ZOO-mesh), and not substantially larger than ZOO-mesh, that is, at least ofthe particles pass through a 200-mesh screen.

The term non-aqueous" used herein with reference to the detergency improver denotes the substantial absence of water associated with the addition of the oily detergency improver to the particulate detergent composition.

The term non-siliceous water-soluble anti conglutinant detergent adjunct refers to those flowpromoting agents within the invention whose molecules are free from silicon. are substantially soluble or dispcmm Hy persible in water. are compatible with soaps and deter- Weight gents, and which improve the flow properties of particulated detergent compositions having an oily deterg gi s' a 71.72 l 0 mm tripo yp osphate 14.35 gency improver added to said composition external to polyvinyl alcohol 9b] the particles thereof. colorant The term after-treating refers to admixing the Nonmnf F of fatty alcohols having lti-ltl carbon atoms l flow-promoting agent and the detergency improver eiand about s50; total molecule basis. of i ther separately or premixed, with a detergent composi to "W' Oxide! l 4.30 tion which has been preprepared in particulate form.

As a further illustration of the invention, reference is made to the following Examples, which are to be considered as illustrative only and not to be construed as lmposmg y llmllatlon p the SCOPe of Said The data set forth in Tables IV to Vl demonstrate the variations encountered in the flow-promoting efficien EXAMPLES H46 cies of some of the flow-promoting agents of the present invention. A prepared mechanical mixture of so- A detergent base having the following composition is dium pal-hora: powder, Sodium tripolyphospham Spray dried yvinyl alcohol (PVA), with small amounts of colorant and nonionic detergent having the PVA Premix" composition hereinbefore described is effective as 21 Percent By flow-promoting agent with a detergcncy improver i wclghl which is a condensate of a long-chain alcohol and 3 Sodium ulkylbenzenesummm M0 molar proportions of ethyleneoxidc in the ratios of Sodium tripolyphosphate 49.00 about 0.4 to 1 part by weight of the former to 1 part of Sodium silicate solids (SiO :Na O 2.4) 3 ill) the uncr (Tabb: IV) Sodium carboxymethylcellulose 0.33 H l Sodium map f u f u acid\ 130 Syloid 1.44. a silica aerogel, is ettectwe with the g i k h m above-mentioned condensate in the proportions of l l r t 3 1:? Ka i VH7 about O f to 10 parts by weight of the silica aerogel to Miscellaneous inert matter associated i part til the CUIldCtlSfllC [Table V).

The same silica aerogel is somewhat less effective Water DUO V I when the detcrgency improvcr is Pluronic L412. In this combination the ratio is about 0.6 to ill parts by weight of the aerogel to 1 part of Pluronic L-oI.

To the spray-dried particles of this base in a rotating Dicaliie 4 l 6 is effective as a flow-promoting agent in drum is added a pour-promoting agent. and after mix the ratio of about 0.6 to about it) parts to each part of ing, an oily liquid detergency improver is sprayed on the aforementioned long-chain alcohol-ethylene oxide the mix while tumbling in the rotating drum. The pourcondensate but not effective at all when the detergency promoting agents and detergency improvers tested are improver is Pluronic L-fit) or L-62 (Table Vi). identified in Tables IV to Vl, below. Examples 4749 illustrate that attapulgite. a well- When polyvinyl alcohol (PVA) is employed in the known oil absorbent. does not meet the requirements composition, it is first diluted with detergent ingredias set forth herein for imparting acceptable flowability.

m to in ur h m g ne istri u i n. as h wn in the percent pour values of the detergent particles of th fOllOWifig COmPOSiIiOW referred I0 hbfcinflfler 88 a these examples being under the low acceptable limit of PVA Premix.

TABLE IV Flow-Promoting Effectiveness of Non-siliceous Additives Percent By Weight l i I2 I 1 Example No. I4 I lo 17 Detergent Base 95 93 94 R8 83.7 9. K2 Deter ency lmprover 5 5 4 5 ill 2 U PVA remix 1 I I 4.5 5 Sodium Perboratc. Powdered Corn Starch ltlll ltlll lllil lllil lll(l lillll) IOU IUU Percent Pour 3] (ii 54.1 5] 5 559 48.9 58.7 Ratio of Flow-Promoting Agent to Dctergcncy lmprover 4 0.4 U5 L4 8 2.5 0.45

TABLE V Flow-Promoting Effectiveness of a Silica Aerogel Exam le N0 l8 I9 2O 21 22 23 24 25 2h Z7 Z8 1? Detergent Base S9 93 87 95 92 90 87 94 87 94 J3 Detergency lmprover"" 5 8 5 8 3 5 l0 Detergency lmprov S 5 8 5 5 PVA Premix 3 Silica Aerogel 2 3 2 5 J 3 5 5 l l 2 um i nn inn inn Hi0 ltltl Hlll I00 IOU lllil ltlU TAB LE V Continued Flow-Promoting Effectiveness of a Silica Aerogel Example No. l8 l) 2] 22 23 24 25 26 27 28 Percent Pour 68 56.4 6L5 67.2 58 53,9 71.4 56.8 38 45.6 2% 2 40.8 Ratio of Flow-Promoting Agent to Detergertcy lmprover 1.0 0.4 0.4 0.6 0.7 0.6 H) 0.6 0.2 U.) 0.2 0.4

TABLE VI Flow-Promoting Effectiveness of Dicalite 416 Percent By Weight Example No. 30 31 32 33 34 36 37 38 39 40 4| Detergent Base 88 87 92 92 92 90 95 95 97 92 94 92 Detergeney lmprovcr 5 5 5 Detergene lmprover 3 5 5 5 Detergeney lmprovcr 5 3 5 3 3 PVA Premix 2 Flow-Promoting Agent 5 8 3 S 3 5 0 (l U 3 3 5 I00 100 l 0 I00 I00 IOU l ()0 100 H10 100 100 [HO Percent Pour 64.! 67.3 50.6 47 I 32.9 38.7 26.6 5.4 23.l 33.4 45,5 48.7 Ratio of FlowPromoting Agent to Detergency lmprover 1.4 L6 0.6 l.7 0.6 H) 0.6 HI I 7 Example No. 42 43 44 45 46 Detergent Base 95 87 93 87 92 Detergency lmprovcr 5 8 5 5 5 Flow-Promoting Agent 5 2 8 3 l 00 l 00 l ()0 l 00 l 00 Percent Pour 3l 39.4 45.l 67.3 506 Ratio of Flow-Promoting Agent to Detergene lmprover 0.6 0.4 [.6 06

I Parts B TABLE \rll W'ctght Sodium alkylbenzenesulfonate"" 12W) Sodium earbox 'mcthvleellulose llSt) How-Promoting Etieet of Attapulglte Sodium Carbonate S "U v Sodium silicate solids lSiO Na O 2.0) 3 (Ill 47 4x 49 Sodium sulfate It in Water 3.0" Detergent Base 93 R7 87 W Delergeney lmprove 5 5 8 Flow-Promoting Agent 2 K 5 I H)" m m ""dorived from a mixture of alkylhenlenes huung about J l 5 carbon atoms in lhe alkyl portion. and wheteln the benzene group is randomly [HNllltlflLd along the Percent Four 43 465 34 alkyl Lhtltn ""A eompound formed by conden ing a lttHltll'C of MI") and All'i monolitdrlc alcohols \uth an average of 3 molar proportions ol ethylene oxide I37; ethylene nude \\Clgl'\ll ""Dicalite 4 l6. a trademark of Grefeo. lne a particulate fused sodium potamum aluminum silicate. hmtng an average particle sire ot about 39 mierons ""Syloid 144. a trademark for a silica aerogel sold h the Dauson ('hemtcal Dl\ Mon of W R Grace and (o Sylord 244 has it mean particle diameter of about 4 to It) microns ""Pluron1el.-h2[).a poltottethylene dcrnatne ol the compound described under lel. below haung ahout Illl to about .tll'i elh \lene OXldL h Clghl "A poltoupropylcne compound prepared h conden ing proplene (IldL' and propylene glycol lo a molecular weight ol about l5(lll-l)ll)(l. "Pluronic l.-6ZD" and "Pluronie l.-6ll" are trademarks of the Wyandotte (hemleals Corporation "Neodol 45-3 A eondensate of a mixture of and C. "oxo" :tleohols wtth 25; of methyl hranchmg and an .uerage ol 3 molar proportions of ethylene oxlde. ""l'he mineral altapulgtte is described m U 5 Pat No 2.594.257 a a eomplm hydrated magnenunt aluminum ilicate oeeurrlng In the form ot spienlar particles having the following ehctttlezil contposttlon 67' Sit] l1 5'.) MM). lltl'? AI O EXAMPLE A drum-dried detergent product within the instant invention is prepared having the following composition:

To 90 parts by weight of the above composition is added 5 parts by weight of dipropyl ntaleztte (a dctergency improver) and 5 parts by weight ot'a silica acro 50 gel having a mean particle diameter of 6 microns (it flowpromoting agent l.

EXAMPLE 5| An aqueous slurry of a detergent composition is prepared and spray-dried to the following formula:

'a mixture having l(] to ill carbon atoms 'a mixture of alkcne. hydroxyalkane'r and dtsulfonatea, haung l2 to IR carbon atoms 90 parts by weight of the above composition is rotated in a revolving drum and parts by weight of dihexyl diglycolate (a detergency improver), is added, followed by 5 parts by weight of wheat starch powder. 100% of which passes through a ZOO-mesh screen.

EXAMPLE 52 An aqueous slurry of a detergent composition is spray-dried to the following formula:

Parts By Weight Sodium alkylbcnzencsulfonate I500 Disodtum carboxymethylsuccinatc 45.00 Sodium silicate tSiO Na O I I 4) solids 6.00 Disodium alphtvsulfo stcarale 5.00 Trisodium orthophosphale 3.00 Sodium sulfate 10.00 Water 8.00 92.00

see footnote lhi To 92 parts by weight of the above composition is added, while tumbling in a revolving drum. 3 parts by weight of dibutyl phthalate. followed by 5 parts by weight of a hydrated silica (Zeofree 80). The product is an excellent free-flowing detergent.

EXAMPLE 53 An aqueous slurry of a soap composition is spray dried to the following formula:

Parts By Weight Soap [from 80: tallow. coconut oil). 76 00 dry basis Sodium silicate solids lSiO LNa O I 2.4) 2.00 Sodium tetrahorate. dry basis 5.00 Water T00 9000 EXAMPLE 54 A crutcher slurry is prepared at a temperature of about 180F. having the following composition:

Parts By Weight Sodium soap derived from cottonseed oil 9.0 Sodium soap derived from tallow 7.0 Sodium soap derived from palm kernel oil 2.0 Sodium carbonate 40.0 Sodium silicate solids lSiO :Na- .O 2.0) H] Water 4L0 100.0

The slurry is cooled on a revolving roll chilled with brine at about 0F, and scraped from the roll in particulate powder form. The powder is aged" by allowing it to travel several minutes on a moving conveyor belt. To parts by weight of the composition is mixed 7 parts by weight of a hydrated sodium silico-aluminate (Zeolex 23A). and 4 parts by weight ofdiethyl isophthalate.

The product is a free-flowing particulated built soap composition having excellent cleaning properties on hard surfaces and textiles.

EXAMPLE 55 The following compositions are prepared:

Parts By Weight A mixture of secondary straight-chain alcohols having lllS carbon atoms 15.00 i500 condensed with molar proportions of ethylene oxide A mixture ot' x-k and at C primary straight-chum alcohols 0 35 0.35 condensed with (159'; (total molecule hasis) ethylene oxide Sodium cnrboxymethylccllulose 0 30 0 K0 l-ln/y me la protease! 0.35 0 25 Sodium \ylenesullonatt: 0.50 0 50 Sodium soap derived from coconut oil 2.00 I 00 Sodium tripolyphosphatc 40.00 40.00 Sodium sthcate solids tSiO Na O 1.4) 4.20 4 10 Optical hriglitencrs and colorants 0 J?- 0 43 Sodium sulfate 2073 l 3 Flow promoter lNu-K-alunnnum slliculel None v100 Dihulyl phthalale 4 00 4 00 Water and misc inert matter assoclated 13.14 ll 24 with the components lilllllll lllll ill! The above components, except for the Howpromoting agent, the dibutyl phthalate. and the enzyme. are mixed an aqueous slurry in a crutcher. and spray-dried. The enzyme is then added followed by the flow-promoting agent (in product B only) and by the dibutyl phthalate. Both products are packed in plain unlined cardboard containers and held in the labora tory under the usual conditions of temperature and humidity for 4 days. At the end of this period the dibutyl phthalate in product A penetrates through the carton material and can be observed as oily spots on the outside. Moreover the product is difficult to pour. In contrast, the carton containing product B. exhibits no oily stains. and the product is readily poured.

EXAMPLE 50 A hydrated silica is effective as a flow-promoting agent when the detergency improver is dibutyl phthal ate in the following compositions:

Percent By Welght Spray'Dried Detergent Base 924 Hydrated Silica 3.0 Dibutyl Phthalate 4.0 Perfume 0.6

lUUlI The hydrated silica used is Zeofree 80. a trademark of the .l. M. Huber Corp.

EXAMPLE 57 The following experiment is conducted to determine the structural characteristics of the particulate units composed of the three essential components of the composition ofthe instant invention, namely the particulate detergent base composition, the particulate flowpromoting agent, and the oily detergency improver.

About 4 pounds of a spray-dried detergent base (A) having the following composition is prepared.

Percent By Weight Nonionic detergent" I656 Trisodium nitrilotriaectate monohydrute 26.50 Sodium carbonate 37,55 Sodium stearute |.l(l Sodium silicate solids tSi() :Nu 1.4) l L04 Sodium carboxymcthylcellulose 0.33 Optical brighleners ll.l9 Blue-green colorants 0.0! Sodium hydroxide l.ll) Water 5.52 Miscellaneous inert matter 0.10

"As described in Example 55 92 parts by weight of the spray-dried composition are intimately mixed in a revolving drum with 3 parts by weight of a representative flow-promoting agent, namely a silica aerogel, thereby forming an oleophilic mixture (B). While the mixture is tumbling in the revolving drum, parts by weight of a representative detergency improver. namely dibutyl phthalate, containing an oil-soluble red dye tracer, is sprayed on the tumbling particles, and the tumbling continued for about 10 minutes, to form composition (C).

The final mixture (C) upon visual microscopic examination at a magnification of 430x appears grossly ho mogeneous. that is. all of the smaller silica particles adhere to the surfaces of the larger particles of detergent base, no free silica particles being observed. All the silica particles are colored red over their entire surfaces. The larger particles of detergent base vary in the extent of red coloration, some being completely covered by the red dye, and others only partly covered. In instances of partial coloration, the line of demarcation is diffused rather than sharp.

It appears from the visual microscopic examination that the bulk ofthe dibutyl phthalate is absorbed by the silica aerogel, rather than by the detergent base. This is confirmed in a separate experiment wherein 3 parts by weight of silica aerogel are admixed with 5 parts by weight of dibutyl phthalate without causing change in the free-flowing properties of the silica aerogel. On the other hand when 5 parts of dibutyl phthalate are added to 95 parts of spray-dried detergent base in particulate form, the resultant product is sticky and does not flow well.

In addition to the visual microscopic examination, electron micrographs of the compositions designated (A). (B), and (C) in Example 57 are taken with a Cambridge Stereoscan Scanning Electron Microscope. as shown in FIGS. 1, 2, and 3.

FIG. 1 is an electron micrograph showing particles of the aforementioned spray-dried detergent base (A).

FIG. 2 is an electron micrograph of composition (B) formed by mixing together 92 parts by weight of detergent base (A) and 3 parts by weight ofa silica aerogel.

FIG. 3 is an electron micrograph of composition (C) consisting of 95 parts by weight of composition (B) and 5 parts by weight of dibutyl phthalate.

Examination of the electron micrographs confirms in detail the visual microscopic examinations. In FIG. 1 it may be observed that the surfaces ofthe particles ofdctergent base have thereon a multiplicity ofcraters gcnerally in the shape of flattened spherical segments. Many of the craters are several times the size of the silica aerogel particles. and it will be noted that in mixture (B) the silica aerogel particles cover and nearly fill the craters, as well as cover the remaining surfaces of the particles of detergent base, which may be seen in FIG. 2. The addition of 5 parts by weight of oily liquid dctcrgency improver to mixture (B) does not alter the appearance of the particles. due to complete absorption of the oily liquid, as shown in FIG. 3.

From the foregoing observations it is concluded that the final product prepared as described above is a free flowing particulate detergent composition wherein the particles of said composition comprise particles of a detergent base. each having adherent thereon a multiplicity of relatively smaller particles of said flow-promoting agent. the relatively smaller particles of flow-promoting agent and probably to some extent at least. the particles of detergent base, having the oily liquid detergency improver absorbed thereon.

Thus the physical form of the product of Example 57 comprises agglomerated particles. each of which comprises one or more particles of detergent base liming adherent thereon a multiplicity of smaller particles of flow-promoting agent. and an oily liquid detergency improver absorbed on at least the adherent particles of flow-promoting agent.

EXAMPLE 58 The presence of dibutyl phthalate has the added advantage of functioning as a dedusting agent. This is demonstrated in the following experiment.

Eighty-five parts ofthe detergent base having the formula described hereinbefore, and 10 parts of a silica aerogel are mixed together in a revolving drum. About 200 grams, or one-half of the weight of the mixture, is placed in a capped 2quart jar. To the other half is added 5 parts by weight of dibutyl phthalate per parts by weight of the above mixture in the revolving drum, and the mixture placed in a second capped 2- quart jar. When the jars are tumbled by hand. considerable dust is generated by the mixture of detergent base and silica aerogel, but substantially no dust is formed by the mixture containing dibutyl phthalate. Both mixtures are free-flowing.

EXAMPLE 59 There is prepared about 4 pounds of a spray-dried detergent base consisting essentially of about 9% of a fatty alcohol-ethylene oxide condensate nonionic detergent, about l7c sodium tallow soap, about 0.47! sodium carboxymethylcellulose, about 38% sodium tripolyphosphate, about 4.5% sodium silicate solids, about 31% sodium sulfate, about l2% water. about 3% borates, and the balance miscellaneous adjuncts. The percent pour of the detergent base is 63.9%

3 parts by weight ofdibutyl phthalate are mixed thoroughly with 97 parts of the above-described detergent base. The percent pour is reduced to 38% To demonstrate the flow-promoting action of an ethylene-maleic anhydride copolymer 93 parts by weight of the above-described detergent base are mixed with 3 parts by weight of dibutyl phthalate and after-treated with 4 parts by weight of a particulate linear ethylene-maleic anhydride copolymer in anhydride form having a molecular weight of about 450,000. and a specific viscosity of 0.5().7 as determined on a V7! solution of the copolymer in dimethyl formamide. the particles being of a size to pass through a 200-mesh screen.

The percent pour is 60.6%, demonstrating that the pouring properties are improved relative to the dibutyl phthalate-detergent base composition by the addition thereto of the above-described copolymer.

To demonstrate the effectiveness of anhydrous magnesium sulfate as a flowpromoting agent. 3 parts by weight of dibutyl phthalate are thoroughly mixed with 93 parts by weight of the above-described detergent followed by 4 parts by weight of anhydrous magnesium sulfate ground to pass a 200-mcsh screen. The percent pour of the final product is 51.1%.

Having described the invention, modifications within the spirit thereof will be readily apparent to those skilled in the art. and it is not intended that the invention be limited to the best modes exemplified. but limited only within the scope of the appended claims.

What is claimed is:

l. A process for improving the flowability of a particulate anionic or nonionic built detergent composition containing an oily detergent-improving additive com prising:

i. preparing a spray-dricd particulate detergent composition comprising about 0.5% to about of an anionic detergent or nonionic detergent selected from the group consisting oft l water-soluble ethylene oxide condensates of a base formed by condensing propylene oxide with propylene glycol. (2) compounds formed by the simultaneous polymerization of propylene oxide and ethylene oxide. and (3) ethoxylates of primary or secondary alcohols. said nonionic having detergent properties. and about 25% to about 80% of a detergent builder.

ii. intimately blending with said detergent composi tion about 0.5% to about 1571 by weight. whole composition basis. of a particulate water-soluble siliceous flow-promoting agent selected from the group consisting of silica aerogels. silica xerogels. diatomaceous earth. sodium silico aluminate. cal- 24 cium alumino silicate. magnesium silicate. and mix tures thereof. said water-insoluble siliceous sub stances having a pore volume of at least 2 milliliters per gram.

iii. blending with said oleophilic mixture about 1% to about 35% by weight. whole composition basis. and sufficient to improve the detergent characteristics of the detergent. of a detergency improver comprising a non-aqueous oily liquid substance selected from the group consisting of:

a. condensates of ethylene oxide and monohydric primary or secondary alcohols having about 8 to lo carbon atoms and having an ethylene oxide content of about i0 7? to about 5 l7r.

b. polymers of propylene oxide having a molecular weight of about 1.500 to about 1.800.

c. condensates of ethylene oxide and polymers of propylene oxide and polymers of propylene oxide having a molecular weight of about I500 to about l800. said condensates having from about 10% to about 20% ethylene oxide by weight in the molecule.

d. dialkyl phathates wherein the alkyl group has from l9 carbon atoms;

said particles of flow-promoting agent having absorbed thereon said oily detergency improver. and said detergcncy improver and said flow-promoting agent being external to the particles of said particulate detergent base composition.

2. A process in accordance with claim 1 wherein said builder is pentasodium tripolyphosphate.

3. A process in accordance with claim I wherein said builder is trisodium nitrilotriacetate.

4. A process in accordance with claim 1 wherein said builder is sodium carbonate.

5. A process in accordance with claim 1 wherein said flow-promoting agent is a silica aerogel.

6. A process in accordance with claim I wherein said oily liquid substance is dibutyl phthalate.

7. A process in accordance with claim 1 wherein said oily liquid substance is chemically inert to said flowpromoting agent.


DATED February 25 1975 |NVENTOR(S) Louis R. Mazzola and Paul Ferreri It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 10 change "from" to -form-.

Column 13, line 21, change "m-provers" to -improvers.

line 40, change "flowlpromoting to flowpromoting.

Column 23, line 40 change "water-soluble" to -waterinsoluble--.

igned and scaled this 24th day 05 June 1175.

(.BEAL) Attest:

C. MARSHALL DANN IZUTI-Z C. IIASOII Commissioner of Patents Attesting Officer and Trademarks

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U.S. Classification510/443, 510/349, 510/360
International ClassificationC11D3/20, C11D1/72, C11D3/12, C11D3/37, C11D11/00, C11D17/06
Cooperative ClassificationC11D3/124, C11D11/0082, C11D3/1246, C11D17/06, C11D3/128, C11D1/72, C11D3/3707, C11D3/2093
European ClassificationC11D3/12G2F, C11D3/12G, C11D17/06, C11D3/12G2, C11D1/72, C11D11/00D, C11D3/20F, C11D3/37B2