CA1268681A

CA1268681A - Controlled sudsing detergent compositions

Info

Publication number: CA1268681A
Application number: CA000514828A
Authority: CA
Inventors: Richard Mark Baginski; Bernard Charles Dems; Linda Ann Ross; Ralph Hayward Soule, Jr.
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1985-07-30
Filing date: 1986-07-29
Publication date: 1990-05-08
Anticipated expiration: 2007-05-08
Also published as: DK164118C; JPS6284197A; SG59392G; ATE58167T1; GB8618357D0; DK363486D0; EP0211589B1; GR861896B; GB2178444A; JPH0823037B2; FI863113A0; DE3675456D1; US4652392A; FI863113A; DK164118B; DK363486A; EP0211589A2; HK60292A; GB2178444B; EP0211589A3

Abstract

CONTROLLED SUDSING DETERGENT COMPOSITIONS
Abstract of the Disclosure Granular detergent compositions having an effective suds controlling agent comprising a suds-controlling silicone material which is substantially removed from contact with the surfactant component or alkaline component of the composition by incorporation in, e.g ., a polyethylene glycol carrier, with preferably a small amount of fatty acid, in an irregularly shaped particle having a minimum dimension of at least about 0.05 cm .
and being substantially free of water soluble inorganic salts.

Description

CONTROLLED SUDSING DETERCENT COMPOSITIONS
Richard M. Baginski Bernarcl C. Dems Linda A. Ross Ralph H. Soule, Jr.
Technical Fleld and Background_Art The present invention relates to detergent compositions containing as an essential ingredient a silicone suds controlling agent which is stable on storage. The concept of "stability" as used herein is in the context of protecting the silicone and pre-serving, maintaining or promoting its capabili~y of suppressing, or controlling, the suds profile of a detergent surface active agent. More specifically, the invention in its broadest context encompasses detergent cornpositions comprising a detergent surfactant component and a silicone suds controlling agent which is separated, or isolated, within a protective matrix from the detergent surfactant.
Silicones are widely known and taught for use as highly effective suds controlling agents. For example, U. S. Patent 3, 455, 839 relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
Useful suds controlling silicones are mixtures of silicone and silanated sllica as described, for instance, in German Patent Application DOS 2 ,124, 526 .
Additionally, German Patent 2,232,262 relates to silicone suds controlling agents comprising sodium tripolyphosphate surface-coated with an organopolysiloxane.
Silicone defoamers and suds controlling agents have been successfully incorporated into a detergent composition by protect-31~ ing them as in UOS. Pate~it 3,933,672, Bartolotta et al, issued :: Janu~ 20, 1976.
The interaction of the detergent material with the silicone on storage, has been minimized by isolating the silicone material from said détergents to provide compositions having controlled suds 3~ patterns even after prolonged storage~

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- ~ -Summary of the Invention The present invention encompasses granular detergent compositions having a controlled suds pattern, comprising:
(a) a suds suppressing amo~Jnt of a stable suds controlling component especially adapted for use in a detergent composition, comprising a silicone suds controlling agent releasably incorporated in a water-soluble or water dispersible, substantially non-surface active, detergent-impermeabie, and non-hygroscopic carrier, said component being substantially free of hygroscopic water-soluble inorganic salts, and in the form of irregularly shaped particles having a minimum dimension not less than about 0 . 05 cm and a maximum dimension being at least about 20% greater than the minimum dimension; and (b) a sudsing cletergent component selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic, and cationic detergents and mixtures thereof.
The silicone suds controlling component of the instant compo-sitions is employed herein in a "suds suppressing amount". By "suds suppressing amount" is meant that the ~ormulator of the compositions can select an amount of this component which will control the suds to the extent desired. l he am~unt of suds controller wiil vary with the detergent component selected. For example, with high sudsing surfactants, retatively more of the controller is used to achieve the desired suds control than with low foa~ning detergents.
The silicone suds controlling component herein comprises a silicone suds controlling agent of the type hereinafter disclosed 3~ which is substantially isolated from the detergent component of the composition. This "isolation" is achieved by inc~rporating the sllicona agent in a water-soluble or water-dispersible organic carrier matrix. As in U.5. Patent 3,933,672, the rnatrix, itself, must be a substantially non-surface active, non-hygroscopic, 3~ materiai which does not interact with the silicone agent.
Moreover, tha carrier must be substantially impenetrable by the detergent component of the detergent composition to prevent undesirable siliconeldetergent andl/or silicone/alkalinity interactions .
Moreover, the carrier matrix herein must not contain added 5 surface active agents, other than the silicone.
Detailed Description of the Invention The compositions of the present invention comprise two essential components, the irregularly shaped particulate silicone suds controlling component substantially free of hygroscopic water 10 soiuble inorganic salts and the detergent component. In order to provide a stable composition which provides good suds control even after storage, it is necessary to isolate the silicone component from the detergent component in the manner hereinaf~er disclosed. The individual components olF the 5 compositions herein are described in detail, below.
Suds Controlling Component The suds controlling component of the instant composition comprises a silicone suds controlling agent which is incorporated in a water-soluble or water-dispersible, substantially nonsurface 20 active, detergent-impermeable and, non-hygroscopic carrier material. The carrier material contains within its interior substantially ali of the silicone suds controlling agent and effectively isolates it from (i.e., keeps it out of contact with) the detergent component of the compositions. The carrier material is 25 selected such that, upon admixture with water, the carrier matrix dissolves or disperses to release the silicone material to perform its suds controlling function.
The silicone materials employed as the suds controlling agents herein can be alkylated polysiloxane materials of several 30 types, either singly or in combination with various solid materials such as silica aerogels and xerogels and hydrophobic silicas of various types. In industrial practice, the term silicone has become a generic term which encompasses a variety of relatively high molecular weight polymers containing siloxane units and 35 hydrocarbyl yroups of various types. In general terms, the I

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silicone suds controllers can be described as siloxanes having the general structural backbone.
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F~' wherein x is from about 20 to about 2,000, and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl or phenyl. The polydimethylsiloxanes (R and R' are methyl) having a molecular weight within the range of from about 20û to abou~
200,000, and higher, are all useful as suds controlling agents.
Silicone materials are commercially available from the Dow Corning Corporation under ~he trade mark "Silicone 200 Fluids. Suitable polydimethylsiloxanes have a viscosity of from about 20 cs to about 60,000 cs, preferabiy from about 20-1500 cs, at 250C when ~5 used with silica and/or siloxane resin.
Additionally, other silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exhibit useful suds controlling properties.
These materials are readily prepared by the hydrolysis of the appropriate al}cyi, aryl or mixed alkaryl or aralkyl silicone dichlorides with water in the manner well known in the art. As specific examples of such silicone suds controlling agents usefui herein there can be mentioned, for example, diethyl polysiloxanes: dipropyl polysiloxanes; dibutyl polysiloxanes;
2S nn0thylethyl polysiloxanes; phenylmethyl polysiloxanes; and the like. The dimethyl polysiloxanes are particularly useful herein due to their low cost and ready availability.
The silicone "droplets" in the carrier matrix should be from about 1 to about S0 microns, preferably from about 5 to about 40 microns, more preferably from about S to about 30 microns in diameter f~r maximum effectiveness. Droplets below about S
microns in diameter are not very effective and above about 30 microns in diameter are increasingly less effective. -Similar sizes are requirecl for the other silicone suds controlling agents disclosed hereinafter.

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A second highly preferred type of silicone suds controlling agent useful in the compositions herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica. Such mi>~tures of silicone and silica can be prepared by 5 affixing the silicone to the surface of silica (SiO2), for example by means of the catalytic reaction disclosed in U. S . Patent 3,235,509, Nitzsche et al, lssued F~bruary 15, 196G. Suds controlling agents comprising mixtures of siiicone and silica prepared in this manner preferably comprise silicone and silica in a silicone:silica ratio of from about 19:1 to about 1:2, preferably from about 10:1 to about 1: 1. The silica can be chemically and/or physically bound to the silicone in an amount which is preferably about 596 to about 20~, preferably from about 1 û to about 15%, by weight, based on the silicone. The particle size of the silica employed in 15 such siliG3/silicone suds controlling agents should preferably be not more than about 1000, preferably not more than about 100 millimicrons, preferably from about 5 millimicrons to about 5û
~illimicronsO more preferably from about 10 to about 20 millimicrons, and the specific surface area of the silica should 20 exceed about 5 m2/g., preferably more than about 50 m21g.
Alternatively, suds controlling agents comprising silicone and silica can be prepared by admixing a silicone fluid of the type hereinabove disclosed with a hydrophobic silica having a particle size and surface area in the range disclosed above. Any of 25 several known methods may be used for making a hydrophobic silica which can be employed herein in combination with a silicone as the suds controlling agent. For example, a fumed silica can be reacted with a trialkyl chlorosilane (i.e., "silanated") to affix hydrsphobic trialkylsilane groups on the sur~ace of the silica. In 30 a preferred and well known process, fumed silica is contacted with trlmethylchlorosilane an~ a preferred hydrophobic silanated silica useful in the present compositions is prepared.~
In an alternate procedure, a hydrophobis: silica useful in the present compositions is obtained by contacting silic~ with any of 35 the following compounds: metai, ammonium and substituted .
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ammonium salts of long chain fatty acids, such as sodium stearate, aluminum stearate, and the like; silylhalides, such as ethyltrichlorosilane, butyltrichlorosilane, tricyclohexylchlorosilane, and the like; and long chain alkyl amines or ammonium salts, such 5 as cetyl trime~hyl amine, cetyl trimethyl ammonium chloride, and the like.
A preferred suds controlling agent herein comprises a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicrons to 10 about 20 millimicrons and a specific surface area above about 50 m2/g intimately admixed with a dimethyl silicone fluid having a molecular weight in the range of from about 500 to about 200,000, at a weight ratio of silicone to silanated silica of from abou~ 10:1 to about 1: 2 . Such suds controlling agents preferably comprise 15 silicone and the silanated silica in a weight ratio of sili-cone:silanated silica of from about 1û:1 to about 1:1. The mixed hydrophobic silanated (especially trimethylsilanated) silica-silicone suds controlling agents provide suds control over a broad range of temperatures, presumably due to the controlled release of the 20 silicone from the surface of the silanated silica.
Another type of suds control agent herein comprises a silicone ma~erial of the type hereinabove disclosed sorbed onto and into a solid. Such suds controlling agents comprise the silicone and solid in a silicone: solid ratio of from about 20:1 to 25 about 1:20, pre~rably from about 5:1 to about 1 :1 . Examples of suitable solid sorbents for the silicones herein include clay, starch, kieselguhr, Fuller's Earth, and the like. l he alkalinity of the solid sorbents is of no consequence to the compositions herein, inasmuch as it has been discovered that the silicones are 30 stable when admixed therewith. As disclosed hereinabo~Je, the sorbent-plus-silicone suds controlling agent must be coated or otherwise incorporated into a carrier materia7 of the type herein-after disclosed to e~fectively isolate the silicone from the deter-gent component of the instant compositions.

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Yet another preferred type of silicone suds controlling agent herein comprises a silicone fluid, a silicone resin and silica. The silicone fluids useful in such suds controlling mixtures are any of the types hereinabove disclosed, but are preferably dirnethyl S siiicones. The silicone " resins" used in such compositions can be any alkylated silicone resins, but are usually those prepared from methylsilanes. Silicone resins are commonly described as "three-dimensional" polymers arising from the hydrolysis of alkyl trichlorosilanes, whereas the silicone fluids are "two-dimensional"
tO polymers prepared by the hydrolysis of diohlorosilanes. The silica components of such compositions are microporous materials such 35 the fumed silica aerogels and xerogels having the particle sizes and surface areas hereinabove disclosed.
The mixed silicone fluid/silicone resin/silica materials useful in the present compositions can be prepared in the manner dis-closed in U.S. Patent 3,455,839. These mixed materials are commercially availabie from the Dow Corning Corporation. Ac-cording to l).S. Patent 3,455,839, such materials can be described as mixtures consisting essentially of:
for each 100 parts by weight o~ a polydimethylsiloxane fluid having a viscosity in the range from 20 cs. to 1500 cs. at 25o~ ~
(a) from about 5 to about 5û, preferably from about 5 to about 29, parts by weight of a siloxane resin composed of ~CH3)3SiO1 12 units and SiO2 units in which the ratio of the (CH3)3SiO1 /2 units to the SiO2 units is within the range of from about 0.6/1 to about 1.211 and (b3 from about 1 to about 10, preferably from about 1 to about 5, parts by weight of a solid silica gel, preferably an aeroyel.
Again, such mixed silicone/silioone resin/silica suds controlling agents must be combined with a detergent-impermeable carrier material to be useful in the compositions herein.

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The silicone suds controlling agents of the aforementioned type must be incorporated within (i.e., coated, encapsulated, covered by, internalized, or otherwise substantially contained within) a substantially water-soluble, or water-dispersible, and 5 non-hygroscopic carrier material which must be impermeablP to detergents and alkalinity and which, itself, must be substantially nonsurface active. By substantially nonsurface active is meant that the carrier material, itself, does not interact with the silicone material in such fashion that the silicone material is 10 emulsified or otherwise excessively dispersed prior to its release in the wash water. I . e., the particle size of the silicone droplet should be maintained above about 1, more preferably above about 5 microns.
Of course, when preparing a dry powder or granulated 15 detergent composition, it is preferable that the silicone suds controlting component thereof also be substantially dry and nontacky at ambient temperatures. Accordingly, it is preferred herein to use as the carrier material, or vehicle, plastic, organic compounds which can be conveniently melted, admixed with the 20 silicone suds contro!ling agent, and thereafter cooled to form solid flakes. There are a wide variety of such carrier ma~erials useful herein. Since the silicone suds controlling agent is to be re-leasably incorporated in the carrier, such that the silicone is released into the aqueous bath upon admixture of the composition 25 therewith, it is pre~erred that the carrier material be water soluble. However, water-clispersible materials are also useful, inasmuch as they will also release the silicone upon addition to an aqueous ba~h.
A wide variety of carrier materials having the requisite 30 solubility/dispersibility characteristics and the essential features of being substantially non-surface active, substantially non-hygroscopic and substantiaily detergent-impermeabie are known. However, polyethylene glycol (PEGl which has sub-stantially no surface active characteristics is highly preferred 35 herein. P~G, having molecular weigt-ts of from about 1,500 to about 100,000, preferably from about 3,000 to about 20,000, more preferably from about 5,000 to about 10,000 can be used.
Surprisingly, highly ethoxylated fatty alcohols such as tallow alcohol condensed with at least about 25 molar proportions of ethylene oxide are also useful herein, Other alcohol condensates containing extremely high ethoxylate proportions (about 25 and above) are also useful herein. Such high ethoxylates apparently lack sufficient surface active characteristics to interac~ or otherwise interfere with the desired suds control properties of the silicone agents herein. A variety of other materials useful as the carrier agents herein can also be used, e.g., gelatin; agar;
gum arabic; and various algae-derived gels.
A very preferred carrier material is a mixture of from about 0.2% to about 15~, preferably from about 0.25% to about 5%, more preferably from about 0. 25% to about 2% of fatty acids containing from about 12 to about 30, preferably from about 14 to about 20, more preferably from about 14 to about 16, carbon atoms and the balance PEG. Such a carrier material gives a more desirable suds pattern over the duration of the washing process, providing more suds at the start and less suds at the end than PEG alone. l he fatty acid delays the solubility of the suds suppressor particle and thereby delays the release of the silicone.
The irregularly shaped particulate silicone suds con~rolling component of the present invention can be conveniently prepared in a highly preferred flake form by admixing the silicone suds controlling agent with a molten carrier material, mixing to form the appropriate silicone droplet size, and flaking, e.g., by milling or extruding to form a thin sheet, cooling to solidi~y the carrier material, and breaking the sheet into particles of the - 30 right size. In another preferred process thin films can be formed by cooling molten carrier material with the suds suppressor dispersed therein on, e.g., a chill roll or beit cooler and then breaking said film into appropriate sized flakes. The thickness of the flake should be ~rom about 0.04 to about 0.15 cm, preferably from about 0.05 to about 0.1 cm. When this procedur~ is used, ::

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the silicone suds controlling agent is contained within the carrier material so effectively that when this material is eventually ad-mixed with, or incorporated into, a detergent composition, the silicone does not substantially come into contact with the deter-s gent surfactant ingredient.
In order to provide a granular, nontacky suds controllingcomponent useful in dry granular detergent compositions, the flake of the silicone suds controlling agent and carrier material should be substantially solidified. This can be achieved by use 10 of belt coolers which quickly cool the sheets or flakes such that the carrier melt is hardened. Extrusion techniques can also be used .
It is to be recognized that the amount of carrier used to isolate the silicone suds controlling agent herein from the deter-15 gent component of the compositions herein is not critical. It isonly necessary that enough carrier be used to provide sufficient volume that substantially all the silicone can be incorporated therein. Likewise, it is preferred to have suff3cient carrier material to provide for sufficient strength of the resultant granule 20 to resist premature breakage. Generally, above about a 2 :1, preferably from about 5:1 to about 10Q:1, more preferably from about 20:1 to about 40:1, weight ratio of carrier to silicone suds controlling agent is employed.
The present invention preferably encompasses detergent 25 compositions comprising a detergent component and a suds controlling component comprising an irregularly shaped particle, preferably a flake, consisting essentially of from about 1% to about 20%, preferably from about 1% to about 5%, most preferably about 2~ to about 596, by weight of a silicone suds controlling 3û agent of any of the types hereinabove disclosed and the remainder being primarily a carrier material of the type hereinabove disclosed.
The size of the particles of the suds controlling component ~Isecl in the present compositions is selected to be compatible with 35 the remainder of the detergent composition. The suds controlling ~.

components herein do not segregate unacceptably within the detergent composition. In general, particles with a maxirnum dimension of from about 600 to about 2000, preferably from about 800 to about 1600 microns are compatible with spray-dried 5 detergent granules. Therefore, the majority of the particles should have these maxin um dimensions. The majority of the particles should have a ratio of the maximum to the minimum diameter of from about 1 . 5 :1 to about 5 :1, preferably from about 1.5:1 to about 4:1.
Detergent compositions comprising the suds control compo-nent and the detergent component can be provided havin~3 various ratios and proportions of these two materials. Of course, the amount of the suds control component can be varied, depending upon the suds profile desired by the formuiator. Moreover, the 15 amount of detergent component can be varied to provide either heavy-duty or light-duty products, as desired.
For most purposes, it is preferred to use a sufflcient amount of the silicone suds controlling component in the detergent compo-sition ~o provide a concentration of from about 0 . 0005% to about 20 10~ by weight of the silicone suds controlling agent in the composition. A preferred amount of silicone suds controlling agent in the detergent composition lies within the range of from about 0.91% to about 0.5% by weight. Accordingly, the amount of suds control component wilJ be adjusted, depending upon the 25 amount of silicone suds control agent contained therein, to provide these desirable percentages of suds control agent.
Detergent Component The amount of the detergent component can, as noted hereinabove, vary over a wlde range which depends on the 30 desires uf the user. In general, the compositions contain from about 5% to about 50%, preferably from about 1096 to about 30% by weight, of detergent.
The detergent compositions of the instant invention can contain all manner of organic, water-soluble detergent compounds 35 so ong as the silicone sods control ayents are isolated therefrom.

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A typical listing of the classes and species of detergent com-pounds useful herein appear in U.S. Patent 3,664,961, Morris, lssued May 23, 1972. ~e foll~wing list Olc detergent compounds and mixtures which can be used in the instant compo-5 sitions is representative of such materials, but is not intended to be limiting.
Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful as the ~etergent component of the composition herein.
This class of detergents includes ordinary alkali metal soaps such 10 as the sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids containing frGm about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms.
Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly us~ful are the 15 sodium and potassium salts of the mixtures of fatty acids der.ved from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap .
Another slass of detergents includes water-soiuble salts, particularly the alkali metal, ammonium and alkanolammonium salts, 20 of organlc sulfuric reaction products having in their molecular structure an a~ky1 group containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester ~roup.
(Included in the term "alkyl" is the alkyl portion of acyl groups.~
Examples of this group of synthetic detergents which ~rm a part ~5 of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sul~ating the higher alcohols (C8-C1E~ carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkylbenzene sulfonates, in which the alkyl group 3û contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g. those of the type described in United S~ates Patents 2,220,099 and 2,477,383.
Especially valuala7 e are llnear straight chain alkylbenzene sulfonates in which the average of the alkyl ~roups 35 is about 12 carbon atoms, abbreviated as C12 LAS.

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Other anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or 5 potassium salts of alkyl phenol ethylene oxide ether sulfate con-taining from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 13 ca rbon atoms .
Water-soluble nonionic synthetic detergents are also useful as 10 the detergent component of the instant composition. Such nonionic detergent materials can be broadly defined as compounds produced by the condensation of ethylene osdde groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyi aromatic in nature. The length of 15 the polyoxyethylene group which is condensed with any particuiar hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
For example, a well-known class of nonionic synthetic deter-20 gents is made available on the market under the trade mark of"Pluronic". These compounds are ~ormed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. Other suitable nonionic synthetic detergents include the polyethylene oxide condensates of 25 alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 13 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to from about 4 to about 15 moles of ethylene oxide 30 per mole of alkyl phenol.
The water-soluble condensation products of aliphatic alcohols ~aving from about 8 to about 22 carbon atoms, in either straight chain or branched configuration, with ethylene oxide, e.g., a coconut alcohol-ethytene oxide condensate having from abo~t 5 to 35 about 30 moles of ethyl~ne oxkle per mole of coconut alcohol, the .

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coconut alcohol fraction having from about 10 to about 14 carbon atoms, are also useful nonionic detergents herein.
Semi-polar nonionic detergents inslude water-soluble amine oxides containing one alkyl moiety of from about 10 to 20 carbon 5 atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety of from about 10 to 20 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and 10 hydroxyalkyl groups containing from 1 to about 3 carbon atoms;
and water-soluble sulfoxide detergents containing one alkyl or hydroxyalkyl moiety of from about 10 to about 20 carbon atoms and a moiety selected from the group consisting of ~Ikyl and hydroxyalkyl moieties of from 1 to about 3 carbon atoms.
Ampholytic detergents include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one aliphatic substituent 20 contains an anionic water-solubilizing group.
Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 25 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group. The quaternary compounds, th~mselves, e.g.
cetyltrimethyl ammonium bromide, can also be used herein.
- Other useful detergent compounds herein include the water-soluble salts of esters of alpha-sulfonated fatty acids con-30 taining from about 6 to about 20 carbon atoms in the fatty asid group and from 1 to about 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group and from about 9 to about 20 carbon atoms in the alkane inoiety; alkyl 35 ether suifates containing from about 10 to about 20 carbon atoms in the alkyl group and from about 1 to about 12 moles of ethylene oxide; water~soluble salts of olefin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Preferred water-soluble organic detergent compounds herein include linear alkylbenzene sulfonates containing from about 11 to about 13 carbon atoms in the alkyl group; C10 18 alkyl sulfates;
the C10-16 alkyl glyceryl sulfonates; C10 18 alkyl ether sulfates, especially wherein the alkyl moiety contains from about 14 to 18 carbon atoms and wherein the average degree of ethoxylation between 1 and 6; C1 0 18 alkyl dimethyl amine oxides, especially wherein the alkyl group çontains from about 11 to 16 carbon atoms; alkyldimethyl ammonio propane sulfonates and alkyldimethyl ammonio hydroxy propane sulfonates wherein the alkyl group in both types contains from 14 to 18 carbon atoms; soaps, as here-inabove defined; and the condensation product of C1 0 18 fatty alcohols with from about 3 to about 15 moles of ethylene oxides.
Specific pre~rred detergents for use herein include: sodium linear C10 13 alkylbenzene sulfonates; sodium C12 18 alkyl sul-fates; sodium salts of sulfated condensation product of C12 18 alcohols with from about 1 to about 3 moles of ethylene oxide: the condensation product of a C10 18 fatty alcohols with from about 4 to about 10 moles of ethylene oxide; and the water-soluble sodium and potassium salts of higher fatty acids containing from about 10 to about 18 carbon atoms.
It is to be recognized that any of the foregoing detergents can be used separately herein, or as mixtures. Examples of preferred detergent mixtures herein are as follows.
An especially preferred alkyl ether sulfate detergent compo-nent of the instant compositions is a mixture of alkyi ether sul-fates, said mixture having an average (arithmetic mean) carbon chain length within the range of from about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, ancl an average larithmetic mean) degree of ethoxylation of from about 1 :

to 4 moles of ethylene oxide, preferably from about l to 3 moles of ethylene oxide.
Optional Additives The detergent compositions of the present invention can 5 contain, in addition to the silicone and detergent, water-soluble builders such as those commonly taught for use in detergent compositions. Such auxiliary builders can be employed to se-quester hardness ions and to heip adjust the pH of the launder-ing liquor. Such builders can be employed in csncentrations of 10from about 5% to about 9596 by weight, preferably from about 10%
to about 50% by weight, of the detergent cornpositions herein to provide their builder and pH-controllin~3 functions. The builders herein include any of the conventional inorganic and organic water-soluble builder salts.
1 SSuch builders can be, for example, water-soiuble salts of phosphates incE~ding tripolyphosphates, pyrophosphates, ortho-phosphates, higher polyphosphates, carbonates, silicates, and organic polycarboxylates. Specific preferred examples of inorganic phosphate builders include sodium and potassium 20 tripolyphosphates ~nd pyrophosphates.
Nonphosphorus-containing materials can also be selected for use herein as builders.
Specific examples of nonphosphorus, inorganic detergent builder ingredients include water-soluble inorganic carbonate, ~5 bicarbonate, and silicate salts. The alkali metal, e.g., sodium and potassium, carbonates, bicarbonates, and silica~es are parti cularly useful herein.
Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available The aluminosilicates 30 useful in this invention can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing alum;nosilicate ion exchange materiais is discussed in U.S. Pat. No. 3,985,669, Krummel et al, issued Oct. 12, 1976.
Preferred synthetic crystalline alyminosilicate i`on -. .

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exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicat~ ion exchange material in Zeolite A and has the formula Nal2~Alo2)12 (SiO2)12i-X~2 wherein x is from about 20 to about 30, especially about 27.
Water-soluble, organic builders are also useful herein. For example, the alkali metal, ammonium and substituted ammonium polycarboxylates are useful in the present compositions. Specific 10 examples of the polycarboxylate builder salts include sodium, potassium, ammonium and suS)stituted ammonium salts of ethylene-diaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, polyacrylic acid, polymaleio acid, and citric acid.
Other desirable polycarboxylate builders are the builders set forth in U.5. Patent 3,308,067, Diehl, dated March 7, 1967 Examples of such materials include the water-soluble salts of homo- and co-polymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, 20 aconitic acld, citraconic acid, and methylenemalonic acid.
Other suitable non-polyrneric polycarboxylates are the polyacetal carboxylates described in U.5. Pat. No. 4,144,226, issued Mar . 13, 1979 to Crutchfield et al, and U . S. Pat. No.
4,246,495, issued Mar. 27, 1979 to Crutchfield et al.
~hese polyacetal carboxylates can ba prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal 30 carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
The detergent compositions herein can contain-all manner Df additional materials comm~nly found in laundering and cleaning compositions. For example, the compositions can contain thick-35 eners and soil-suspending agents such as carboxymethylceliulose s~

and the like. Enzymes, especially the proteases, amylases and lipases, can also be present herein. Various perfumes, optical bleaches, fillers, anticaking agents, ~abric softeners and the like can be present in the compositions to provide the usual benefits 5 occasioned by the use of such materials in detergent compositions.
It is to be recognized that all such adjuvant materials are useful herein inasmuch as they are compatible and stable in the presence of the isolated silicone suds suppressor.
The compositions herein can additionally contain from about l 0 0.1~ to 10~6 by weight of one or more bleaching agents . Pre-ferred bleaching agents are hydrogen peroxide addition com-pounds. The hydrogen peroxide addition compounds may be organic, but are preferably inorganic in nature.
A great variety of these compounds exist. Most of them are 15 prepared by crystallization from solutions containing H2O2.
Others are prepared by drying a slurry containing the corre-sponding salts and H2O2. The most useful hydrogen peroxide addition compounds are the perborates, e.g., sodium perborate mono- and tetrahydrates. Sodium perborate monohydrate is 20 preferred. ()ther valuable hydrogen peroxide addition compounds are the carbonate peroxyhydrates, e.g., 2Na2CO3 3H2O2o and the phosphate peroxyhydrates, e.g., sodium pyrophosphate peroxyhydrate Nal~P207 2H202. The most suitable organic hydrogen peroxide addition compound which can be incorporated 25 into the detergent compositions of the present invention is the urea hydrogen peroxide addition compound of the formula . CO(N~232 H2O2, because it is one of the few free flowing dry organic hydrogen peroxide addition compounds.
Activators for these bleaches are also desirable additives.
30 Preferred are tl-e activators of lJ.S. Patent 4,412,934, Chung et al .
Other bleaching agents which can be used include oxygena-ting bleaches such as sodium or pota*ssium persulfate, for instance the mixed salt marketed as "(:)xone", and organic per acids and 35 perox~des, such as fflose di`sclosed ~n Bri~tish Patents 886,188 and *TradQrk ,:
. ' ~ `

.: . , . :

1,293,063 and U.S. Patent N~. 4,483,781, Hartman, issued N~vember 20, 2984. ~gnesium salts of the peraclds and peracids with high (graater than abou~ 100) melting po mts and magnesium salts there-of are preferred. Suitable magnesium salts are disclosed in U.S.
S Patent 4,483,781, Hartman, issued November 20, 1984.
Halogen bleaches, for example hypochlorites, or hypobromi~es, and compounds providing these ions in solution, can also be used in, or with, the compositions herein. Examples are sodium hypochlorite itself, chlorinated trisodium phosphate, and organic N-chloro-compounds such as cnlorinated isocyanuric acid compounds. These are particularly useful in automatic dishwashing detergent compositions at concentrations of from 0.1 to 109~ by weight.
A finished deter~ent composition of this invention can con-tain minor amounts of materials which make the product more attractive. The following are mentioned by way of. example: a tarnish inhibitor such as ben~otriazole or ethylene thiourea can be added in amounts up to 2% by weight; fluorescers, perfumes and dyes, while not essential, can be added in small amounts. An alkaline material such as sodium or potassium carbonate or hydroxide can be added in minor amounts as supplementary pH
adjusters. There may also be mentioned, as suitable additives:
bacteriostats, bactericides, corrosion inhibitors such as soluble alkali silicates (preferably sodium silicates having an SiO21 Na2O
ratio of from 1:1 to 2.8:1), and textile softening agents.
All percentages, parts and ratios herein are by weight unless otherwise specified.
The ~ollowing examples illustrate ~he compositions herein.
EXAMPLE I
Desi~n of Fxperiment Flakes containing ~10% by weigh~ of a commercially available silicone/silica fluid ~7S% polydimethyl siloxane having a viscosity of 20 cs - 1,500 cs at 25.0C; about 15~ siloxane resin; and about 10% silica aerogel having an average ultimate particle size of 35 about l 2 millimicrons agglomerated to an average of 1, 3 - 1 . 7 , , ,,, ,:
, . , ., ~ . , ,; ~
, :- ~ -.. . :
.
, , : .. . .
.. , - :: ., microns and having a surface area of ~325 m lg ) and ~90% by weight of polyethylene glycol having a molecular weight of about 8,000 (PEC;-8000) were produced using a chill roll flaker pilot plant unit. Particle size was controlled by controlling flake thickness and selectively sizing/screening the ground flakes.
Prills containing ~3.5~ by weight silicone/silica fluid, ~63~ by weight sodium tripolyphosphate ~STPP) and the balance PEG -8000 were produced using a fluid bed process. Particle size was controlled by sizing/screening the prills and controlling atomization and fluid bed conditions.
The flakes or prills were admixed into a spray-dried detergent composition containing an anionic/nonioniclcationic surfactant system at levels to deliver a .035% siliconelsilica level.
Produc~ was stored in open cartons under high temperature/high humiclity condi~ions I varying from 79F and 50% relative humidity (R.H. ) to 93F and 86% R.H. each 24 hours] for up to 12 weeks.
At regular intervals, the suds profile was measured by conducting a washing machine test in which the suds level is evaluated at several times throughout the wash according to a picture grade scale ranging from 0 to 100, where 0 = no suds and 100 = full washer, and the results averaged.
Resul ts Suds Suppressor Stabili~y of Flakes with Different Minimum_Particle_Dimension as_Compared to Pri!ls Containing Hy~roscopic Powder Relative Suds Level vs. Inltial*
Tyler Mesh Hygro-Screen ~ Weeks Storage---------- scopic Size 0 4 6 8 12 ~owder Prill -10/+35** ~i ~ ~2 i~7 i~ ~es .025cm thick flake -10/+20 û +30 +28 ~34 ~33 No . 051 cm thick flake -10/+20 0 -3 ~1 ~2 ~1 No .112cm thick***
lale -IO 0 -~9 N.A. ~4 14 No ::

: :

~2D~;tf368~

~A ehange of more than +5 is significant. A change of more than ~10 is unaceeptable.
** -10/+35 refers to a distribution which passes a 10 mesh Tyler screen and is retained on a 35 mesh screen.
***-Made by process of Example I i .
As can be seen From the above, the prills which are the only particles containing water-soluble inorganic salts and particles with a minimum dimension of less than about 0.95cm 1.02 inch) are unacceptable and particles with a minimum dimension of at least about 0. 05 cm and no water-soluble inorganic salt are acceptable .
EXAMPLE I I
A. Flakes containing 310~6 by weight of silicone/siliea ~luid, O to 7% by weight of palmitic acid or "Hyfac" fatty acids, and the balance PEG-8000 were made in the laboratory by mixing the ingredients together such that the silicone droplets were dispersed as small droplets (1-301J), spreading the mix on a flat surface to allow it to freeze, grinding the solid sheet in a '~aring"
blender, and screening the particles to achieve particles -101~35 Tyler mesh.
Prills containing ~3.5% by weight of silicone/silica fluid, ~33.5% by weight PEG-8000 and ~63% by weight STPP were produced using a fluid bed process. Partiele size was controlled by si~ing/screening the prills and controlling atomization and fluid bed conditions~
The fiakes, or prills, were admixed into a spray-dried detergent composition containing an anionic/nonionic/cationic ~urfactant system at levels to deliver a 0.03596 silioone/silica level.
~he suds profile was measured at one, three, nine and twelve minutes in the wash cycle and in the rinse and the suds level graded according to the scaie described in Example 1.
B. Flakes cont~ining a carriPr material compr~sing 0 to 3.3%
palmitie acid or ~Hyfac~ fatty acids and the balànce PEG-8000 were made accordirig to the flake procedure described in A. A known weight of flakes was added to a known volume of deionized water : :

*Irademark **Trademark and allowed to sit for a specified time. The volume was then filtered and the percent insolubles determined by the weight trapped on filter paper.
Resu Its 5 A. P~elative Suds Picture Grade V5. Prill without fatty acid as in Exan~ple 1.
Wash ~ AC d Hyfac fatty acids temp (F) /
hardness 96 Fatty 10grains/ acid in ---------Minutes in the Wash-------- ------gallon) the flake 1 3 9 12 Rinse 1 3 9 12 Rinse 95r5 7 ~ i~ i~ 0 :;~ +6 +33 ~20 +32+19 -4 -8 -12 +34 +18 +5 0 -2 3 ~21+6 -5 -~ 0 +28 +1 2 -5 -1 0 -2 1 . 5 +13~5 -4 -7 -5 +16 +B -11 -13 -7 . 75 ~9 ~ -1 3 -1 4 0 125/2 1.5 +~ +5 -7 0 -4 -1 10 16-17 -1 . 75 ~4 ~3 -7 -1 3 0 60/10 5 +30 +24 +14 +11 -1 +43 ~25 +21+17 +5 3 +23+13 ~13 +10 +2 +25 ~19 +19 +13 +1 1~5 +22 +11 +2 +4 +2 +32 +20-1 0 0 .75 +14 +5 -11 -18 -10 As can be seen from the aboYe, fatty acids allow too many suds in the wash initially at normal wash conditions unless the level is kept below about 1 . 5~6. At that level the suds level is at a desirable and acceptable level at the start of the wash and lower at the end and in the rinse, which is also desirable.
25 8. Rate of Suds Suppressor Solubility lMeasured by Insolubles) as a Function of Fatty Acid LeYel Fatty ~ lJndissolved Temperature AcidPalmitic Acid Hyfac Hot 1~125F) 0 0.5 0.5 0.8 1.7 1.2 3.3 6.6 3.9 Warm (~95F~ 0 1.5 1.5 3~ 0.8 302 ~.1 3.3 ~ 10.8 8.3 ., . . ,~ . .

~2~

Cold (~60F) o 3.7 3.7 0.8 7.6 6.2 3.3 13.2 11.8 As can be seen from the above, fatty acids retard the 5 dissolution of the suds suppressor particles thus providing less suds suppression at the start of the wash and more suds suppression later. Once the suds suppressor is in the water it is slowly deactivated by emulsification by the detergent surfactant and bv alkalinitv.

. . .:
- ~ . . . : . ::

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A granular detergent composition comprising:
a) a suds suppressing amount of a stable suds controlling component especially adapted for use in a detergent composition, comprising a silicone suds controlling agent having an average droplet diameter of from about 1 to about 50 microns releasably incorporated in a water-soluble or water dispersible, substantially non-surface active, detergent-impermeable, and non-hygroscopic carrier, said component being substantially free of water-soluble relatively non-hygroscopic inorganic salts and in the form of an irregularly shaped particle having a minimum dimension of not less than about 0.05 cm and the maximum dimension being at least about 20% greater than the minimum dimension; and b) a sudsing detergent component selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic, and cationic detergents and mixtures thereof.

2. The composition of Claim 1 in which there is from about 10%
to about 50% of said detergent component and from 0. 005% to about 1096 of the silicone suds controlling agent in a carrier at a greater than about 2:1 ratio of carrier to silicone.

3. The composition of Claim 2 in which said dropiet diameter is from about 5 to about 30 microns; there is from about 10% to about 30% detergent component; and from about 0.01% to about 0.5% silicone suds controlling agent in a polyethylene glycol carrier at a ratio of carrier to silicone of from about 5:1 to about 100:1,

4. A composition according to Claim 3 wherein the detergent compound comprises a water-soluble salt of an organic sulfuric reaction product having in its molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group.

5. A composition according to Claim 3 wherein the detergent compound is selected from the group consisting of sodium linear C10-C13 alkylbenzene sulfonate; sodium C10-C18 alkyl sulfate; the sodium salt of a sulfated condensation product of a C10-C18 alcohol with from about 1 to about 3 moles of ethylene oxide; the condensation product of a C10-C18 fatty alcohol with from about 4 to about 10 moles of ethylene oxide; the water-soluble sodium and potassium salts of higher fatty acids containing from about 10 to about 18 carbon atoms; and mixtures thereof.

6. A composition according to Claim 5 containing, as an additional component, from about 5% to about 95% by weight of a water-soluble detergency builder.

7. A composition according to Claim 6 wherein there is from about 10% to about 50% of said detergency auxiliary builder which is selected from the group consisting of sodium tripolyphosphate and potassium tripolyphosphate.

8. A composition according to Claim 6 wherein the detergency builder is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium nitrilotriacetate, and mixtures thereof.

9. The composition of Claim 1 in which said droplet diameter is from about 1 to about 50 microns; there is from about 10% to about 50% detergent component; and from about 0.01% to about 0.5% silicone suds controlling agent in a polyethylene glycol carrier at a ratio of carrier to silicone of from about 5:1 to about 100: 1, and in which the carrier also comprises from about 0.2% to about 15% of fatty acids containing from about 12 to about 30 carbon atoms .

10. The composition of Claim 9 in which the carrier comprises from about 0.25% to about 2% of fatty acids containing from about 14 to about 20 carbon atoms.

11. A composition according to Claim 9 wherein the detergent compound comprises a water-soluble salt of an organic sulfuric reaction product having in its molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group.

12. A composition according to Claim 11 wherein the detergent compound is selected from the group consisting of sodium linear C10-C13 alkylbenzene sulfonate; sodium C10-C18 alkyl sulfate; the sodium salt of a sulfated condensation product of a C10-C1 8 alcohol with from about 1 to about 3 moles of ethylene oxide; the condensation product of a C10-C18 fatty alcohol with from about 4 to about 10 moles of ethylene oxide; the water-soluble sodium and potassium salts of higher fatty acids containing from about 10 to about 18 carbon atoms; and mixtures thereof.

13. A composition according to Claim 11 containing, as an additional component, from about 5% to about 95% by weight of a water-soluble detergency builder.

14. A composition according to Claim 13 wherein the auxiliary builder is selected from the group consisting of sodium tripolyphosphate and potassium tripolyphosphate,

15. A composition according to Claim 13 wherein the detergency builder is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium nitrilotriacetate, and mixtures thereof.

RBA:pw/sp(A721A21)