CA1085697A - Detergent compositions - Google Patents

Abstract

DETERGENT COMPOSITIONS

Terrell W. Gault and Edward J. Maguire, Jr.
ABSTRACT OF THE DISCLOSURE
Detergent compositions, including compositions for use in automatic dishwashing machines, are prepared by incorporating into the composition an intimate mixture of a nonionic surfactant and a silicone-containing suds suppressing agent. The compositions have reduced or controlled sudsing characteristics even after extended storage periods. The use of preferred self-emulsified silicone suds suppressors permits the production of low-sudsing spray-dried detergent granules without necessitating separate incorporation of the suds suppressors.

Description

~ lQ85697 ; BACKGROUND OF THE INVENTION
; This invention relates to detergent compositions and, in particular, to detergent compositions which have controlled ' sudsing characteristics, especially those useful in auto-` matic dishwashing.
Detergent compositions normally contain surfactants which tend to produce foam when agitated in aqueous solution.
For many applications, especially in automatic washing and dishwashing machines, excess foam production is a serious problem with detergent compositions and with many effective surfactants it is necessary to add foam inhibiting compounds, hereinafter called suds suppressors, in order to achieve acceptable sudsing characteristics.
Unfortunately, it has been found that the addition ~
of suds suppressors can in itself create new problems. For ~ ;
example, monostearyl acid phosphate, which is one conventional suds suppressor, is very effective and useful at low levels in the product, but as the level of suds suppressor is increased ~ to cope, for example, with increased surfactant, then the suds - 20 suppressor becomes incompletely soluble in a wash solution and precipitates out of solution onto utensil and machine surfaces leaving them coated with unsightly streaks and deposits.
Another type of suds suppressor which has often been suggested is that based on silicones, especially polydimethyl-siloxane. These materials, referred to generically herein-after as silicone suds suppressors, are known to be very useful in industrial applications where the silicone suds suppressor is added directly to an aqueous solution containing a sur-factant. However, they have not lived up to their promise when incorporated into detergent compositions; frequently, for example, they beco~e inactivated in the presence of other de-tergent incredients and require some type of special protection.

, ,, ~38S69~ :
It has now been found that stable suds suppressed detergent compositions can be prepared by incorporating silicone materials into the compositions in a particular manner.
Accordingly, it is an object of the invention to provide detergent compositions which are storage-stable and which include silicone suds suppressors.
It is a further object of the invention to provide a process for the incorporation of silicone suds suppressors into detergent compositions to provide storage-stable suds- ;
suppressed compositions.
Another problem exhibited by conventional silicone suds suppressors, such as polydimethylsiloxane, is that they are either completely inactivated in the spray-drying process or they lose their activity very quickly after the spray-dried granules have been made.
In the preparation of spray-dried detergent granules an aqueous mixture of the various components of the granules (the crutcher mix) is sprayed or otherwise introduced into what is essentially a drying tower. As the droplets of the crutcher mix proceed through the drying tower, the water is flashed off and solid or semiporous detergent granules are secured. The advantage of spray-dried detergent granules over granules obtained by simple dry mixing of the individual ingredients is their homogeneity. That is to say, each granule contains the various ingredients ln the same ratio proportions introduced into the original crutcher mix. This provides obvious advantages over simple dry mix detergent formulations inasmuch as dry mixing can result in a lack of homogeneity in the final detergent formulations such that the user is never certain of the composition of any given portion of the product.

In order to provide a homogeneous spray-dried granule ~L~856~

it is necessary that the crutcher mix, itself, by substantially homogeneous. In some instances, a crutcher mix may be a homogeneous solution. However, in order to provide a crutcher solution, excess amounts of water are needed to dissolve all the components. Use of excess amounts of water requires additional drying capacity in the spray-dry tower and is not economically attractive. For the most part, the crutcher mixes employed in the preparation of spray-dried detergent compositions are semidissolved aqueous slurries of the various components desired in the final spray-dried granules.
The crutching and spray-drying process, while possess-ing the above advantages, does create a problem with regard to the incorporation into the granules of relatively sensitive ingredients, such as the conventional silicone suds suppressors, at least partly as a result of the high alkalinity and temper-; atures present during the crutching stage. Such ingredients can of course be incorporated into the composition after spray-drying, for example, by dry mixing or spraying on. But the necessity of such an extra step in the process is unde-sirable. In addition, certain ingredients, especially those present in minor amounts, are not easy to distribute uniformly throughout a spray-dried granular composition. Clearly then, a very desirable way to include a silicone suds suppressor into a detergent composition would be simply to add the material directly to the crutcher mix before spray-drying.
Furthermore, it is known that the introduction of alkoxylated nonionic surfactants into an aqueous detergent crutcher mix tends to cause inhomogeneity in the mix. This is because the nonionic materials tend to be oily and to exist in a separate phase. This problem can be helped by the use of agents such as certain alkyl phosphate esters ~al8~69t7 .`

or preferably, as is taught in Canadian Patent No. 1,039,141 of R. M. Wise, granted September 26, 1978, by using kaolinite or bentonite clays. However, this problem of inhomogeneity in the crutcher mix is exacerbated by the addition of conven-tional silicone suds suppressors, such as polydimethysiloxane, since these materials are themselves oily and do not disperse well either in water or in nonionic surfactant.
It is therefore an additional object of this invention to provide spray-dried detergent granules which include a nonionic surfactant and also a silicone suds suppressor. ;
It is a further object herein to provid~ an improved process for the incorporation of certain silicone suds suppress-ors into spray-dried detergent granules containin~ substantial quantities of nonionic surfactant.
DESCRIPTION OF THE PRIOR ART
Silicones are widely known as useful suds suppressing ;
agents in aqueous systems. For example, U.S. Patents 3,250,727;
3,383,327; and 3,455,839 relate to suds suppressors based on polydimethyl-siloxane and their use in defoaming aqueous solutions.
U.S. Patent 3,235,509 relates to silicone suds suppressors which are absorbed into a solid silica material in order to improve their stability towards alkaline materials.
However, even this silicone/silica material has been found unsatisfactory for certain applications and U.S. Patent 3,933,672, Bartolotta et al, issued January 20, 1976, relates to the further protection of silicone/silica materials by their incorporation into a solid, substantially non-surface active matrix.
Clearly, the additional step of encapsulating or otherwise protecting the silicone material in an inert carrier is both expensive and time-consuming, and it has therefore - 16~1 3S69~7 been suggested in Canadian Patent No. 525,433 and in U.S.
Patent 3,829,386 that a silicone suds suppressor can be incorporated into a base product (for example, a carrier granule which may be alkaline) using a normally liquid surfactant as an incorporation medium. Unfortunately, this approach has not been found to be entirely satisfactory since most conventional silicone materials, for example polydimethylsiloxane itself, do not disperse wèll in liquid surfactants and tend to migrate out of the surfactant into contact with other more harmful con-stituents of the compositions. ~
It has further been suggested, in French Patent ! :

2,279,843, that certain silicone suds suppressor materials may be formed into a powder and then mixed together with detergent granules. As above, this procedure introduces additional steps into the detergent-making process.
SUMMARY OF THE INVENTION
; According to the present invention there is provided a detergent composition comprising an intimate mixture of from about 2.5% to about 100% by weight of the composition of a nonionic surfactant and a suds suppressing amount of a silicone suds suppressor, said intimate mixture being selected from the group consisting of (a) a mixture of a normally solid nonionic surfactant with a non-self-emulsified silicone suds suppressor and (b) a mixture of a normally liquid or solid nonionic surfactant with a self-emulsified silicone suds suppressor. Self-emulsified suds suppressors are characterized ~ by the presence of an emulsifying component, are highly dis-; persible in solid nonionic surfactants and will self-emulsify in liquid nonionic surfactants.
The silicone suds suppressor of the instant compo-sitions is employed herein in a "suds suppressing amount".

569~7 By "suds suppressing amount" is meant that the formulator of the compositions can select an amount of the suppressor which will control the suds to the extent desired. For example, for use in automatic dishwashers, a suds height of zero or near-zero is desirable; accordingly relatively more of the suds suppressor will be used. For hand dishwashing, relatively less suds suppressors will be used. For laundry washing machines, the amount of suds which can be tolerated may vary widely depending on the particular application, and accordingly more or less of the suds suppressors will be used. The amount of suds controller will also vary with the detergent component selected. For example, with high sudsing surfactants, relatively more of the controller is used to achieve the desired suds control than when low foaming detergents are selected for use in the compositions herein.
The term "nonionic surfactant" is not intended to include compounds which, although they have certain surface active properties, provide substantially no detergent ability.
; Typical of such materials not encompassed by the invention are the polyethyleneglycols and condensates of more than about 20_ moles of ethylene oxide with a long-chain alcohol. -Preferred self-emulsified silicone suds suppressors are those which contain a modified polysiloxane having poly-oxyalkylene moieties in the polymer. When these materials are utilized, the present invention provides a process for pre-paring an aqueous crutcher mix containing a nonionic surfactant, comprising the addition to the crutcher mix of this specific type of silicone suds suppressor and blending the crutcher mix at a temperature of at least 150F ~preferably 150F to 210F) until homogenous. The crutcher mix is then dried, preferably spray-dried, to provide homogenous detergent granules.

;~ i :l.O~S69r~' In its compositional aspect, this embodiment provides for homogeneous, granular, spray-dried detergent compositions comprising (a) from about 2% to about 60go tpreferably 5% to 35%) of an alkoxylated nonionic surfactant; and (b) a suds suppressing amount of a self-emulsi~ied silicone suds suppressor containing a modified polysiloxane having at least one polyoxyalkylene moiety in the polymer.

DETAILED DESCRIPTION OF THE INVENTION
The compositions of the pxesent invention comprise -two essential components, a nonionic surfactant and a silicone suds suppressor, which, it is believed, are in intimate ad- ~
mixture. By the term "intimate admixture" is meant that the `-silicone suds suppressor is dispersed in and is in direct con-tact with the nonionic surfactant and does not tend to migrate - out of the surfactant during storage of the composition.
It will be understood that the compositions can additionally comprise a wide range of other materials conven-tionally found in detergent compositions of various types andit will also be appreciated that the compositions may contain additional nonionic surfactant which are not mixed with the silicone suds suppressors.
Silicone Suds Suppressor The silicone materials employed as the suds suppres-sors herein can be alkylated polysiloxane materials of several 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 ~ ~ ` ,' ` !

69~
siloxane units and hydrocarbyl groups of various types. In general terms, the silicone suds controllers can be described as containing siloxane moieties having the general structure R
sio ) x R' wherein x is from about 20 to about 2,000, and R and R' are each alkyl or aryl ~roups, especially methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes (R and Rl are methyl) having a molecular weight within the range of from about 200 to about 200,000, and higher, are all useful as suds con-trolling agents. Such silicone materials are commercially available from the Dow Corning Corporation under the trade mark "Silicone 200 Fluids".
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 alkyl, aryl or mixed alkylaryl `~
silicone dichlorides with water in the manner well known in the art. As specific examples of such silicone suds controll-ing agents useful herein there can be mentioned, for example, diethyl polysiloxanes; dipropyl polysiloxa~es; dibutyl poly-siloxanes; methylethyl polysiloxanes; phenylmethyl polysiloxanes;
and the like. The dimethyl polysiloxanes are particularly useful herein due to their low cost and ready availability.
A second type of silicone suds controlling agent use- -~
ful in the compositions herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica. Such mixtures of silicone and silica can be prepared by affixing the silicone to the surface of silica ~85ti~7 (SiO2), for example by means of the eatalytie reaction disclosed in U.S. Patent 3,235,509. Suds eontrolling agents comprising mixtures of silicone and silica prepared in this manner preferably comprise silieone and siliea in a silicone:silica ratio of from l9:1 to 1:2, preferably 10:1 to l:l. The silica can be chemically and/or physically bound to the silicone in an amount which is preferably about 10% to 15~ by weight, based on the silicone. The particle size of the silica employed in sueh silica/silicone suds controlling agents should prefer-ably be not more than lO0 millimicrons, preferably from 10millimicrons to 20 millimierons, and the specific surface area of the silica should exeeed about 50 m /g.
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 several known methods may be used for making a hydrophobic silica which can be employed herein in eombination with a silicone as the suds eontrolling agent. ;~
For example, a fumed silica can be reacted with a trialkyl chlorosilane (i.e., "silanated") to aPfix hydrophobic tri-alkylsilane groups on the surfaee of the silica. In a preferred and well known process, fumed silica is eontaeted with trimethyl-chlorosilane and a preferred hydrophobic silanated silica use-ful in the present eompositions is seeured.
In an alternate procedure, a hydrophobic silica useful in the present compositions and processes is obtained by eontacting silica with any of the following compounds: metal, ammonium and substituted ammonium salts of long chain fatty acids, such as sodium stearate, aluminum stearate, and the like;
silylhalides, sueh as ethyltrichlorosilane, butyltrichlorosilane, tricyclohexylehlorosilane, and the like; and long chain alkyl 3S69~
:;

amines or ammonium salts, such as cetyl trimethyl amine, cetyl trimethyl ammonium chloride, and the like. ;
A preferred suds controlling agent herein comprises a hydrophobic silanated ~most preferably trimethylsilana-ted) silica having a particle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m2/g intimately admixed with a dimethyl sili-cone 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 about 19:1 to about 1:2. Such suds controlling agents preferably comprise silicone and the silanated silica in a weight ratio of silicone:silanated silica of from 10:1 to `
1:1. The mixed hydrophobic silanated (especially trimethylsilan-ated) silica-silicone suds controlling agents provide suds con-trol over a broad range of temperatures, presumably due to the ~
controlled release of the silicone from the surface of the ,~ -silanated silica.
Yet another 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 di-methyl silicones. The silicone "resins" used in such composi~
tions can be any alkylated silicone resins, but are usually those prepared from methylsilanes. ~ilicone resins are common- ~
ly described as l'three-dimensional" polymers arising from the -hydrolysis of alkyl trichlorosilanes, whereas the silicone fluids are "two-dimensional" polymers prepared from the hydrolysis of dichlorosilanes. The silica components of such compositions are the micro-porous materials such as the fumed silica aerogels and xerogels having the particle sizes and surface areas hereinabove disclosed.

-- 10 ~

~8S69q The mixed silicone fluid/silicone resin/silica materials useful in the present compositions can be prepared in the manner disclosed in U.S. Patent 3,455,839. These mixed materials are commercially available from the Dow Corning Corporation. According to U.S. Patent 3,455,839, such materials can be described as mixtures consisting essentially of:
(a) from about 10 parts of about 100 parts by weight of a polydimethylsiloxane fluid having a viscosity in the range from ~0 cs. to 1500 cs. at 25C.
10~b) 5 to 50 parts by weight of a siloxane resin composed of (CH3)3SiOl/2 units and SiO2 units in which the ratio of the (CH3)3SiOl/2 units to the SiO2 units is within the range of from 0.6/1 to 1.2/1; and ~ ~
(c) 1 to 10 parts by weight of a silica aerogel. ~-Such mixtures can also be sorbed onto and into a water-soluble solid as disclosed above.
The above-discussed silicone suds suppressors are, in general, not readily dispersible in nonionic surfactants~ :
and if they are aispersed by agitation, they tend to settle or migrate out of the surfactant. For the purposes of the present invention, therefore, these relatively non-dispersible silicone suds suppressors are used in admixture with nonionic surfactants which are normally-solid, i.e. solid at room temperature. This will be discussed in greater detail here-inafter.
There is a type of silicone suds suppressor which ~ -is highly dispersible in solid surfactants and which self-emulsifies in liquid surfactants. This type of suppressor ~;
has little or no tendency to migrate out of the surfactant phase and, with this type of silicone material, the present invention encompasses the use of liquid, as well as solid, ~L~85~7 nonionic surfactants.
The above-mentioned self-emulsifiable silicone suds suppressors are characterized by the presence of an emulsify-ing component in the suds suppressor compositions. The pre-ferred self-emulsifiea suds suppressors are those which contain emulsifiers which ha~e at least one polyoxyalkylene moiety incorporated into a basic polysiloxane structure~ The polyoxy-alkylene moieties are preferably incorporated as polymer groups substituted on silicone atoms and pendant on the basic poly- --siloxane chain. However, provided that the silicone compound is rendered into an emulsifier, the polyoxyalkylene moieties can -~
be in other positions and may, for example, form a part o* the basic polymer chain; i.e., as a block co-polymer. The use of these preferred emulsifiers in the silicone suds suppressor composition permits the inclusion of the suds suppressors in an aqueous, alkaline crutcher mix, and the formation of a spray-dried, granular detergent composition containing the suds suppressors in active form.
Highly-preferred emulsifiers of the type described ``~
above are typically represented by the formula a 4-a wherein a is 0 or an integer from 1 to 3; R is selected from the group consisting of (a) alkyl groups containing from 1 to about 30 carbon atoms, (b) groups having the formula -R'--(OR')bOR
wherein R' is an alkylene group containing 1 to about 6, preferably from 2 to 4, carbon atoms, b has a ~alue of from 1 to about 100; and R" is a capping group which can be selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, aralkyl or alkenyl groups containing up to 20 carbon atoms;
acyl groups containing up to 20 carbon atoms, sulfate, sulfonate, phosphate, phosphonate, borate or isocyanate groups, or mixtures ~(~856~7 thereof; and Y is a group having the formula ~ , (-O-Si-) -OSiR
R
wherein R has the formula given hereinbefore, and c has a value from 1 to 200; and wherein at least one R group in the compound has the aforesaid formula [-R'(OR'~b-R"]
in which b is sufficiently large to create an emulsifier.
Preferred emulsifiers and self-emulsifiable silicone suds controlling agents containing them are those described in Morehouse, U.S. Patents 3,233,986 and 3,511,7~8. The agents of U.S. Patent 3,511,788 are most preferred. Preferred combinations of these emulsifiers together with silicone suds controlling agents are disclosed in British Patent 1,373,903 and U.S. Patent 3,746,653. Preferably, the mixtures will contain at least 50% of RaSiY4 a' from about 5% to about 45% of a polydimethylsiloxane li~uid and from 0.05% to about 5% ~; ;
of silica. The mixture can additionally comprise a minor `amount of a polydimethylsiloxane resin. `
Other effective self-emulsified silicone suds -suppressors are those which contain a high ethoxylate of a fatty acid as the emulsifying component. The condensation products of from about 300 to about 2,000 moles of ethylene oxide for each mole of fatty acid are particularly useful.
~atty acids are straight-chain saturated and unsaturated mono-carboxylic acids, usually containing an even number of carbon atoms (from about 10 to about 20), preferably around eighteen in number. Examples of common fatty acids include palmitic acid, stearic acid and oleic acid.
The emulsifying component may also be a ~witterionic ~8S69~

surface active agent. Zwitterionic surfactants useful herein include derivatives of aliphatic quaternary ammonium, phos-phonium and sulfonium compounds, in which the aliphatic moieties can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing :.' group. Preferred 2witterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patent

3,925,262, Laughlin et al, issued December 9, 1975; and U.S.
10Patent 3,939,678, Laughlin et al, issued December 30, 1975. .
Particularly preferred ethoxylated zwitterionic sur-factants are those having the formula:

C16H33 1 (C2H4OlgC2H4X wherein X is SO3 or SO4. ~ ~

CH .~ :
Additional preferred zwitterionic surfactants include those having the formula: :

16 33 N (C2H4)yC2H4S4 t 2 4 )x wherein the sum of x + y is equal to about 15. ;
The amount of silicone suds suppressing composition :.
~ used is from about 0.01% to about 5%, preferably from about ; 0.05% to about 0.5%, and most preferably from about 0.1%
to about 0.4% by weight of the detergent compositions of the present invention.
Nonionic Surfactan-t "
As indicated above, the nonionic surfactants use-ful in the present invention may be solid or, when in admix-ture with self-emulsifiable silicone materials, liquid.
Most commonly, nonionic surfactants are compounds produced by the condensation of an alkylene oxide (hydrophilic ~8S6~7 in nature) with an organic hydrophobic compound which is usually aliphatic or alkyl aromatic in nature. The length of the hydrophilic polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
The balance between the hydrophobic and hydrophilic moieties of the nonionic surfactant and, more importantly, the chain length of each of the moieties, determines whether the surfactant is normally solid (i.e. melting point ~18C) or normally liquid.
Examples of suitable types of nonionic surfactant (without particular reference at this point to their phase) include:
1. The polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of -alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene ``
oxide being present in amounts equal to 5 to 20 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived, for example, from polymerized propylene, diisobutylene, octene, or nonene. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol, dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol, dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol, di- ;
isoctylphenol condensed with about 15 moles of ethylene -oxide per mole of phenol. Commercially available nonionic surfactants of this type include "igepal CO-610*
*Trademark :1~8S6~7 marketed by ~he GAF Corporation; and "Triton X-45"**, "Triton X-114"***, "Triton X-100" and "Triton X-102" , all marketed by the Rohm and Haas Company~ ~' 2. The condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol may either be straight or branched and generally contains from about 8 to about 22 carbon atoms. Pre~erably, there are from about 3 to about 18 moles of ethylene oxide per mole of alcohol. Examples of such ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the above-described coconut alcohol. Examples of commercially available nonionic sur-factants of this type include "Tergitol 15-S-9"1 marketed by the Union Carbide Corporation, "Neodol 23-6.5"2 marketed by `
the Shell Chemical Company and "Kyro EoB"3 marketed by the Procter & Gamble Company.
3. The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from about 1,500 to 1,800 and of course exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends ** Trademark *** Trademark t Trademark tt Trademark Trademark 3 Trademark Trademark 35~97 to increase the water-solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50%
of the total weight of the condensation product. Examples of compounds of this type include certain of the commerically available "Pluronic"4 surfactants marketed by the Wyandotte Chemicals Corporation.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic base of these products consists of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of from about 2,500 to about 3,000. This base is condensed `
with ethylene oxide to the extent that the condensation product contains from about 40 to about 80 percent by weight ~-of polyoxyethylene and has a molecular weight of from about

5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available "Tetronic" compounds marketed by the Wyandotte Chemicals ., Corporation.
Mixtures of the above surfactants are also useful in ~;
the present invention.
Of all of the above-described types of nonionic sur~
- factants, preferred surfactants which are normally solid include the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide per mole of nonyl phenol, the condensation product of tallow fatty alcohol with about 9 moles of ethylene oxide per mole of fatty alcohol, the condensation product of ; a C15-C20 aliphatic alcohol with from about six to twenty ~ 30 moles of ethylene oxide, and the ethylene oxide/propylene ": 4Trademark 5Trademark -, ~s~q oxide copolymer marketed under the designation of "Pluronic 2.5R5"6. Preferred surfactants which are normally liquid include the condensation product of a C12-C13 alcohol with 3 moles of ethylene oxide per mole of alcohol, the conden-sation product of a C14-C15 alcohol with 7 moles of ethylene oxide per mole of alcohol, the condensation product of a C12-C15 aliphatic alcohol with from about 3 to ~ moles of ethylene oxide, and the ethylene/propylene oxide condensate marketed by Wyandotte Chemicals Corporation under the trademark of "Pluradot HA 430".
The preferred self-emulsified suds suppressors, containing a modified polysiloxane having polyoxyalkylene moieties in the polymer, may be combined with any of the detersive alkoxylated surfactants well-known in the art and be formed into granular spray-dried detergent compositions.
In general terms, these nonionics are water-soluble detersive surfactants of the formula R-O-(cyH2yo)a~(czH2zo)b CwH2w wherein R is selected from the group consisting of primary, secondary and branched chain alkyl hydrocarbyl moieties;
primary, secondary and branched chain alkenyl hydrocarbyl moieties; and primary, secondary and branched chain alkyl-and alkenyl-substituted phenolic hydrocarbyl moieties; said hydrocarbyl moieties having a hydrocarbyl chain length of from 8 to about 20, preferably 10 to 16, carbon atoms. In the general formula for the alkoxylated nonionic surfactants herein, y and z are each integers of from 2 to about 3, pre-ferably 2, either z or y being 2 when the other integer is 3 (i.e., excluding the all-P0 surfactants); w is an integer of from 2 to about 3, preferably 2, and a and b are each integers of from 0 to about 8, the sume of a ~ b being in the range of : ~ 6Trademark 1~85~9~7 ~rom 6 to about 25, pre~erabl~ 6 to 10. The formula of the surfactants therein encompasses ethylene oxide (EO) as well as mixed etheylene oxide-propylene oxiae ~EO-PO~ alkoxylates, all of which are useful herein. The all~PO surfactants do not provide cleaning advantages in detergent compositions and are not contemplated for use herein.
Preferred nonionic surfactants used herein are the ethoxylated nonionics, both from the standpoint of avail ability and cleaning performance.
Specific examples of alkoxylated nonlonic surfactants include, but are not limited to, the di~ throu~h hexadeca-alkoxylates of C8-C18 straight chain, primary alcohols, the di- through hexadeca-alkoxylates of C~-C2Q straight chain, secondary alcohols; the di- through hexadeca-alkoxylates of ~
alkyl phenols, the di- through hexadeca-alkoxylates of primary ~ -and secondary alkenyl alcohols and alkenyl phenols; and the di- through hexadeca-alkoxylates of branched chain primary and secondary alcohols.
Particularly preferred alkoxylated nonionic surfactants include C8-C18 aliphatic alcohols condensed with 3 to about 15 moles of ethylene oxide per mole of alcohol and (C6-C9 alkyl) phenols condensed with from about 6 to about 16 moles of ethylene oxide per mole of phenol.
One mixed alkoxylated nonionic system which is useful herein comprises one or more of the foregoing detersive alkoxylated nonionic surfactants having an HLB in the range of from about 11 to 17 (preferably 12 to 15) and, as a "co-surfactantl', one or more water-soluble alkoxylates having an HLB in the range of 7 to 10.5 (preferably 9 to 10.5). The two types of alkoxylated materials are combined in appropriate ~-weight ratios to provide an overall HLB of the mixture of ~8S6~7 from about 10 to about 12.5 (preferably 10 to 12; most prefer-ably 10.5 to 12.0). Such mixtures of nonionic surfactant and nonionic co-surfactant provide superior fabric cleaning per-formance and are particularly useful for removing greasy soil from polyester and cotton/polyester fabric blends. These preferred nonionic suxfactant-plus-nonionic "co-surfactant"
alkoxylate mixtures are more fully described in Belgian Patent No. 821,093 issued April 15, 1975.
A further highly preferred alkoxylated nonionic sur-factant system is that disclosed and claimed in the commonly assigned Canadian Patent 2~o. 1,059,865 of Jerome H. Collins, granted August 7, 1979. This surfactant system comprises a base-catalysed primary alcohol eth~xylate having the formula Rl-R2-O (CH2cH2O)n H wherein Rl i5 a linear alkyl residue and R2 has the formula CH R3 CH2, R3 being selected from hydrogen and mixtures thereof with Cl-C4 alkyl groups there being not more than 70% by weight of said groups in the mixtures, wherein Rl and R2 together form an alkyl residue containing `
a mean of 9 to 15 carbon atoms at least 65% by weight of said residue having a chain length within ~ 1 carbon atom of the mean, wherein 3 5 ~naV~ 6 5. Such a system is also character-ised by an unethoxylated alcohol content of < 5 wt% and by at ; least 63 wt% of ethoxylates containing two to seven ethylene oxide groups, the HLB of the system lying in the range 9 5-11.5. The system is otherwise free of alkoxylated non-ionic surfactants.
Nonionic surfactant systems o~ the above described type are produced by ethoxylating a suitable alcohol to less than the desired degree with a base catalyst and then stripping off the unethoxylated alcohol and lower ethoxylates to give a product having the desired ethoxylate distribution.

- 20 - `

: L~18~

A preferred material of this type can be prepared from "Neodol 23"*, a primary C12-C13 OXO alcohol sold by Shell Chemical Company and containing approximately 20~ of 2-alkyl (predominantly methyl) branching. To make the preferred nonionic surfactant, "Neodol 23" is ethoxylated with an average 3 moles of ethylene oxide per mole of alcohol and the ethoxylated material is then stripped to remove unethoxyl-ated alcohol and lower ethoxylates. Approximately 34% by weight ~;
of the ethoxylate is removed and the residue has an HLB of about 10.55 and an ethoxylation level of about 4.9 moles per mole of alcohol.
Other Ingredients In the broadest aspect of the present invention, the intimate mixture of the above-described two essential com-ponents can be incorporated into any of a wide variety of non-liquid detergent compositions. It will be understood that the process of incorporation must be such that the physical properties of the intimate mixture are not destroyed.
In general, a sufficient amount of the intimate mixture is used to provide a concentration of from about 0.01% to about 5%, preferably 0.05% to 0.5~, by weight of the silicone suds suppressors in the composition.
; The present invention encompasses detergent composi-tions which contain surfactant materials other than the essential nonionic surfactant. Such other surfactants are selected from anionic, nonionic, zwitterionic and ampholytic : .
surfactants.

Examples of the above type of surfactants are listed in U.S. Patent No. 3,862,058 of Nirschl and Gloss.

Useful anionic surfactants include alkyl sulfates *Trademark iO~3S6~
and sulfonates containing from about 8 to about 18 carbon atoms; alkyl benzene sulfonates having ~rom about 9 to -about 20 carbon atoms in the alkyl chain, especially sodium or alkanolamine salts of linear straight chain alkyl benzene sulfonates in which the average chain length of the alkyl -group is from about 10 to about 14, especially about 11.8 carbon atoms (normally abbreviated NaC11 8LAS); alkyl ether ;~
sulfates of the formula R O (C H O) SO M
wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, n is 1 to 30 and M is an alkali metal cation; and olefin sulfonates derived by the sulfonation of C12-C24 ~-olefins with sulfur trioxide. Other useful anionic sur-factants in combination with the silicone/surfactant mixture ~;
used in the present invention are alkaline earth metal, pre-ferably magnesium or calcium, salts of linear alkyl benzene ~-sulfonic acid. Useful nonionic surfactants, apart from those already mentioned, include amine oxides, phosphine oxides and ~;~
sulfoxides. Specific examples of such surfactants include dimethyldodecylamine oxide, dimethylstearylamine oxide, bis- ~-(2-hydroxyethyl) dodecylamine oxide, dimethyldodecylphosphine ; ~;
oxide, dodecylmethyl sulfoxide and octadecyl methyl sulfoxide. ~
Preferred zwitterionic surfactants include higher ;-alkyl or alkaryl ammonio propane sulfonates, such as ~; 3-(N,N-dimethyl N-hexadecylammonio~ propane -l-sulfonate, 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy propane-l-sul- ~ -fonate and 3-(N,N-dimethyl-N-alkylammonio-2-hydroxy propane-l-sulfonate, the alkyl group being derived from middle cut coconut fatty alcohol and higher alkyl or alkaryl ammonio-carboxylates such as (N-dodecylbenzyl-N,N-dimethyl ammonio) acetate, (N,N-dimethyl-N-hexadecylammonio) acetate and - 22 - ~-t 1~1856~7

6-(N-dodecylbenzyl-N,N-dimethyl ammonio) hexanoate. Other ;
useful zwitterionic materials are the ethoxylated ammonio-sulfonates and sulfates disclosed in U.S. Patent 3,929,678, Laughlin et al, issued December 30, 1975.
Detergent compositions of the present invention nor-mally include builder salts, especially alkaline, poly-valent anionic builder salts. These alkaline salts serve to maintain the pH of the cleaning solution in the range from about 7 to about 12, preferably from about 8 to about 11.
When the compositions of the present invention are formed by spray-drying, such builders may be employed in the crutcher mix at concentrations of from about 1~% to about 80% by weight (preferably 15% to 50%) to yield dry detergent compositions containing from about 15% to about 90% by weight, preferably from about 20% to 60%, of said builders.
Suitable detergent builder salts useful herein can be of the poly-valent inorganic or poly-valent organic types, or mixtures thereof. Non-limiting examples of suitable water soluble, alkaline detergent builder salts include alkali metal phosphates, pyrophosphates, orthophosphates, polyphosphates, phosphonates, carbonates, polyhydroxysulfonates, silicates, polyacetates, carboxylates, polycarboxylates and succinates. Specific examples of such salts include the sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyph~sphates, orthophosphates and hexa~
metaphosphates.
Examples of suitable organic alkaline detergency builder salts are: (1) water-soluble amino polyacetates, ~: e.g., sodium and potassium ethylenediamine tetraacetates, nitrilotriacetates and N-(2-hydroxyethyl) nitrilodiacetates;
(2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates; (3) water-soluble polyphosphonates, - 23 - ~ -~L~B5~9~7 including, sodiumr potassium and lithium salts of ethane-l~hydroxy-l, 1-diphosphonic acid; sodium potassium and lithium salts of methylenediphosphonic acid and the like.
Additional organic buildeL salts useful herein include the polycarboxylate materials described in U.S.
Patent No. 2,264,103, including the water-soluble alkali metal salts o~ mellitic acid. The water-soluble salts of polycarboxylate polymers and copolymers such as are described in U.S. patent No, 3,308,067, are also suitable herein. It is to be understood that while the alkali metal salts of the foregoing inorganic and organic poly-valent anionic builder salts are preferred for use herein from an economic standpoint, the ammonium, alkanolammonium, e.g., triethanolammonium, di-ethanolammonium, and the like, water-soluble salts of any of the foregoing builder anions are useful herein.
A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those disclosed in Belgian Patent 814,874, issued November 12, 1974. This patent discloses and claims ~
detergent compositions containing sodium aluminosilicates ~ -of the formula Na (AlO ) (SiO ) xH O
wherein z and y are in~egers equal to at least 6, the molar ;
-~ ratio of z to y is in the range of from 1.0:1 to about 0.5:1 and x is an integer from about 15 to about 264, said aluminosilicates having a calcium ion exchange capacity of - at least 200 mg. eq/gram and a calcium ion exchange rate of at least about 2 grains/gallon/minute/gram. A preferred ; -material is Nal2(SiO2 A1O2)12 2 Mixtures of organic and/or inorganic builders can be used herein. One such mixture o~ builders is disclosed in Canadian Patent No. 755,038, e.g., a ternary mixture of ~-~

~085697 sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane-l-hydroxy-l, l-diphosphonate.
While any of the foregoing alkaline poly-valent builder materials are useful herein, sodium tripolyphosphate, sodium nitrilotriacetate, sodium mellitate, sodium citrate and sodium carbonate are preferred herein for this builder use. Sodium tripolyphosphate is especially preferred herein as a builder both by virtue of its detergency builder activity and its ability to suspend illite and kaolinite clay soils and retard their redeposition on the ~abric surface.
In the non-spray-dried compositions of the present invention the detergent builders are generally used at con-centrations of from about 10~ to about 60~, preferably 20%
to 50%, by weight.
Bleaching agents may also be incorporated into the compositions of the present invention and examples of typical bleaching agents are chlorinated trisodium phosphate and -` the sodium and potassium salts of dichloroisocyanuric acid. ~, The detergent compositions disclosed herein can of ~ :
course contain other materials commonly used in such com-positions. For example, various soil-suspending agents such as carboxymethylcellulose, corrosion inhibitors, dyes, fillers such as sodium sulfate and silica, optical brighteners, ;~
germicides, anti-tarnishing agents pH adjusting agents such as mono-, di- or tri-ethanolamine, enzymes, and the like, well-known in the art for use in detergent compositions, can also s be employed herein.
- Proce-ssing of the Co-mpositions In a highly preferred processing aspect of the ~ ~
present invention, the intimate mixture of silicone suds ~ -suppressors and nonionic surfactant is formed in a liquid ~ -(if necessary molten) phase and the liquid mixture is sprayed, ~56~

coated onto, adsorbed onto or absorbed into a carrier granule which contains the other ingredients of the detergent composition.
When a self-emulsified silicone material is used in conjunction with a liquid or molten liquid surfactan-t, then the silicone can readily be mixed into the surfactant and form a stable emulsion or dispersion. Where the less dis-persible silicones are concerned, then it is necessary that the silicone/surfactant mixture (using molten surfactant) is subjected to ag~tation o shear shortly before being incorporated into the product. In this way, the silicone material remains sufficiently dispersed in the molten sur-factant that it does not migrate out before the surfactant ~` cools and sets after being sprayed on to product. Clearly, after the surfactant has set, there is no likelihood that the silicone material can escape.
When a normally solid surfactant is used, it is usual -~
to heat the surfactant to form a liquid phase, although the use of a solvent to bring the surfactant into solution is not excluded. ~In the heating process, it is important that ~-~ 20 the time during which silicone material isin contact with hot surfactant is minimized. In certain cases, silicone materials -can lose their efficacy if contacted by hot, i.e. in the temperature range 120-200F., surfactant over relatively long periods of time, for example, over 30 minutes~
In a preferred process, therefbre, liquid surfactant is sprayed continuously on to carrier granules and the silicone suds suppressor is injected into a conduit leading ~
to the spra~ nozzle, mixing means being provided down- -stream of the point of injection. The mixing means may comprise baffles in a conduit, or a foraminous plate in the conduit which would cause the silicone material to disperse effectively throughout the surfactant.

~856g7 For ease of mixing in the process, the self-emulsified silicone compounds are preferred both in admixture with solid and liquid surfactants.
Highly preferred detergent compositions of the present invention are those intended for use in automatic dishwashing machines. In these compositions, the intimate mixture of nonionic surfactant and silicone suds suppressors can be ;
sprayed on to a base granule comprising, for example, sodium tripolyphosphate, chlorinated trisodium phosphate and sodium silicate. Such base granule can be prepared by agglomerating the sodium tripolyphosphate and the chlorinated trisodium ~ phosphate with a solution of sodium silicate. Examples of A~ useful processes for preparing such granules are found in U.S. Patents 3,598,743 and 3,888,871. ` '-, In the case of automatic dishwashing machine products `, the compositions preferably comprise from about 20% to about 60% sodium tripolyphosphate, from about 10% to about 60%
sodium silicate and from about 15% to about 35% of chlorinated trisodium phosphate in the base granule. Incorporated into ~`
- 20 this base granule is the intimate mixture of nonionic sur-factant and silicone suds suppressor to give a level of sur~
factant in the composition of from about 2.5% to about 12.5%
and a level of suds suppressor from about 0.05% to about 0.5%.
The detergent compositions of the present invention are preferably in granular form, but they can also be formulated in other non-liquid forms, for example as powders, tablets, pastes and gels.
When the particularly preferred self-emulsified silicone suds suppressors containing a modified polysiloxane having polyoxyalkylene in the polymer are used, the process herein may be carried out by preparing a detergent crutcher mix comprising the various components which are to be present in `

:
the final detergent composition in an aqueous medium.
The crutcher mixes employed in this process can conveniently comprise an aqueous slurry containing from about 15% to about 50~ (preferably from about 25% to about 40 by weight of water, from about 1~ to about 40% (preferably from about 5% to about 20%) by weight of a water-soluble organic detergent component comprising predominantly a non-ionic surfactant as hereinbefore described, and ~rom about 10% to about 80~ (preferably from about 15% to about 50%) by weight of detergency builder and adjunct materials as hereinbefore disclosed. . .
Use of the foregoing crutcher mixes in combination ~.
. with an amount of from about 0.005~ to about 5% by weight of :~
.. the crutcher mix of the preferred self-emulsified suds suppressors results in the formation of substantially homo- ; :
geneous mixes suitable for preparing homogeneous powdered and . granular detergent compositions. Of course, such detergent ..
: compositions contain the various ingredients originally pre-~: sent in the crutcher mix. However, th-e final concentrations of ~
such ingredients in the dry detergent compositions may differ ::
somewhat from their concentrations in the crutcher, inasmuch as a major portion of the water is removed on drying~
The preferred self-emulsified silicone suds suppressor, although generally stable in the presence of nonionic sur-factant, can become inactivated if subjected to extremes of heat in the presence of surfactant. It is therefore preferred that the crutcher mix is formed and blended as quickly as possible and then spray-dried without undue delay.
Generally, residence time in the crutcher of the silicone-containing mix should not exceed about 10-15 minutes.
It is preferred that the silicone suds suppressor is intimately mixed with the nonionic surfactant be~ore being s~

added to the crutcher, as it is believed to be important that the silicone material remains in the same phase as the nonionic surfactant.
The crutcher mix is generally prepared at a tempera-ture of 140F to 150F and the hot mix is introduced into a spray-drying tower and sprayed to provide a granular detergent composition. The spray-drying part of the process is con-ventional.

~.
The ~ollowing examples are representative of the compositions and processes of the present invention.

EXAMPLE I

, A detergent composition for an automatic dishwashing -machine was prepared having the following ingredients:

Component ~ by Wt. of the Composition ~ Sodium tripolyphosphate (STP) 43.0 `

:~! Sodium silicate (SiO :Na O
ratio 2.8) 2 2 16.0 .
Chlorinated trisodium phosphate (Cl TSP) 26.0 Tallow alcohol condensed with 9 moles of ethylene oxide per mole of alcohol (TAEg~ 7.5 "Dow Corning DB 544"* suds suppressor 0.4 Moisture and minors to 100 ;
To prepare the above composition, the STP and the Cl TSP were mixed and agglomerated in a pan granulator using a solution of the sodium silicate. After granulation was complete, the TAEg was heated to above its melting point and the "DB 544" suds suppressor was mixed into the TAEg to form a stable emulsion. The molten emulsion was then sprayed onto the granular material to form the detergent composition.
, , A silicone suds suppressor containing a siloxane/glycol copolymer.
* Trademark ~L~8~

The above composition was tested in the following manner:
Production of foam in an automatic dishwashing machine causes a reduction in the speed of revolution of the rotor arm which is activated by the force of water or detergent solution passing throu~h the arm. Using the speed of the rotor arm with pure water as a control (100% efficiency), the speed of the rotor in a soiled surfactant solution is measured.
- In general, when a low-sudsing surfactant is used together -; with a suds suppressor, the rotor arm revolves at around 90% of its speed in waterO The figure of 90% is termed the "suds efficiency". The higher the figure, the more effective is the suds suppressor.
The composition of Example I, freshly made, had a ;~
suds efficiency of 90%. After nine weeks storage at 90F, the composition was tested again and was found still to have a suds efficiency of 90%.
Substantially similar results are obtained where the "DB544", in the above composition, is replaced by "DB31"*, a silicone/silica suds suppressor containing a high ethoxylate fatty acid emulsifying component, marketed by Dow Corning. ~;~
EXAMPLE II
A composition analogous to that of Example I but containing 0.3% of polydimethylsiloxane in place of the "DB
544" suppressor was prepared. No substantial change in suds efficiency of the composition was noted after three weeks.
EXAMPLE III
A composition analogous to that of Example I but containing 0.4% of "Dow Corning DB 100"* suds suppressor (a silicone/silica suppressor) in place of the "DB 544" suppressor * Trademark ~3569~7 i was prepared.
EXAMPLE IV
Using the procedure of Example I, the following composition was prepared:
`` Component % by Wt.
Sodium tripolyphosphate 26.0 Sodium silicate (SiO2:Na2O ratio 2.4~ 5.0 Sodium silicate (SiO2:Na2O ratio 2~8) 12.0 Chlorinated trisodium phosphate 22.0 TAEg 5 0 ;~ 'SAG loo~** 0.2 `, Moisture and minors to 100 ~' Using the suds test detailed above, the above -' composition was tested before ahd after three weeks storage 1 at 90F. No sig~iificant change in suds efficiency was observed.
EXAMPLE V
A detergent composition suitable for use in an auto-matic dishwashing machine and having a normally liquid .. .
nonionic surfactant was prepared in a manner analogous to that described in Example I and having the following com-position:
Component % by Wt.
STP 46.0 Sodium silicate (SiO2:Na2O ratio 2.8)17.0 Cl TSP 26.0 Coconut fatty alcohol condensed with 6 ~ `
moles of ethylene oxide per mole of alcohol 7.5 "DB 544 Moisture and minors to 100 ~ ~ .
A polydimethylsiloxane marketed by Union Carbide. ~;
* Trademark ** Trademark ;'' ~S6~7 This composition was relatively high-sudsing and, ~'~
freshly made, had a suds efficiency of 57%. After three ;:
weeks storage at 90F, the suds efficiency was measured .
and was found to be 54% which is not significantly reduced.
'. Substantially similar results were obtained where '~ ~, : - ~
: the "DB 544" in the above composition was replaced by "DB 31"*, ~ a silicone/silica suds suppressor containing a high ethoxylate :' (containing from about 300 to 2000 ethoxy groups per moleculeq~
::
fatty acid emulsifying component, marketed by Dow Corning.
.~, 10 Comparable results are also obtained where the "DB 544" :.
'~ in the above composition is replaced by "DB 100 " suds suppressor ,~
together with a zwitterionic surfactant as an emulsifying . component, such as I H3 16H33 1 (C2H40) 9C2H4S04 ~ ' CH3 ~-EXAMPLE VI ;~
A composition similar to that of Example V was pre-; pared, but using "Pluradot HA 430" (Wyandotte Chemical Cor- .' '~
poration) as the sole nonionic surfactant (a liquid surfactant). ':: , In this case, only 0.1% of "DB 544" was employed and the composition was found to be storage-stable and to have good .
suds suppression.
All of the above examples provided compositions with good storage stability as evidenced by the continued '' activity of the suds suppressor after from three to nine weeks ~'~
of storage at 90F.
A composition comprising a carrier granule based on sodium carbonate and sodium silicate and using the liquid nonionic surfactant of Example V together with polydimethyl-silox~n,e s,-uds suppressor was found to have a suds efficiency ~ '' * Trademark . ~

`:

~.~6lS69~7 ~

' of 89% when freshly made, but this dropped rapidly to 80 after two weeks and continued to fall thereafter.
EXAMPLE VII
A spray-dried detergent composition was prepared, using the preferred self-emulsifying suds suppressors o~
the present invention and having the following composition:

Component ~ by Wt. of ~`
the Composit`ion `~

1 "Neodol 23" ethoxylated with 3 moles of ethylene oxide and stripped to HLB 10.55 11.0 ~ ~ 10 i~, Sodium tripolyphosphate 32.0 ;
Sodium silicate (1.6 ratio Na2O:SiO2~ 10.0 "DB 544" 0.2 Sodium sulfate 38.0 Moisture and minors to 100 ~
To prepare the above composition, all the ingredients ;
of the composition were slurried in water and blended at 150F to give a homogeneous crutcher mix. The mix was then introduced into a spray-drying tower and spray-dried to form homogeneous granules. .`
`
The resultant composition exhibited controlled sudsing , characteristics which were maintained after storage at 90F
and 80% relative humidity for three weeks.
The sa~e composition as above but with "Dow Corning DB
100"* suds suppressor replacing "DB 544" showed no suds suppression after spray-drying, even when fresh. "DB 100" does not contain a polyoxyalkylene-modified polysiloxane emulsifying component. `~
:' 1 "Neodol 23" is obtainable from Shell Chemical Company ,~

From Dow Corning, a silicone suds suppressor containing a copolymer of polydimethylsiloxane and a polyalkylene oxide.
* Trademark 1(~15 5~;9~7 `

EXAMPLE VI I I
A granular heavy-duty detergent composition was pre-pared by spray-drying in a conventional manner a detergent slurry. The slurry has the following composition:
Ingredient Parts by Wt.

Condensate of C14-C15 1:1 blend alcohol with 7 moles of ethylene oxide 17.0 4,4' thiobis t6-tertbutyl-m cresol~ 0.02 "~erol 525"* 0.7 Pentasodium tripolyphsophate anhydrous46.0 ~, Saturated C16-C22 fatty acid 0~7 Silicate solids, ratio SiO2:NaO 2.0 8.0 Sodium sulfate 14.0 Minor ingredients 3.0 Water 40.0 Suds regulating agent ("Dow Corning DB 544") 0.3 Substantially similar compositions were prepared (a) without the addition of the "DB 544" suds regulator, and ~
(b) replacing the "DB 544" regulator by an identical amount ;

of the suds regulator described in Belgian Patent 803,101 of February 1, 1974 to Bartolotta et al.
Seventy-five parts by weight of the granular base powder obtained after spray-drying the above slurry were dry-mixed with 25 parts by weight granular perborate tetrahydrate and 1% of additional minor ingredients inclusive of a proteolytic enzyme, a perfume and a polyethylene glycol having a molecular weight of about 400.
The suds regulating capacity of the granular bleach-containing finished product so formulated was tested ~1) freshly made, and (2) after an eccelerated storage test as ~ ;
more fully defined hereinafter. The suds regulating capacity * Trademark , ~ 5697 .'. :
was measured with a front-loading Miele drum washing machine under the following conditions.
Cloth load : 4, kg Product concentration : 0.65% (weight/volume) Temperature : mainwash up to the boil The suds height, expressed in centimeters, was :~
measured at a temperature of 90C through the front window.
The results were as ~ollows~
. ~ .

"~

~` ~LO~!3S~i9~7 ~ ` ~
,i~ ~ ~ :

~ C~
~ ~1 ., ! ~
~r~ '`
U~ ~9 , U~ ~ . ~' ~ .`,' m ~
,. : ~ -:
~ .

~ ~ r m ~ ~j 8 .cl ~`
u~ ~tr ~: i~ ~ o N
. . . ~ m . . .~ .~ ~
. . I ~ `':
0 .. , z~ .~ , ~
. . ~
~ ~ ': `
a~ ~ , .~ 3 p; 3 ~ ~ o\ ~ '~
o ~
~ a) o~ a) :
lQ ~ O
o oo oO
o . 1~ `

- 3 6 - .. `

~ 35697 ; ~
In the above scale, 6 cm. represents a consumer acceptable suds level at up to the boil conditions (90C).
Suds levels of 8 cm. and above are undesirable. Thus `
compositions according to this invention are at leas~ as good as or better than identical compositions wherein the suds regulator has been replaced with an equivalent amount ;`
of a suds suppressor which is known to be suitable for commercial purposes. -~

,. ~, ~ ~ ' ~ ~

. ~:

;..- ' :;

Claims (33)

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

1. A non-liquid detergent composition comprising an ingredient capable of inactivating silicone suds suppressors and, in intimate admixture therewith, from about 2.5 to about 100% by weight of the composition of an intimate mixture of a nonionic surfactant and from about 0.01 to about 5% by weight of silicone suds suppressor, said intimate mixture being selected from the group consisting of (a) a mixture of a normally solid nonionic surfactant with a non-self-emulsified silicone suds suppress-or, and (b) a mixture of a nonionic surfactant with a self-emulsified silicone suds suppressor, wherein the nonionic surfactant is selected from the group consisting of (a) the condensation product of alkyl phenols with from about 5 to 20 moles of ethylene oxide;
(b) the condensation product of C8-C22 aliphatic alcohols with from about 3 to 18 moles of ethylene oxide;
(c) the condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, wherein the molecular weight of the hydrophobic portion is from about 1,500 to about 1,800;

(d) the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine, wherein the molecular weight of the hydrophobic portion is from about 2,500 to about 3,000 and the conden-sation product contains from about 40 to about 80% by weight of polyoxyethylene; and (e) mixtures thereof.

2. A detergent composition according to Claim 1 wherein the suds suppressor comprises a self-emulsified sili-cone suds suppressor.

3. A detergent composition according to Claim 2 wherein the self-emulsified silicone suds suppressor contains, as an emulsifier, a modified polysiloxane having at least one polyoxyalkylene moiety in the polymer.

4. A detergent composition according to Claim l wherein said intimate mixture is incorporated into a carrier granule comprising a detergent builder salt.

5. A detergent composition comprising (A) from about 10 to about 60% of a detergent builder salt, and (B) an intimate mixture consisting essentially of (i) from about 2.5 to about 12.5% by weight of the composition of a normally solid nonionic surfactant, and (ii) from about 0.05 to about 0.5% by weight of the composition of a non-self-emulsified silicone suds suppressor;

wherein said nonionic surfactant is selected from the group consisting of (a) the condensation product of alkyl phenols with from about 5 to 20 moles of ethylene oxide;
(b) the condensation product of C8-C22 aliphatic alcohols with from about 3 to 18 moles of ethylene oxide;
(c) the condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, wherein the molecular weight of the hydrophobic portion is from about 1,500 to about 1,800;
(d) the condensation product of ethylene oxide with the product resulting from the reaction of pro-pylene oxide and ethylene diamine, wherein the molecular weight of the hydrophobic portion is from about 2,500 to about 3,000 and the condensa-tion product contains from about 40 to about 80%
by weight of polyoxyethylene; and (e) mixtures thereof.

6. A detergent composition according to Claim 5 wherein the suds suppressor is a polydimethylsiloxane fluid.

7. A detergent composition according to Claim 5 wherein the nonionic surfactant is a C15-C20 aliphatic alcohol condensed with from 6 to about 20 moles of ethylene oxide per mole of alcohol.

8. A detergent composition according to Claim 5 wherein the suds suppressor is a mixture of a polydimethyl-siloxane fluid and silica.

9. A detergent composition according to Claim 5 wherein the suds suppressor is a mixture which comprises:
(a) from about 10 parts to about 100 parts by weight of a polydimethylsiloxane fluid having a viscosity in the range from 20 cs. to 1500 cs.
at 25°C;
(b) from 5 to 50 parts by weight of a siloxane resin composed of (CH3)3 SiO1/2 units and SiO2 units in which the ratio of the (CH3)3SiO1/2 units to the SiO2 units is within the range of from 0.6/1 to 1.2/1; and (c) from 1 to 10 parts by weight of a silica aerogel.

10. A detergent composition comprising (A) from about 10 to about 60% of a detergent builder salt, and (B) an intimate mixture consisting essentially of (i) from about 2.5 to about 12.5% by weight of the composition of a nonionic sur-factant, and (ii) from about 0.05 to about 0.5% by weight of the composition of a self-emulsified silicone suds suppressor;

wherein said nonionic surfactant is selected from -the group consisting of (a) the condensation product of alkyl phenols with from about 5 to 20 moles of ethylene oxide;
(b) the condensation product of C8-C22 aliphatic alcohols with from about 3 to 18 moles of ethylene oxide;
(c) the condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, wherein the molecular weight of the hydrophobic portion is from about 1,500 to about 1,800;
(d) the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine, wherein the molecular weight of the hydrophobic portion is from about 2,500 to about 3,000 and the condensation product contains from about 40 to about 80% by weight of polyoxyethylene; and (e) mixtures thereof.

11. A detergent composition according to Claim 10 wherein the nonionic surfactant is normally liquid.

12. A detergent composition according to Claim 11 wherein the self-emulsified silicone suds suppressor contains as an emulsifier the condensation product of from about 300 to 2000 moles of ethylene oxide with a fatty acid.

13. A detergent composition according to Claim 10 wherein the self-emulsified silicone suds suppressor contains, as an emulsifier, a modified polysiloxane having at least one polyoxyalkylene moiety in the polymer.

14. A detergent composition according to Claim 13 wherein the self-emulsified silicone component contains an emulsifier having the general formula RaSiY4-a' wherein a is 0 or an integer from 1 to 3; R is selected from the group con-sisting of (a) alkyl group containing from 1 to about 30 carbon atoms, and (b) groups having the formula -R'-(OR')bOR'' wherein R' is an alkylene group containing from 1 to about 6, preferably from 2 to ~ carbon atoms, b has a value of from 1 to about 100;
and R" is a capping group which can be selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, aralkyl or alkenyl groups con-taining up to 20 carbon atoms, sulfate, sulfonate, phosphate, phosphonate, borate or isocyanate groups, or mixtures thereof; and Y is a group having the formula wherein R has the formula given hereinbefore, and c has a value from 1 to 200; and wherein at least one R group in the compound has the formula [-R'(OR')b-R''], in which b is sufficiently large to create an emulsifier.

15. A detergent composition according to Claim 14 wherein the suds suppressor additionally comprises a polydi-methylsiloxane fluid.

16. A detergent composition according to Claim 15 wherein the suds suppressor consists essentially of at least 50% by weight of a compound of the formula RaSiY4-a' from about 5% to about 45% of a polydimethylsiloxane liquid and from 0.05 to about 5% of silica.

17. A detergent composition according to Claim 16 wherein the nonionic surfactant is a C12-C15 aliphatic alcohol condensed with from 3 to about 9 moles of ethylene oxide per mole of alcohol.

18. A process for preparing the granular detergent composition of claim 1 comprising the steps of:
(A) preparing an intimate mixture in a liquid phase of a nonionic surfactant and a silicone suds suppressor, said intimate mixture being selected from the group consisting of (i) a mixture of a normally solid nonionic surfactant with a non-self-emulsified silicone suds suppressor, and (ii) a mixture of a nonionic surfactant with a self-emulsified silicone suds suppressor;
wherein said nonionic surfactant is selected from the group consisting of (a) the condensation product of alkyl phenols with from about 5 to 20 moles of ethylene oxide;
(b) the condensation product of C8-C22 aliphatic alcohols with from about 3 to 18 moles of ethylene oxide;
(c) the condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, wherein the molecular weight of the hydrophobic portion is from about 1,500 to about 1,800;
(d) the condensation product of ethylene oxide with the product resulting from the reaction of pro-pylene oxide and ethylene diamine, wherein the molecular weight of the hydrophobic portion is from about 2,500 to about 3,000 and the conden-sation product contains from about 40 to about 80% by weight of polyoxyethylene; and (e) mixtures thereof;
(B) spraying said intimate mixture in liquid phase onto a carrier granule comprising a detergent builder salt.

19. A process according to Claim 18 wherein the suds suppressor is a self-emulsified silicone suds suppressor con-taining, as an emulsifier, a modified polysiloxane having at least one polyoxyalkylene moiety in the polymer.

20. A process according to Claim 18 wherein the nonionic surfactant is normally liquid and the process is carried out at room temperature.

21. A process according to Claim 20 wherein the self-emulsified silicone suds suppressor contains, as an emulsifier, the condensation product of from about 300 to 2,000 moles of ethylene oxide with a fatty acid.

22. A process according to Claim 18 wherein the nonionic surfactant is normally solid and said intimate mixture is formed by melting the nonionic surfactant, passing the molten surfactant along a conduit to a spray nozzle and introducing said silicone suds suppressor into the conduit immediately upstream of said spray nozzle.

23. A process according to Claim 22 wherein at least one mixing means is provided in the conduit downstream of the point of introduction of the silicone suds suppressor.

24. A spray-dried granular detergent composition comprising (a) from about 2 to about 60% by weight of an alkoxylated nonionic surfactant, (b) from about 0.01% to about 5% by weight of the composition of a self-emulsified silicone suds suppressor containing a modified polysiloxane having polyoxyalkylene moieties in the polymer, and (c) from about 10% to about 80% by weight of a detergency builder;
said alkoxylated nonionic surfactant being selected from the group consisting of (i) the condensation product of alkyl phenols with from about 5 to 20 moles of ethylene oxide;
(ii) the condensation product of C8-C22 aliphatic alcohols with from about 3 to 18 moles of ethylene oxide;
(iii) the condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, wherein the molecular weight of the hydrophobic portion is from about 1,500 to about 1,800;
(iv) the condensation product of ethylene oxide with the product resulting from the reaction of propy-lene oxide and ethylene diamine, wherein the molecular weight of the hydrophobic portion is from about 2,500 to about 3,000 and the condensa-tion product contains from about 40 to about 80%
by weight of polyoxyethylene; and (v) mixtures thereof.

25. A detergent composition according to Claim 24 wherein the alkoxylated nonionic surfactant is present in an amount of from about 5 to about 35% by weight of the composition.

26. A detergent composition according to Claim 25 wherein the self-emulsified silicone component contains an emulsifier having the general formula RaSiY4-a wherein a is 0 or an integer from 1 to 3; R is selected from the group consisting of (a) alkyl groups containing from 1 to about 30 carbon atoms, and (b) groups having the formula -R'-(OR')bOR" wherein R' is an alkylene group containing from 1 to about 6, preferably from 2 to 4 carbon atoms, b has a value of from 1 to about 100; and R" is a capping group which can be selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, aralkyl or alkenyl groups containing up to 20 carbon atoms;
acyl groups containing up to 20 carbon atoms, sulfate, sulfonate, phosphate, phosphonate, borate or isocyanate groups, or mixtures thereof;

and Y is a group having the formula wherein R has the formula given hereinbefore, and c has a value from 1 to 200; and wherein at least one R group in the compound has the formula [-R'(OR')b-R"] in which b is sufficiently large to create an emulsifier.

27. A detergent composition according to Claim 26 wherein the suds suppressor additionally comprises a polydimethyl-siloxane fluid.

28. A detergent composition according to Claim 27 wherein the suds suppressor consists essentially of at least 50%
by weight of a compound of the formula RaSiY4-a' from about 5 to about 45% of a polydimethylsiloxane liquid and from 0.05 to about 5% of silica.

29. A detergent composition according to Claim 28 wherein the nonionic surfactant is selected from the group consisting of C8-C18 aliphatic alcohols condensed with from 3 to about 15 moles of ethylene oxide per mole of alcohol and (C6-C9 alkyl) phenols condensed with from about 6 to about 16 moles of ethylene oxide per mole of phenol.

30. A detergent composition according to Claim 29 wherein the nonionic surfactant is prepared by ethoxylating a C12-C13 alcohol containing approximately 20% of 2-alkyl, predominantly methyl, branching, with 3 moles of ethylene oxide per mole of alcohol and stripping the ethoxylated material to remove low-molecular weight components to yield an ethoxylated alcohol with an average of about 4.9 moles of ethylene oxide per mole of alcohol and an HLB of about 10.55.

31. A detergent composition according to Claim 30 wherein the detergency builder is selected from the group consisting of water-soluble alkali metal phosphates, pyrophosphates, orthophosphates, polyphosphates, phosphonates, carbonates, polyhydroxysulfonates, silicates, polyacetates, carboxylates, polycarboxylates and succinates.

32. A process for preparing the detergent composition of Claim 24 comprising the steps of (a) forming a homogeneous, aqueous slurry comprising (i) from about 1 to about 40% by weight of the slurry Of said alkoxylated nonionic surfactant, (ii) from about 0.005 to about 4% by weight of the slurry of a self-emulsified silicone suds suppressor containing a modified polysiloxane having polyoxyalkylene moieties in the polymer, (iii) from about 10% to about 80% by weight of a detergency builder, and (iv) from about 15 to about 50% by weight of the slurry of water; and (b) drying the homogeneous slurry to form a granular detergent composition.

33. A process according to claim 32 wherein the drying step is performed by spray-drying the slurry.