CA1039141A - Detergent composition and process - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Improved detergent compositions comprising a nonionic surfactant are prepared by sorbing the nonionic surfactant on kaolinite or bentonite clay, preferably at an elevated temperature. The high temperature sorption of the nonionic surfactant on the clay provides processing advantages as well as superior properties of the resulting spray-dried detergent granules.

Description

BACKGROUND OF THE INVENTION
The present invention relates to spray-dried detergent compositions comprising a nonionic surfactant which is sorbed on kaolinite or bentonite 10 clay, and processes for preparing same. The use of kaolinite or bentonite clay in a detergent crutcher mix, in the manner disclosed hereinafter, provides a homogeneous, non-oily mix which can be conveniently spray-dried.
Detergent granules spray-dried from crutcher mixes prepared in the manner of this invention have improved properties over spray-dried detergent granules containing nonionic surfactants heretofore known.
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 20 water is flashed off and solid or semi-porous detergent granules are secured. The advantage of spray-dried detergent granules over granules obtained by simple dry mixing of the individual ingredients is their homo-geneity. That is to say, each granule contains the various ingredients in the same ratios and proportions introduced into the original crutcher mix.
This provides obvious advantages over simple dry-mixed detergent formu-lations, inasmuch as dry mixing can result in inhomogeneity in the final detergent formulation such that the user is never certain of the composition of any given portion of such products.
In order to provide a homogeneous spray-dried granule it is neces-30 '~sary that the crutcher mix, itself, be substantially homogeneous. In someinstances, a crutcher mix may be a homogeneous solution. However, in order to provide a crutcher solution, excessive amounts of water are needed - 1 - J~! i .

to dissolve all the components. Use of excessive 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 prepara-tion of spray-dried detergent compositions are semi-dissolved aqueous slurries of the various components desired in the final spray-dried granules.
This causes problems in maintaining the homogeneity of such mixesO
The introduction of alkoxylated nonionic surfactants into an aqueous detergent crutcher mix adds a new dimension to the problems encountered with maintaining a relatively homogeneous mixture. Nonionic surfactants tend to be oily and exist as a separate phase within the crutcher mixO Such non-homogeneity in the crutcher mix is intolerable when preparing a homo-geneous spray-dried detergent granule. Of course, the separation problem is accentuated by the increased amounts of nonionics used in modern deter-gent compositions.
A variety of methods have heretofore been employed to provide the requisite homogeneity of crutcher mixes containing nonionic surfactants.
Perhaps the most widely used method involves the addition of certain alkyl phosphate esters to the crutcher mix. While the exact mechanism is not known, the phosphate esters appear to "couple" the nonionic to the other components of the mix, thereby providing the requisite homogeneity.
The use of phosphate esters in crutcher mixes is not without its drawbacksO While effective for the intended purpose, the phosphate esters tend to leave a residual greasy feel on the surface of the spray-dried granules.Moreover, the introduction of phosphorus in a detergent composition, in any form, may be undesirable when such detergent compositions are used in areas of the country having improperly treated sewage. Accordingly, it is desirable to provide an alternate method for securing a substantially homo-geneous crutcher mix containing relatively large amounts of nonionic sur-factants .
It has now been found that kaolinite and bentonite clays, when em-ployed in combination with an alkoxylated nonionic surfactant in the manner hereinafter disclosed, provide stable, homogeneous crutcher mixes. Such 103~14~

stabilized crutcher mixes do not experience separation of an oily phase comprising the nonionic surfactant. Moreover, the spray-dried detergent granules prepared from the crutcher mixes herein have unexpected advan-tages over other spray-dried granules containing nonionic surfactants, but without added kaolinite or bentonite clays D
The use of clays in detergent compositions for a variety of purposes is wellknown; see, for example, U.S. Patents 2,118,310; 2,205,021;

2,296,639; 2,344,268; 2,491,051; German Patent 361,520; and British Patents 469,344; and 579,835.
More particularly, Schwartz, Perry and Birch, "Surface Active Agents and Detergents" ~ol. II, Interscience Publishers, ~c., 1958 at page 299, broadly teach that clays have been used to sorb the normally liquid nonionic detergents used in powdered household detergent formulations.
U.S. Patents 2,594,257 and 2,594,258 specifically relate to the sorption of nonionic surfactants of various types on sorbents such as kieselguhr and attapulgite, and the use of such compositions in dry-mixed detergent com-positions. The sorbed nonionics are taught not to "bleed" from such compo-s itions .
The prior art teachings regarding the use of clay to sorb nonionic 20 surfactants in detergent compositions are useful for formulating dry mix-tures, but the use of clays to provide homogeneous crutcher mixes suitable in spray-drying processes has not been disclosed heretofore.
Moreover, the problem of heterogeneous crutcher mixes is not solved by a random selection of sorbent clay carriers for the nonionics. The water and alkalinity of the crutcher mix~tend to displace the nonionics from most carrier materials, resulting in phase separation. Other surfactants which may be present in the crutcher mix, especially the anionics, aid in this displacement and add to the problem.
In contrast with other clays, the kaolinite and bentonite employed as 30 a sorbent carrier for nonionic surfactants in the particular manner disclosed hereinafter provide a stable, homogeneous crutcher mix. This is especially surprising with kaolinite since this clay is not recogniz;ed as being a useful 1035~4~
sorbent for most nonionic surfactants in aqueous media and, hence, is not generally used in combination therewith.
In addition, it has been found that the spray-dried detergent granules prepared in the manner disclosed herein have desirable properties over spray-dried granules containing nonionic surfactants heretofore prepared.
It is an object of this invention to provide homogeneous crutcher mixes containing substantial quantities of nonionic surfactants without the need for phosphate ester couplers.
It is another object herein to provide improved spray-dried detergent 10 granules containing kaolinite or bentonite clay and substantial quanti~;~s of nonionic surfactants, and improved processes for preparing same.
These and other objects are obtained herein as will be seen by the following disclosureO
SUMMARY OF THE INVENTION
, The present invention encompasses processes for preparing homo-geneous crutcher mixes containing a substantial quantity of alkoxylated - nonionic surfactants. By a "substantial" quantity of nonionic surfactant is meant amounts of nonionic surfactant of about 4%by weight, and greater, of the total crutcher mix. The formation of a substantially homogeneous 20 crutcher mix in the manner disclosed herein provides a means for preparing homogeneous spray-dried detergent granules containing nonionic surfactants, In its broadest method aspect, the instant invention encompasses a process for preparing a homogeneous, aqueous crutcher mix containing a substantial amount of a nonionic surfactant, comprising adding a kaolinite or bentonite clay and said nonionic surfactant to said crutcher mix at a weight ratio of nonionic surfactant:clay of from about 20:1 to about 1:2 (preferably 3:1) and maintaining the crutcher mix at a temperature of at least 150F (preferably 150F to 210F~, The hot mix is blended until homo-geneous and then dried, preferably spray-dried, to provide homogeneous 30 detergent granules.
In its compositional aspect, the invention encompasses granular (preferably spray-dried) detergent compositions, comprising:

a) from about 0. 5% to about 40% (preferably 1% to 10%) by weight of kaolinite or bentonite clay; and b) from about 2% to about 60% (preferably 5% to 35%) of an alkoxylated nonionic surfactant at a weight ratio of said surfactant to said clay in the range of from 20:1 to 1:2, preferably 6:1 to 1:2, most preferably 3:1 to 1:1, said surfactant being sorbed on said clay at a temperature of at least 150F (preferably 150F to 210F). In their most preferred embodiment, the compositions herein are prepared by mixing the kaolinite or bentonite clay and nonionic at a tempera-10 ture of at least 150F prior to additionto the hot aqueous crutcher mix and spraydryingO The compositions can optionally conti~in additional surfactants, especially the anionics, as well as other ingredients commonly employed in commercial detergent compositions.
DETAILED DESCRIPTION OF THE IN~ENTION
The non-homogeneity problem with crutcher mixes containing all~oxy-lated nonionic surfactants depends on at least two factors: (a) the amount of nonionic surfactant present in the mix; and (b) the presence or absence of anionic surfactantsO Moreover, when anionic surfactants are present in the mix, the ratio of nonionic surfactant:anionic surfactant can affect the pro-20 cedures required to establish a homogeneous system.
Crutcher mixes containing minor amounts ~caO<4%) of all~oxylatednonionic sur~ifactants can be maintained in a relatively homogeneous state by simple mechanical agitation. However, such mixes are only useful for preparing dry detergent compositions containing minor amounts of the nonionics. While kaolinite or bentonite clay can be employed to advantage in crutcher mixes containing minor amounts of nonionic surfactants, the clay is particularly useful when a substantial quantity of nonionic is being used in the mix.
Modern detergent compositions usually contain a mixture of various 30 surfactants. Detergent compositions containing anionic surfactants, for sudsing and particulate soil removal, admixed with nonionic surfactants, for greasy soil removal, are particularly advantageous. The preparation 1(~3~t~
of homogeneous granular detergent compositions containing mixtures of non-ionic and anionic surfactants requires the use of crutcher mixes containing mixtures of said surfactant types.
The presence of anionic surfactants in aqueous crutcher mixes con-taining nonionic surfactants adds to the problem of maintaining the homo-geneity of the mixO This problem is caused by certain concentrations of anionic surfactants which are insufficient to aid in maintaining homogeneity of the mixes, but which are sufficient to "strip" the nonionic from the surface of most carrier materials.
By the present process, the addition of kaolinite or bentonite clay to an aqueous crutcher mix establishes and maintains the desired homogeneity in the presence of substantial quantities of nonionic surfactants, even in the presence of anionic surfactants. The details of the process will vary some-- what, depending on the presence or absence of anionic surfactant and the nonionic:anionic ratio.
In general terms, the present process comprises adding from 1% to 60% by weight of kaolinite or bentonite clay and about 2% to about 50% by weight of a nonionic surfactant, at a nonionic:clay weight ratio of 6:1 to 1:2, to a crutcher mix which is maintained at a temperature of at least 150F.
20 In its simplest aspect, the crutcher mix can comprise water. More often, the mix will also contain additional materials such as various detergent compounds, builders, soil release polymers, soil suspending agents, and the like, commonly found in commercial detergent compositions. Such additional materials can be optionally present in the crutcher mix, depending on the desired formula of the final granular product. The additional mater-ials do not interfere with the process herein.
In a preferred mode, the nonionic surfactant and clay are pre-slurried at the weight ratios disclosed above, at a temperature of at least about 150F, before being added to the aqueous crutcher mix. Pre-slurrying at elevated 30 temperatures appears to establish the nonionic in and on the water-insoluble clay particles in optimal fashion. When prepared in this manner, the non-ionic is not displaced from the clay by the water present in the hot crutcher mix. Moreover, even in the presence of anionic surfactants which can be 1(~39~1 optionally added to the crutcher, the nonionic remains affixed to the clay particle .
Accordingly, a preferred mode of the present invention encompasses a process for preparing a homogeneous detergent crutcher mix containing a substantial quantity of an alkoxylated nonionic surfactant, comprising:
a) admixing said nonionic surfactant and kaolinite or bentonite clay at a weight ratio of nonionic surfactant:said clay of from about 6: 1 to about 1:2 to provide a hot slurry having a tempera-ture of at least about 150F (preferably 150F to 210F); and b) admixing the hot slurry of step (a) with an aqueous detergent crutcher mix which is also maintained at a temperature of at least 150F (preferably 150F to 210F).
The hot mix of step (b) is then dried, preferably by spray-drying, to provide a granular detergent composition.
When thsre are to be no anionic surfactants present in the crutcher mix, the clay and nonionic do not need to be pre-slurried at an elevated temperature, but can simply be added to the crutcher mix separately. The nonionic will sorb on the clay from the aqueous mediumO Alternatively, the nonionic and clay can be pre-slurried at ambient temperatures (prefer-ably 150F, and higher) and added to the crutcher mix~ The crutcher mix can be preheated to the 150F to 210F temperature range, or can be heated after addition of the clay and nonionic surfactant.
When minor proportions of anionic surfactants are to be present in the crutcher mix, i. e ., at nonionic:anionic weight ratios of les s than about 1:3, the nonionic surfactant must be pre-slurried with the clay in the above-disclosed proportions prior to admixing with the hot crutcher mix. The pre-slurry can be prepared at ambient temperature and added to the hot mix, but is preferably prepared and added at temperatures of 150F, and above, as set forth hereinabove.
When major proportions of anionic surfactants are to be present in the crutcher mix, io e., at nonionic:anionic weight ratios more than about 1:3, the predominance of anionic surfactant aids in providing crutcher mix 1~)39~41 homogeneity. In such cases, the clay and nonionic usually can simply be added to the crutcher mix. Again, however, the hereinab~>ve-disclosed preferred procedure of adding a hot pre-slurry of the nonionic surfactant and kaolinite or bentonite clay to the hot crutcher mix results in superior homogeneity of the mix, From the foregoing it is seen that the present process can be varied in its details, depending on the presence or absence of anionic surfactants in the crutcher mix, and the proportions thereof.
The various processing aspects and ingredients employed herein are set forth in detail belowO As noted hereinabove, the crutcher mix can simply consist of water to which the nonionic and clay are added, either separately, or as a pre-slurry. More often, the crutcher mix comprises water and one or more detergents, builders and the like.
Ao Crutcher Mix The crutcher mixes employed in the process of the present invention can conveniently comprise an aqueous slurry containing from about 15% to about 50% (preferably 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 as hereinafter described, and from about 10% to about 80% (preferably from about 30% to about 60%) by weight of the optional builder and adjunct materials hereinafter disclosedO
Use of the foregoing crutcher mixes in combination with the kaolinite or bentonite clay and the nonionic surfactant in the manner of this invention results in the formation of substantially homogeneous mixes suitable for preparing homogeneous powdered and granular detergent compositions. Of course, such detergent compositions contain the various ingredients origi-nally present in the crutcher mix. However, the final concentrations of such ingredients in the dry detergent compositions may differ somewhat from their concentrations in the crutcher, inasmuch as the clay/nonionic mixture is added to the crutcher and a major portion of the water is removed on drying. The compositions prepared herein will optionally contain from 1%to 50% (preferably 1%to 20%) of auxiliary, preferably anionic, detergents, as set forth below.

1~3~.4~
.
Deter~ent Coml~onent The crutcher mixes of the instant invention (as well as the dry detergent compositions prepared therefrom) can contain all manner of anionic, semi-polar, zwitterionic and amphoteric organic, water-soluble detersive surfactant (detergent) compounds, inasmuch as the nonionic surfactants are compatible with all such materials in the presence of kaolinite clay. A typical listing of the classes and species of detergent compounds useful herein (exclusive of nonionics) appears in U.S. Patent

3,664,961 of Norris, issued May 23, 1972. The following list of detergent 10 compounds and mixtures which can be used in the instant compositions and processes 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 detergent component herein. This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from 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 useful are the sodium 20 and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap~
Another class of detergents includes water-soluble salts, particu-larly the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the al~yl portion of acyl groups. ) Examples of this group of synthetic detergents which can be used in the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols 30 (C8 - Clg carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight 39~1 ~; chain or branched chain configuration, e.g., those of the type described `~ in U.S. Patents 2,220, 099 and 2,477,383~ Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the allcyl groups is about 13 carbon atoms, abbreviated as C13 LAS, Cther anionic detergent compounds herein include the sodium all~yl glyceryl ether sulfonates, especially those ethers of higher alcohols derived t from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride , ` s~lfonates and sulfates; and sodium or potassium salts of all~yl phenolethylene oxide ether sulfate containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atomsO
Semi-polar detergents useful herein include water-soluble amine oxides containing one al~yl moiety of from about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of al~yl groups and hydroxy-allcyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxide detergents containing one all~yl moiety of about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of all~yl groups and hydroxyall~yl groups containing from about 1 to 3 carbon atoms;
and water-soluble sulfoxide detergents containing one all~yl moiety of from about 10 to 28 carbon atoms and a moiety selected from the group consisting of all~yl and hydroxyal~yl moieties of from 1 to 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 18 carbon atoms and at least one aliphatic substituent 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 8 to 18 carbon atoms and one contains an anionic water solubilizing group.

~(339~L4'1 Other useful detergent compounds herein include the water-soluble salts of esters of o(-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates con-taining from about 10 to 20 carbon atoms in the allcyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and ,~-alkyloxy alkane sulfonates 10 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 alkyl benzene sulfonates containing from about 11 to 14 carbon atoms in the alkyl group; the tallow range alkyl sulfates; the coconut range alkyl glyceryl sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from about 14 to 18 carbon atoms and wherein the average degree of ethoxy-lation varies between 1 and 6; the sulfated condensation products of tallow alcohol with from about 3 to 10 moles of ethylene oxide; olefin sulfonates containing from about 14 to 16 carbon atoms; alkyl dimethyl amine oxides 20 wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyl-dimethyl-ammonio-propane-sulfonates and alkyl-dimethyl-ammonio-hydroxy-propane-sulfonates wherein the all~yl group in both types contains from about 14 to 18 carbon atoms; and soaps, as hereinabove definedO
Specific preferred detergents for use herein include: sodium linear C 10 - C 18 alkyl benzene s ulfonate; tr iethanolamine C 10 - C 18 alkyl benzene sulfonate; sodium tallow alkyl sulfate; sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with from about 3 to about 10 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutall~ylammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-30 dimethyl-N-coconutalkylammonio)-propane-1-sulfonate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; dodecyl dimethyl amine oxide; coconut alkyl dimethyl amine oxide; and the water-soluble sodium and potassium salts of higher fatty acids containing 8 to 24 carbon atoms, 103~
, It is to be recognized that any of the foregoing detergents can be used separately herein or as mixtures. Examples of preferred detergent mix-tures herein are as follows.
An especially preferred alkyl ether sulfate detergent component use-ful in the instant compositions and processes is a mixture of alkyl ether sulfates, 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, and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide, preferably from about 2 to 3 moles of ethylene oxide; see Canadian Patent 1,005,310 of Jacobsen and Krummel, granted February 15, 1977.
Specifically, such preferred mixtures comprise from about 0. 05%
to 5% by weight of a mixture of C12_13 compounds, from about 55% to 70%
by weight of a mixture of C14_1s compounds, from about 25% to 40%by weight of a mixture of C16_17 compounds and from about 0.1% to 5% by weight of a mixture of C18_ 1g compounds. Further, such preferred alkyl ether sulfate mixtures comprise from about 15% to 25% by weight of a mixture of compounds having a degree of ethoxylation of 0, from about 50%
to 65% by weight of a mixture of compounds having a degree of ethoxylation 20 from 1 to 4, from about 12% to 22% by weight of a mixture of compounds having a degree of ethoxsTlation from 5 to 8 and from about 0O 5% to 10% by weight of a mixture of compounds having a degree of ethoxylation greater than 8.
Examples of alkyl ether sulfate mixtures falling within the above-specified ranges are set forth in Table I~

1(~3S~

~ w ~ o t~ f-~ . ~ t- o~ ~ o oo ~ ~U~ ~7 XH ~1~ ~ ~ ~ ~ N ~ ., ~3 ,S ¢ `D ~ n ~
~1 H . H1~ ~ . ~ l . ~13 W H ~ ~ ~) N t~ o ~;
_ =

p:~ ~ Ei~ ~1 ~ t~
~ . ~ ~ . ~ ~ ~ l7 1~1 H ~ ~D t~l t~ ~11~_I ~cl H . = .
H

E-~ H ~D t~ 00 H H ~ ~Ll') ~D~ _IU~ ~_I ~1 H ~-- ~ ~

¢ ~ ~o ~ 1 ~o x o o o o o ,~
~¢ g ~ ~v V V g o o g h ~ o O
~; ~ h h ~d ~ ~ o C~
H h ~ ~u-) ~ O` h ~ ~ ~ ~ O
~ ¢ H ~ ~ ~C) 0~ ¢ O ~ O~ U~

1(~3~
Preferred "olefin sulfonate" detergent mixtures utilizable herein comprise olefin sulfonates containing from about 10 to about 24 carbon atoms.
Such materials can be produced by sulfonation of o(-olefins by means of uncomplexed sulfur dioxide followed by neutrali~7ation under conditions such that any sulfones present are hydrolyzed to the corresponding hydroxy-alkane sulfonates. The a(-olefin starting materials preferably have from 14 to 16 carbon atoms. Said preferred o(-olefin sulfonates are described in U.S. Patent 3,332,880 of Kessler et al., issued July 25, 1967.
Preferred ~-olefin sulfonate mixtures herein consist essentially of from about 30% to about 70~0 by weight of a Component A, from about 20%
to about 70% by weight of a Component B, and from about 2% to about 15% of a Component C, wherein (a) said Component A is a mixture of double-bond positional isomers of water-soluble salts of all~ene-l-sulfonic acids containing from about 10 to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of a gamma-delta unsaturated isomer, and about 5% to about 10% of a delta~epsilon unsaturated isomer;
(b) said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 10 to about 24 carbon atoms, the functional units being hydroxy and sulfonate groups with the sulfonate groups always being on the terminal carbon and the hydroxyl group being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms at least 90% of the hydroxy group substitutions being in 3, 4, and 5 positions; and (c) said Component C is a mixture comprising from about 30%-95% water-soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5% to about 3t3~1 70% water-soluble salts of hydroxy disulfonates containing from about 10 to about 24 carbon atoms, said all~ene disulfo-nates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about siæ carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate group attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroæy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.
Adjunct Materials The herein-disclosed crutcher mixes and the detergent compositions prepared therefrom can contain, in addition to the organic detergent com-pounds, all manner of detergency builders commonly taught for use in 20 detergent compositions. Such builders can be employed in the crutcher mix at concentrations of from about 10% to about 80% by weight (preferably 30%
to 60%) to yield dry detergent compositions containing from about 5% to about 50% by weight, preferably from about 10% to about 35% by weight, of said builders~ Useful builders herein include any of the conventional inorganic and organic water-soluble builder salts.
Such detergency builders can be, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, phos-phonates, carbonates, polyhydroxysulfonates, silicates, polyacetates, carboxylates, polycarboxylates and succinates~ Specific examples of 30 inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates, and hexametaphosphates. The polyphosphonates specifically include, for example, the sodium and potassium salts of ethylene diphos-phonic acid, the sodiuln and potassium salts of ethane l-hydroxy-l,1-diphosphonic acid and the sodium and potassium salts of ethane-l,1,2-triphosphonic acid. Examples of these and other phosphorous builder com-pounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021;
3,42Z,137; 3,400,176 and 3,400,148.
Non-phosphorus containing sequestrants can also be selected for use herein as detergency builder.
Specific examples of non-phosphorus, inorganic builder ingredients include water-soluble inorganic carbonate, bicarbonate, and silicate salts.
The al~ali metal, e.g., sodium and potassium, carbonates, bicarbonates, and silicates are particularly useful herein.
Water-soluble, organic builders are also useful herein. Eor example, the all~ali metal, ammonium and substituted ammonium polyacetates, car-boxylates, polycarboxylates and polyhydroxysulfonates are useful builders in the present compositions and processes. Specific examples of the poly-acetate and polycarboxylate builder salts include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
Highly preferred non-phosphorus builder materials herein include sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodium oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, and sodium ethylenediaminetetraacetate, and mixtures thereof.
Other highly preferred builders herein are the polycarboxylate builders set forth in U.S. Patent 3,308,067 of Diehl, issued 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, aconitic acid, citraconic acid and methylene-malonic acid.
Additional, preferred builders herein include the water-soluble salts, especially the sodium and potassium salts, of carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclo-pentanetetracarboxylate and phloroglucinol trisulfonate.

- 16 _ lQ391~1 Another type of detergency builder material useful in the present compositions and processes comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations in combination with a crystallization seed which is capable of providing growth sites for said reaction product. Such "seeded builder" compositions are fully disclosed in Canadian Patent 991,942 of Lawrence Benjamin, granted June 29, 1976 to The Procter and Gamble Company.
More particularly, the seeded builders useful herein comprise a crystallization seed having a maximum particle dimension of less than 20 microns, preferably a particle diameter of from about 0. 01 micron to about 1 micron, in combination with a material capable of forming a water-insoluble reaction product with free metal ions.
Many builder materials, e. g., the water-soluble carbonate salts, precipitate water hardness cations, thereby performing a builder function.
Unfortunately, many of the precipitating builders used in detergent composi-tions do not reduce the free metal ion content of laundry baths quickly, and such builders only compete with the organic detergent and the soil for the free metal ions. The result is that while some of the free metal ions are removed from the solution, some ions do react with the organic detergent and the soil, thereby decreasing the detersive action. The use of the crystallization seed suickens the rate of precipitation of the metal hardness, thereby removing the hardness ions before they can adversely affect the detergency performance.
By using a materi~l capable of forming a water-insoluble product with free metal ions in combination with a crystallization seed, the combined free metal ion concentration of an aqueous laundering liquor can be reduced to less than 0.5 grains of hardness within about 120 seconds. In fact, the preferred seeded builders can reduce the free metal hardness to less than O . 1 grains /gallon within abo ut 3 0 s e c onds .
Preferred seeded builders consist of: a water-soluble material capable of forming a reaction product having a solubility in water of less than about 1. 4 x 10-2 wt. % (at 25C) with divalent and polyvalent metal ions such as calcium, magnesium and iron; and a crystallization seed (0O 001-20 micron diameter) which comprises a material which will not completely dissolve in water within 120 seconds at 25C.
Specific examples of materials capable of forming the water-insoluble reacticn product include the water-soluble salts of carbonates, bicarbonates, sesquicarbonates, silicates, aluminates and oxalates. The alkali metal, especially sodium, salts of the foregoing materials are preferred for convenience and economy.
The crystallization seed employed in such seeded builders is pre-10 ferably selected from the group consisting of calcium carbonate; calciumand magnesium oxalates; barium sulfate; calcium, magnesium and aluminum silicates; calcium and magnesium oxides; calcium and magnesium salts of fatty acids having 12 to 22 carbon atoms; calcium and magnesium hydroxides;
calcium fluoride; and barium carbonate. Specific examples of such seeded builder mixtures comprise: 3:1 wt. mixtures of sodium carbonate and calcium carbonate having a 5 micron particle diameter; 207:1 wt. mixtures of sodium sesquicarbonate and calcium carbonate having a particle diameter of 0. 5 microns; 20:1 wto mixtures of sodium sesquicarbonate and calcium hydroxide having a particle diameter of 0. 01 micron; and a 3:3:1 wt.
20 mixture of sodium carbonate, sodium aluminate and calcium oxide having a particle diameter of 5 microns.
The process herein can be successfully carried out to provide detergent compositions containing all manner of additional materials com-monly found in laundering and cleaning compositions. Such additional materials can simply be included in the crutcher mix, as desired. Accord-ingly, the crutcher mixes (and resulting detergent compositions) herein can contain thickeners and soil suspending agents such as carboxymethyl-cellulose and the likeO Various perfumes, optical bleaches, fillers, anti-caking agents, fabric softeners and the like can be present to provide the 30 usual benefits occasioned by the use of such materials in detergent compo-s itions .

1()39~
Perborate bleaches commonly employed in European detergent compositions can also be present as a component of the instant detergent compositions, and are added thereto as dry admixes.
Enzymes, especially the thermally stable proteolytic and lipolytic enzymes used in laundry detergents, can be dry~mixed in the compositions herein.
It is to be recognized that all such adjuvant materials are useful, inasmuch as they are compatible in the presence of the clay and nonionic surfactant .
Gelling agents such as the amorphous silicas and the various alkyl-and hydroxyalkyl-cellulose derivatives are particularly useful adjuncts in the present compositions and processes. While such gelling agents are not particularly useful in detergent crutcher mixes at high concentrations due to the formation of intractable gelled masses, they can be employed herein in relatively low (0.1% to 3%) concentrations in the crutcher mix to provide additional advantages in the final detergent compositions. More particularly, the use of the gelling agents helps to "fix" the nonionic surfactant on the kaolinite or bentonite clay, thereby preventing "bleeding" of the nonionic on prolonged storage of the detergent granules. Apparently the gelling 20 agents, when used in low concentrations, preferentially gel at the surface of the clay particles containing the nonionic surfactant, thereby providing an additional fixative action, but without unduly thickening the crutcher mix, itself .
Suitable inorganic gelling agents which can be optionally employed in the present process include the microfine silicas such as silica gels, silica xerogels, fumed colloidal silica, and the like. Specific examples of useful organic gelling agents include the various alkyl and hydroxyalkyl, e.g., methyl, ethyl, propyl, butyl, hydroxymethyl, hydroxyethyl, hydroxy-propyl and hydroxybutyl, cellulose derivatives well known in the art.
30 Hydroxybutylcellulose and mixed hydroxypropylmethylcellulose are preferred herein.

:

1()39~41 The gelling agents can be employed in the present invention by simply adding them to the crutcher mix, either before or after addition of the clay and nonionic surfactant. Preferably, the gelling agent is added to a pre-slurry of the nonionic surfactant and clay; the resulting mixture is then added to the crutcher mix, in the manner described above, Dried detergent compositions which are prepared using the instant process and the optional gelling agents comprise the nonionic surfactant and the kaolinite or bentonite clay in the ratios and proportions hereinabove disclosed, and from about 0.1% to about 5% by weight of said gelling agent.
B. Nonionic Surfactant Component The nonionic surfactants employed in the present compositions and processes can be any of the detersive all~oxylated surfactants well-known in the art. In general terms, the nonionics herein are water-soluble detersive surfactants of the formula R- O-(CyH2yO)a~(czH2zO)b-cwH2woH

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;
20 said hydrocarbyl moieties having a hydrocarbyl chain length of from 8 to about 20, preferably 10 to 16, carbon atomsO In the general formula for the alkoxylated nonionic surfactants herein, y and z are each integers of from 2 to about 3, preferably 2, either z or y being 2 when the other integer is 3 (i.e., excluding the all-PO 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 sum of a + b being in the range of from 6 to about 16, preferably 6 to 10.
The formula of the surfactants herein encompasses ethylene oxide (EO) as well as mixed ethylene oxide-propylene oxide (EO-PO) alkoxylates, all of which are useful herein. The all-PO surfactants do not provide cleaning 30 advantages in detergent compositions and are not contemplated for use herein.

` 1(?3~141 The nonionic surfactants herein are further characterized by a hydro-philic-lipophilic balance (HLB) of from about 11 to about 17, preferably about 12 to about 15.
Preferred nonionic surfactants used herein are the ethoxylated non-ionics, both from the standpoint of availability and cleaning perforrnance.
Specific examples of nonionic surfactants useful herein are as follows.
The examples are only by way of exemplification and are not ;ntended to be limiting of such materials.
Straiç~ht-chain, primary alcohol alkoxylates -The hexa-, hepta-, octa-, nona-, deca-, undeca-, dodeca-, tetradeca-and hexadeca-alkoxylates of n-octanol, n-decanol, n-dodecanol, n-tetra-decanol, n-hexadecanol and n-octadecanol having an HLB within the range recited herein are useful surfactants in the context of this invention; the respective ethylene oxide condensates are the most preferred alkoxylates.
Exemplary alkoxylated primary alcohols useful herein as the surfactant component of the mixtures are: n-CloEO(6); n-CloEO(9); n-ClzEO(9);
n-C14EO(10); n-CloEO(10); n-CgEO(9); n-C16EO(14); and n-CloEO(6)PO(3).
The ethoxylates of mixed natural or synthetic alcohols in the "coconut" chain length range are also useful herein. Specific examples of such materials 20 include coconutall~ylEO(6) and coconutalkylEO(9).
Strai~ht-chain, secondary alcohol alkoxylates -The hexa-, hepta-, octa-, nona-, deca-, undeca-, dodeca-, tetra-deca- and hexadeca-alkoxylates of 2-decanol, 2-tetradecanol, 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol having an HLB within the range recited herein are useful surfactants in the context of this invention; the respective ethylene oxide condensates are the most preferred alkoxylates.
Exemplary alkoxylated secondary alcohols useful herein as the surfactant component of the mixtures are: 2-CloEO(9); 2-C12EO(9); 2-C14EO(10);
2-C~6EO(11); 4-C2oEO(11); 2-C16EO(14); and 2-CloEO(6)PO(3)~ The most 30 preferred straight chain, secondary alcohol alkoxylates herein are the materials marketed under the trademarks "Tergitol 15-S-9" and "Tergitol 15-S-7", which comprise a mixture of secondary alcohols having an average 1~39~41 hydrocarbyl chain length of 13 carbon atoms condensed with an average of 9 and 7 moles of ethylene oxide per mole equivalent of alcohol, respectively.
Alkyl phenolic alkoxylates -As in the case of the alcohol alkoxylates, the hexa- through hexadeca-alkoxylates of alkylated phenols, particularly monohydric alkylphenols, having an HLB within the range recited herein are useful as the surfactant component of the instant mixtures. The respective ethylene oxide conden-sates are the most preferred alkoxylates. The hexa- through hexadeca-alkoxylates of p-hexaphenol, m-octylphenol, p-octylphenol, p-nonylphenol and the like are useful herein; most preferred are the ethoxylates of p-octylphenol and p-nonylphenol, inasmuch as these materials are readily available. Exemplary alkoxylated alkyl phenols useful as the surfactant component of the mixtures herein are: p-octylphenol EO(9), p-nonylphenol EO(9); p-decylphenol EO(9); o-dodecylphenol EO(10); and p-octylphenol EO(9)PO(2). The most preferred alkylphenol alkoxylates herein are p-octylphenol (nonoxyethylene) and p-nonylphenol (nonoxyethylene).
Olefinic alkoxylates -The alkenyl alcohols, both primary and secondary, and alkenyl phenols corresponding to those disclosed immediately hereinabove can be alkoxylated to an HLB within the range recited herein and used as the surfactant component of the instant mixtures. Typical alkenyl alkoxylates herein are 2-n-dodecenol EO(9); 3-n-tetradecenol EO(9); p-(2-noneyl)phenol EO(9)PO(2); and 2-tetradecen-4-OE EO(9) Branched chain alkoxvlates -Branched chain primary and secondary alcohols which are available by the well known "OXO"process can be alkoxylated and employed as the surfactant component of mixtures herein. Exemplary branched-chain alkoxylates are as follows: 2-methyl-1-dodecanol EO(9); 3-ethyl-2-tetra-decanol EO(9); 2-methyl-1-hexadecanol EO(9)PO(2) and the like.
The foregoing alkoxylated nonionic surfactants are useful in the present compositions and processes singlSr, or in combination, and the term "nonionic surfactant" encompasses mixed nonionic surfactant systems containing multiple alkoxylated nonionic surface active agents.

i(~3~41 One mixed alkoxylated nonionic system which is particularly useful herein comprises a mixture of 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-surfactant", one or more water-soluble a*oxylates having an HLB in the range of 7 to lOo 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 from about 10 to about 12. 5 (preferably 10 to 12; most preferably 10. 5 to 12. 0). Such mixtures of nonionic surfactant and nonionic co-surfactant provide superior 10 fabric cleaning performance and are particularly useful for removing greasy soil from polyester and cotton/polyester fabric blends. These preferred nonionic surfactant-plus-nonionic "co-surfactant" alkoxylate mixtures are more fully described in Canadian Patent Application 210,835, filed October 7, 1974.
In general, the alkoxylated nonionic co-surfactants have the general formula Rl _O(CyH2yO)a~(CzH2zo)b-cwH2woH
wherein R' is selected from the group consisting of primary, secondary and branched chain (primary and secondary) alkyl hydrocarbyl moieties having 20 8 to 15 carbon atoms; primary, secondary and branched chain (primary and secondary) alkenyl hydrocarbyl moieties having 8 to 15 carbon atoms; and primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl moieties wherein the a*yl and alkenyl portions have 5 to 7 carbon atoms; y and z are each integers of from 2 to 3; w is an integer from 2 to 3; a and b are each integers of from 0 to 5, the sum of a and b being in the range of 1 to 5; and said co-surfactant having an HLB of from 7 to about 10. 5.
Specific examples of alkoxylates which can be employed as co-sur-factants to prepare nonionic mixtures useful in the present invention are as 30 follows. The examples are only by way of exemplification and are not intended to be limiting of such materials.

iO3~41 Strai~ht-chain, primarv alcohol alkoxylates -The di-, tri-, tetra-, and penta-alkoxylates of n-octanol, n-nonanol, n-decanol, and n-undecanol having an HLB of from 5 to 11 are useful co-surfactants in the context of this invention; the respective ethylene oxide condensates are the most preferred alkoxylates. Exemplary alkoxylated primary alcohols useful herein as the co-surfactant component of the mix-tures are: n-CgEO(2); n-CgEO(3); n-CgEO(3); n-CloEO(3); n-CllEO(3);
n-CloEO(4); n-CloEO(3)PO(l); and n-CloEO(2)PO(2). The most preferred straight chain, primary alcohol alkoxylate co-surfactant herein is n-CloEO(3).
Strai~ht-chain, secondarv alcohol alkoxvlates -The di-, tri-, tetra- andpenta-alkoxylates of 2-nonanol, 3-decano], 2-decanol, 3-tetradecanol, and 5-pentadecanol having an HLB within the range recited herein are useful co-surfactants in the context of this invention;
the respective ethylene oxide condensates are the most preferred alkoxylates.
Exemplary alkoxylated secondary alcohols useful herein as the co-surfactant component of the mixtures are: 2-CloEO(3); Z-C12EO(5); 2-C~EO(2~;
2-CloEO(2)PO(2); and 2-C12EO(3)PO(l). The most preferred straight chain, secondary alcohol alkoxylate herein is the material marketed under the trademark "Tergitol 15-S-5", which comprises a mixture of secondary ?0 alcohols having an average hydrocarbyl chain length of 13 carbon atoms condensed with an average of 5 moles of ethylene oxide per mole equivalent of alcohol.
Alkyl phenolic alkox~,rlates -As in the case of the alcohol alkoxylates, the di- through penta-alkoxylates of alkylated phenols, particularly monohydric alkylphenols, having HLB's within the ranges recited herein are useful as the co-surfactant component of the mixtures herein. The respective ethylene oxide conden-sates are the more preferred alkoxylates. The mono- through penta-alkoxylates of p-hexylphenol, m-octylphenol, p-octylphenol and the like are 30 useful herein; most preferred are the alkoxylates of p-octylphenyl, inasmuch as this material is readily available. Exemplary alkoxylated alkyl phenols useful as the co-surfactant component of the mixtures herein include:

~ 039~l41 p-octylphenol EO(3); p-hexylphenol EO(3); p-octylphenol EO(5); p-octylphenyl EO(4); and p-octylphenol EO(5)PO(2). The most preferred alkylphenol alkoxylate co-surfactants herein are p-octylphenol EO(5).
Olefinic alkoxylates -The alkenyl alcohols, both primary and secondary, and alkenylphenols corresponding to those disclosed immediately hereinabove can be alkoxylated to an HLB within the range recited herein and used as the co-surfactant component of the instant mixtures. Typical al~enyl alkoxylates - ~ useful herein are 2-n-decenol EO(3); 2-pentadecen-4-ol EO(5); and p-(2-octenyl)phenol EO(3).
Branched chain alkoxylates -Branched chain primary and secondary alcohols which are available by the well-known "OXO" process can be alkoxylated to an HLB within the co-surfactant range disclosed herein and employed in the instant mixtures.
Exemplary branched-chain alkoxylated co-surfactants are as follows:
2-methyl-1-dodecanol EO(3); 3-ethyl-2-decanol EO(3); 2-methyl-1-decanol EO(3)PO(l) and the like. The ethylene oxide condensates of branched chain alcohols a~e preferred herein.
The foregoing co-surfactant alkoxylates are combined with the above-disclosed surfactants to provide mixtures characterized by an overall HLB in the range of from 9 to 13. The HLB's of the surfactants, co-surfactants and mixtures herein can be calculated in the manner set forth in Becker, "Emul~ions Theory and Practice" Reinhold 1965 pp. 233 and 248. For example, the relation HLB = E/5 where E is the weight percent of oxyethylene content, can be used to calculate the HLB of the normall fatty alcohol ethoxylates employed herein.
For mixtures of surfactant (A) and co-surfactant (B), the composite HLB is calculated as follows:
HLB(Mix) = wt. fraction A x HLBA +
wt. fraction B x HLBB

1()3~l4~
Alternatively, the weight fraction of the co-surfactant which must be used with a given surfactant to provide a mixture having an HLB within the range recited herein can be calculated as follows:
wt. fraction HLB surf. - HLB mixt.
co-surfactant HLB surf. - HLB co-surf.
On the basis of the foregoing, it i9 possible to calculate the weight of alkoxylated co-surfactant of the type disclosed herein which must be combined with the alkoxylated surfactant of the type disclosed herein to provide a surfactant mixture having a mixture HLB within the specified 10 range. Such mixtures effect the solubilization of oil in aqueous media;
hence, the mixtures exhibit superior cleaning performance with oily soil.
Mixtures of nonionic surfactants and nonionic co-surfactants par-ticularly useful herein by virtue of their superior oil dispersion and deter-gency properties include:
n-GloEO(3)/n-CloEO(9) 60:40 wto ratio(HLB 11.2) n-CloEO(3)/n-CloEO(9) 65:35 wt. ratio (HLB 10.9) n-CloEO(3)/n-CloEO(6) 50:50 wt. ratio (HLB 10.8) n-CloEO(3)/"~Tergitol 15-S-9" 55:45 wt. ratio (HLB 11. 0) "Tergitol 15-S-5"/"Tergitol 15-S-9" 55:45 wt. ratio (HLB 11.8) n-CloEO(4)/"Tergitol 15-S-7" 60:40 wt. ratio (HLB 11. 1) The present process of sorbing alkoxylated nonionic materials on clay is particularly useful when mixtures of the aforesaid surfactants and co-surfactants are to be used in a crutcher mix. The nonionic co-surfactants have low molecular weights, as compared with the surfactants, and tend to volatilize. Sorption on the clay reduces the volatility of the low molecular weight nonionics and allows them to be added to the hot crutcher mix and later spray-dried without excessive evaporative losses O
C. Clay The clay materials useful in the present compositions and processes are kaolinite and bentonite. Kaolinite clay is well-recognized as a white, powdery mineral having the approximate formula A1203.SiO2- 2H2 1039~l4~
and a specific gravity of about 2. 6. Natural kaolinite clay often contains minor proportions (~2%) of iron, calcium, magnesium and titanium oxides.
The presence or absence of these minor constituents of natural kaolinite clay is of no consequence in the present invention. Kaolinite clay is available from natural sources, or can be synthetically prepared from mixtures of water-soluble aluminates and silicates. The kaolinite clay useful in the present invention preferably has a particle size of less than about 25 microns and most preferably has a particle diameter of from about 0. 01 microns to about Z microns.
Various kaolinite clays can be obtained commercially. Particularly useful kaolinite clays are those which are treated by the so-called "wet process", io e, are purified by a water washing procedure.
Specific, non-limiting examples of commercial kaolinite clay useful herein include "Hydrite 10" 1, "Kaophile 2" 2 and "Hydrite UF" 3, all available from the Georgia Kaolin Company, and "Hydrasheen 90"4, avail-able from the J.M. Huber Corporation.
The bentonite clays of this invention have the following approximate formula [ (Al4-xMgx)si8o2o(oH)4]x [X Mn+ ]
Z0 where x = 0. 5 - 1. 0 and M = Na+ or Ca++.
Such materials in the calcium form are a well-known class of material that are available from natural sourcesO These calcium clays are preferred herein. The sodium form of the clay is obtained from the natural calcium form by known methods, e. gO, ion exchangeO
Examples of commercially available clays are "CECA KC-1"5 and 2 from CARBONIFATION et CHARBONS. "ACTIFS"6 of France; yellow Texas calcium bentonite from the Georgia Kaolin Company; and "Super-ventilata" 7, from Industria Mineraria of Italy.

1. Trademark 2. Trademark 30 3. Trademark

4. Trademark

5. Trademark

6. Trademark

7. Trademark 1~39~l41 D. Proces sin~
The manner in which the present process is carried out depends on the presence or absence of anionic surfactants in the crutcher mix, as noted hereinabove, When anionic surfactants are not used in the crutcher mix, the process herein is somewhat simplified in that a pre-slurry of the nonionic and the clay is not required, but is preferred.
In general terms, the process herein is 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. When there 10 are no anionic surfactants present in the mixture, the clay and nonionic surfactant are simply added to the crutcher mix which is maintained at a temperature of about 150F, and higher, and dried to form a granular product .
For most purposes, an anionic surfactant will be present in the detergent crutcher mix and this occasions the need for pre-slurrying the clay and nonionic surfactant prior to addition to the crutcher mix. The various processing aspects are set forth in detail in the following examples.
EXAMPLE I
The following illustrates a lab-scale test which was used to determine 20 the effect of various additives on the homogeneity of detergent crutcher mixes. In order to visually observe the phases of the crutcher mix, a soluble yellow-green dye, D&C Green No. 8, and a dispersible blue pigment, ultramarine blue, were added to the crutcher mix. When any perceptible phase separation occurred, the yellow dye preferentially dissolved in the surfactant-rich phase and the blue pigment remained in the aqueous/electro-lyte phase. By following this procedure, even minor inhomogeneity problems could be visualized as a change in color or texture of the mix. Severe phase separation problems were readily visualized as a yellow streaking or filming even during mixing. The stability of the crutcher mix could be further 30 assessed by allowing the mix to stand, without stirring, and visually observing the separation of the colored phases.

1~)39~41 The composition of the crutcher mix varied in each test, depending on whether the proposed stabilizing ingredient was pre-slurried with the nonionic surfactant component or added directly to the crutcher mix, In the former case, 180 grams of a representative nonionic surfactant ("Tergitol 15-S-9") was pre-slurried with the stabilizing ingredient being tested at a weight ratio of nonionic surfactant:stabilizing ingredient of 3.6:1, at a temperature of ca. 150F-160F. In the latter case, 180 grams of the "Tergitol 15-S-9" was simply admixed with the remaining components of the crutcher mix and the stabilizing ingredient to be tested was added to the I0 total crutcher mix to provide a weight ratio of nonionic surfactant:added stabilizing ingredient of 3.6:1.
The composition of the crutcher mix, exclusive of the nonionic surfactant and stabilizing ingredient being tested was as follows:
Grams Sodium silicate (SiO2:Na O =
2.0:1.0; solution at 56~water) 227 Sodium sulfate 390 Sodium carbonate 250 Water 15 0 The results of the series of tests employing a variety of added particulate stabilizing ingredients are set forth in Table II.

1(~3~
Table II
CRUTCHER HOMOGENEITY
In~redient Mode of Addition Result Kaolinite Clay Directly to Crutcher Good Kaolinite Clay Hot Pre-Slurry Excellent Bentonite Clay Hot Pre-Slurry Moderate Bentonite Clay Directly to Crutcher Moderate Attapulgite Clay Directly to Crutcher No Effect Attapulgite Clay Hot Pre-Slurry No Effect 10 Calcium Silicate Directly to Crutcher No Effect Calcium Silicate Hot Pre-Slurry No Effect Calcium Carbonate Directly to Crutcher Moderate Calcium Carbonate Hot Pre-Slurry Moderate Sodium Aluminosilicate Directly to Crutcher No Effect Sodium Aluminosilicate Hot Pre-Slurry No Effect Aluminum Silicate Directly to Crutcher Moderate Aluminum Silicate Hot Pre-Slurry Moderate Alumina Directly to Crutcher No Effect Alumina Hot Pre-Slurry No Effect 20 Magnesiurn Silicate Directly to Crutcher No Effect Magnesium Silicate Hot Pre-Slurry No Effect Silica* Directly to Crutcher No Effect Silica* Hot Pre-Slurry No Effect *A variety of colloidal and amorphous silicas were tested with similar results.
As can be seen from the results in Table II, kaolinite clay is superior to the other materials tested for the purpose of providing crutcher homogeneity. Moreover, the preferred use of a hot pre-slurry of the kaolinite and nonionic surfactant is clearly demonstrated.
30 Bentonite clay also provided useful results and is also suitable for preparing homogeneous crutcher mixes suitable for spray-drying to provide homogeneous detergent granules. Bentonite is especially useful when high 1(~3~
t25%-60% wt. ) concentration of phosphate builders are present in the crutcher mix.
In the foregoing example, the crutcher mix is modified by the addition of 15%wt. of sodium linear alkylbenzene sulfonate (alkyl = Cll-C14) and the crutcher mix temperature is varied. The nonionic surfactant and kaolinite clay are added to the anionic surfactant containing crutcher mix, with the following results: no pre-slurry (poor homogeneity); hot (150F) pre-slurry of kaolinite and nonionic added to cool crutcher mix (poor homogeneity); hot (150F) pre-slurry of kaolinite and nonionic surfactant 10 added to hot (150F) crutcher slurry (substantially improved homogeneity).
The following example illustrates the preparation of a granular detergent composition in the manner of the present invention. In the process, sodium toluene sulfonate is employed as a hydrotrope in the crutcher mix and further aids in the maintenance of crutcher homogeneity when employed .:, in combination with the hot pre-slurry procedure herein.

EXAMPLE II

Crutcher Mix In~redient Grams Sulfated tallow alcohol 2 O 0 Linear alkylbenzene sulfonate (alkyl = C11.8 avg.) 2.0 Calcium carbonate (1. 0 micron) 9O0 Sodium carbonate 30 . 0 Sodium sulfate 9 . 7 Sodium sulfosuc cinate 2, 0 Sodium toluene sulfonate 2. 0 Sodium silicate (SiO2:Na2O = 2 . 0)10 . 0 Water 45 i(~3~
Pr e -Slurry InLredient Grams "Tergitol 15-S-9" 10.0 "Tergitol 15-S-3" * 10.0 Kaolinite clay 6.5 * Trademark Following the procedure set forth hereinabove, the kaolinite clay and the nonionic surfactants are admixed separately from the crutcher at a temperature of 150F iand blended thoroughly at this temperature for about 5 minutes until a smooth slurry is obtained. The crutcher mix ingredients are separately mixed and raised to a temperature of 150F. The hot kaolinite-nonionic slurry is then admixed with the hot crutcher mix and blended. A homogeneous crutcher mix suitable for spray-drying is obtained.
The hot total mixture is introduced into a spray-dry tower and sprayed to provide a granular detergent composition.
In the foregoing example, the sodium toluene sulfonate hydrotrope is replaced by an equivalent amount of sodium m-xylene sulfonate, sodium o-xylene sulfonate, sodium p-xylene sulfonate and mixed sodium cumene sulfonate hydrotropes, respectively, and equivalent results are secured.
The use of such hydrotroping materials at concentrations of from about 0.1% to about 5% by weight in the crutcher mixes herein, which results in detergent compositions containing from about 0~ 3% to about 7.0~0 by weight of said hydrotropes, aids in the formation of homogeneous, easily-worked crutcher mixes when employed in combination with the kaolinite clay in the manner of the present invention.
In the foregoing example, the 1:1 mixture of "Tergitol 15-S-3" and "Tergitol 15-S-9" employed in the pre-slurry is replaced by an equivalent amount of n-CloEO(3)/n-CloEO(9) 60:40 wt. ratio; n-CloEO(3)/n-CloEO(9) 65:35 wt. ratio; n-CloEO(3)/n_CloEO~6) 1:1 wt. ratio; n-CloEO(3)/"Tergitol 15-S-9" 55:45 wt. ratio; and n-C1oEO(4)/"Tergitol 15-S-7" 60:40 wt. ratio, respectively, and equivalent results are secured.

- 32 ~

~39141 In the foregoing example, the anionic surfactant co~nponent of the crutcher mix comprising the sulfated tallow alcohol and the linear alkyl-benzene sulfonate is replaced by an equivalent amount of sodium linear Clo-Clg alkylbenzene sulfonate; triethanolamine Clo-Clg alkylbenzene sulfonate; sodium tallow alkyl sulfate; sodium coconut alkyl glycerylether - sulfonate; the sddium salt of a sulfated condensation product of a tallow alcohol containing from about 3 to about 10 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammonio)-propane-l-sulfonate; 6-(N-dodecylbenzyl-10 N,N-dimethylammonio)-hexanoate; dodecyl dimethyl amine oxide; coconut-alkyldimethyl amine oxide; and the water-soluble sodium and potassium salts of higher fatty acids containing 8 to 24 carbon atoms, respectively, and equivalent results are secured.
In the foregoing example the seeded builder compri~ing the mixture of sodium carbonate and calcium carbonate is replaced by a total of 40 grams of the following builders, respectively: sodium tripolyphosphate; sodium nitrilotriacetate; sodium citrate; sodium oxydisuccinate; sodium mellitate;
sodium ethylenediaminet~raacetate; sodium carboxymethyloxymalonate;
sodium carboxymethyloxysuccinate; sodium cis-cyclohexanehexacarboxylate;
20 sodium cis-cyclopentanetetracarboxylate; and the sodium salt of phloro-glucinol trisulfonate, and equivalent results are secured.
In the foregoing example the kaolinite clay is replaced by an equivalent amount of bentonite (avg. particle diameter 5 microns) and homogeneou~
- compositions are secured.
The following example illustrates the use of gelling agents in the - present compositions and processes to provide a dry detergent granule having a decreased tendency to bleed nonionic surfactant.
.... -. .

1~3~14~
EXAMPLE III
Crutcher Mix In~redient Grams Sulfated tallow alcohol 5~ 0 Linear alkylbenzene sulfonate (alkyl = Cll 8 avg.) 5~0 Sodium sulfate 6 . 0 Sodium sulfosuccinate 2. 0 Sodium silicate (SiO2:Na20 = 20 0) 15~ 0 Colorants, optical brighteners 1. 3 Water 25~ 0 Pre-slurry In~redient _rams Coconut alcohol ethoxylate (6) 20~ 0 Kaolinite clay 5~ 0 Hydroxybutylcellulose 0. 2 The crutcher mix ingredients are separately blended and raised to a temperature of 150F-155Fo The clay and coconut ethoxylate nonionic surfactant are admixed in the pre-slurry and the temperature raised to 150F~ The materials are blended for about 5 minutes to provide a creamy 20 consistency. The hydroxybutylcellulose is then mixed with the pre-slurry and blending is continued for an additional 10 minutes at 150F~ The hot pre-slurry is added to the hot crutcher mix and blended to provide a homo-geneous systemO The hot total mix is then introduced into a drying column and sprayed through a column of air at a temperature of about 200Fo to provide spray-dried granulesO On storage, the granules prove to be crisp and free-flowing, and possess superior storage properties in that they demonstrate improved retention of the nonionic surfactantO
In the foregoing example the hydroxybutylcellulose is replaced by an equivalent amount of powdered amorphous silica, hydroxyethylcellulose, 30 hydroxypropylcellulose, methylcellulose, and ethylcellulose, respectively, and equivalent results are securedO

103~4~
As can be seen by the foregoing examples, the processes of the present invention result in superior detergent compositions characterized by their ease of processing. The following examples are typical of the detergent compositions prepared in the manner of the present invention, but are not intended to be limiting thereof.
EXAMPLE IV
In~redient Wt. %
Sulfated tallow alcohol 2 . 0 Linear alkylbens~ene sulfonate (alkyl = Cll 8 avgO) 2.0 10 Nonionic surfactant (1:1 wt. mixture of "Tergitol 15-S-9" and "Tergitol 15-S-3") 20.0 Kaolinite clay (0, 5 micron diam . ) 6 ~ 5 Calcium carbonate (1 micron diamO ) 9. 0 Sodium carbonate 30 . 0 Sodium sulfate 9.7 Sodium sulfosuccinate 2 . 0 Sodium toluene sulfonate 2 . 0 Sodium silicate ~SiO2:Na2O = 2.0) 10.0 Colorants, optical brighteners 1. 3 20 Water 3- 5 Total spray-dr ied granules 98 . 0 Dry powder adm~x * 2 . O
Total 100. 0%
* Powdered amorphous silica dusted onto spray-dried granules as a free-flow aid.

The foregoing composition is prepared by pre-slurrying the nonionic surfactant with kaolinite clay at a temperature of about 150F and adding the pre-slurry to a crutcher mix at 150F, followed by spray-drying. When the procedure is carried out at pre-slurry and crutcher mix temperatures 30 of 160F, 170F and 210F, respectively, equivalent detergent compositions are secured.

1()3~
The composition of Example IV is modified by replacing the mixture of sulfated tallow alcohol and linear alkylbenzene sulfonate with an equivalent amount of the anionic detergent mixtures set forth herein in Table I, and equivalent results are secured.
EXAMPLE V
A spray-dried granular detergent composition prepared in the manner of this invention is as follows:
In~redient Wt. %
Branch-chain alkylbenzene sulfonate (alkyl = C12 avg ) 20. 0 tlNeodol 23-E6.5"* 5. 0 Sodium tr ipolyphosphate 3 3 . 0 Sodium toluene sulfonate 2 . 0 Carboxymethylcellulose 0. 6 Sodium sulfate 21.9 Kaolinite clay 2 O 5 Sodium silicate (SiO2:Na2O = 2.0) 5 4 Colorants 0 . 1 Water 9- 5 * Synthetic alcohol alkoxylate approximating coconutalkyl range.
("Neodol 23-E6. 5" is a trademark. ) The foregoing composition is prepared by pre-slurrying the kaolinite clay and the coconut ethoxylate surfactant at 150F and admixing the pre-slurry with a crutcher mix comprising the remaining components set forth, also at 150F. The resulting mix is spray-dried in a tower with an inlet air stream of 600F to provide the detergent granules.
In the foregoing procedure the kaolinite is replaced by an equivalent amount of 5 micron bentonite and equivalent results are secured.
EXAMPLE VI
An automatic dishwashing detergent composition prepared in the 30 manner of this invention is as follows.

In~redient 1~)3~14~ Grams Coconutalkyl ethoxylate (6) 25.0 Kaolinite clay 15.0 Coconutalkyl EOt3 ) PO(6 ) * 2 O 0 Sodium tripolyphosphate 100 . 0 Sodium silicate 25.0 Potas s ium dichlorocyanurate 2 . 0 Water 9 * Suds suppressing agent The foregoing composition is prepared by admixing the coconutalkyl ethoxylate nonionic and kaolinite clay at a temperature of 150F and blending therewith the ethylene oxide-propylene oxide suds suppressing agent. The resulting mixture, at 150F, is admixed with the remaining components, also maintained at a temperature of 150F, to provide a homogeneous mix-ture. The resulting mixture is sprayed through a drying tower to provide a homogeneous detergent composition especially adapted for use in automatic dishwasher s .
As can be seen by the disclosures hereinabove, the present invention constitutes a significant improvement in the preparation of detergent granules 20 containing alkoxylated nonionic surfactants which comprises adding kaolinite or bentonite clay to a crutcher mix in the ratios and proportions set forth.
In a preferred mode, the nonionic surfactant is separately sorbed on the clay at a temperature of from 150F to 210F before addition to the hot crutcher mix. Thermogravimetric analyses show that the kaolinite clays employed as disclosed herein substantially and con~istently decrease the loss of non-ionic surfactants by volatilization in a hot (100C-250C) spray-drying tower.
Additional advantages are secured by using various gelling agents and/or hydrotropes in the process, in the manner described.

Claims (22)

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

1. A homogeneous, spray-dried, granular detergent composition comprising:
(a) from about 0.5% to about 40% by weight of kaolinite or bentonite clay; and (b) from about 2% to about 60% of an alkoxylated nonionic surfactant, or mixtures of said alkoxylated nonionic surfactants, at a weight ratio of said surfactant to said clay in the range of from about 6:1 to about 1:2, said surfactant being sorbed on said clay at a temperature of at least 150°F.

2. A composition according to Claim 1 wherein the weight ratio of nonionic surfactant to clay is from about 3:1 to about 1:1.

3. A composition according to Claim 1 wherein the nonionic sur-factant is separately sorbed on the clay at a temperature of from 150°F to 210°F.

4. A composition according to Claim 3 containing, as an additional component, from about 1% to about 50% by weight of a member selected from the group consisting of anionic, semi-polar, zwitterionic and amphoteric water-soluble detergent compounds.

5. A composition according to Claim 4 wherein the detergent com-pound is a member selected from the group consisting of sodium linear C10-C18 alkylbenzene sulfonate; triethanolamine C10-C18 alkylbenzene sulfonate; sodium tallow alkyl sulfate; sodium coconut alkylglycerylether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with from about 3 to about 10 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammonio)-propane-1-sulfonaate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; dodecyl dimethyl amine oxide; coconutalkyl dimethyl amine oxide; and the water-soluble sodium and potassium salts of higher fatty acids containing 8 to 24 carbon atoms.

6, A composition according to Claim 4 wherein the detergent com-pound is an alkyl ether sulfate comprising from about 0.05% to 5% by weight of a mixture of C12-13 compounds, from about 55% to 70% by weight of a mixture of C14-15 compounds, from about 25% to 40% by weight of a mixture of C16-17 compounds and from about 0.1% to 5% by weight of a mixture of C18-19 compounds, said mixture further characterized as comprising from about 15% to 25% by weight of a mixture of compounds having a degree of ethoxylation of 0, from about 50% to 65% by weight of a mixture of compounds having a degree of ethoxylation from 1 to 4, from about 12% to 22% by weight of a mixture of compounds having a degree of ethoxylation from 5 to 8 and from about 0.5% to 10% by weight of a mixture of compounds having a degree of ethoxylation greater than 8.

7. A composition according to Claim 4 wherein the detergent com-pound comprises an .alpha.-olefin sulfonate mixture consisting essentially of from about 30% to about 70% by weight of a Component A, from about 20%
to about 70% by weight of a Component B, and from about 2% to about 15%
of a Component C, wherein (a) said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-1-sulfonic acids containing from about 10 to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of a gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;
(b) said Component B is a mixture of water-soluble salts of bi-functionally-substituted sulfur-containing saturated aliphatic compounds containing from about 10 to about 24 carbon atoms, the functional units being hydroxy and sulfonate groups with the sulfonate groups always being on the terminal carbon and the hydroxyl group being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atoms at least 90% of the hydroxy group substitutions being in 3, 4, and 5 positions; and (c) said Component C is a mixture comprising from about 30% to 95% water-soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 10 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic com-pounds having a sulfonate group attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

8. A composition according to Claim 1 containing, as an additional component, from about 5% to about 50% by weight of a detergency builder.

9. A composition according to Claim 8 wherein the detergency builder is an inorganic builder.

10. A composition according to Claim 8 wherein the detergency builder is an organic builder.

11. A composition according to Claim 8 wherein the detergency builder is a seeded builder.

12. A composition according to Claim 1 containing, as an additional component, from about 0.1% to about 5% by weight of a gelling agent.

13. A composition according to Claim 1, comprising:
(a) from about 1% to about 10% by weight of kaolinite clay;
(b) from about 5% to about 35% by weight of a mixture of an alkoxylated nonionic surfactant having an HLB in the range of from 11 to 17 and an alkoxylated nonionic co-surfactant having an HLB in the range of 7 to 10.5, said mixture having a mixture HLB of from 10 to 12.5, said mixture being separately sorbed on said clay at a temperature of from 150°F to 210°F;
(c) from about 1% to about 50% by weight of a water-soluble, anionic detergent compound; and (d) from about 5% to about 50% by weight of a detergency builder.

14. A composition according to Claim 13 containing, as an additional component, from about 0.1% to about 5% by weight of a gelling agent.

15. A composition according to Claim 14 wherein the gelling agent.
is a member selected from the group consisting of microfine silica, alkyl cellulose derivatives and hydroxyalkylcellulose derivatives.

16. A composition according to Claim 15 wherein the gelling agent is selected from the group consisting of hydroxybutylcellulose and hydroxy-propylmethylcellulose.

17. A composition according to Claim 13 containing, as an additional component, from about 0.3% to about 7% by weight of a hydrotrope.

18. A composition according to Claim 17 wherein the hydrotrope is sodium p-toluene sulfonate.

19. In a process for preparing a homogeneous, spray-dried detergent granule containing a substantial quantity of alkoxylated nonionic surfactants comprising the steps of:
(a) preparing a 150°F to 210°F crutcher mix containing the granule components; and (b) spray-drying said crutcher mix, the improvement which comprises adding kaolinite or bentonite clay to said crutcher mix to provide a nonionic surfactant:clay ratio of from 6:1 to 1:2.

20. A process according to Claim 19 wherein the nonionic surfactant is separately sorbed on the clay at a temperature of 150°F to 210°F and added to the crutcher mix.

21. A composition according to Claim 1, wherein said alkoxylated nonionic surfactants have the general formula R - O - (CyH2yO)a - (C2H2zO)b - CWH2wOH
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 from 8 to about 20 carbon atoms; y and z are each integers of from 2 to about 3, either z or y being 2 when the other integer is 3; w is an integer from 2 to about 3; a and b are each integers of from 0 to about 8, the sum of a + b being in the range of from 6 to about 16;
and said nonionic surfactants having an HLB of from about 11 to about 17.

22. A process according to Claim 19, wherein said alkoxylated non-ionic surfactants have the general formula R - O - (CyH2yO)a - (CzH2zO)b - CwH2wOH
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 from 8 to about 20 carbon atoms; y and z are each integers of from 2 to about 3, either z or y being 2 when the other integer is 3; w is an integer from 2 to about 3; a and b are each integers of from 0 to about 8; the sum of a + b being in the range of from 6 to about 16;
and said nonionic surfactants having an HLB of from about 11 to about 17.