CA1050379A - Controlled sudsing detergent compositions - Google Patents

Abstract

CONTROLLED SUDSING DETERGENT COMPOSITIONS
Ronald Edward Atkinson ABSTRACT OF THE DISCLOSURE
A detergent composition is provided which comprises a nonionic polyethoxy surface active agent with an HLB value of 11 to 14.5, a nonionic ethoxylated alcohol surface active agent in which 15% to 30% of the alcohol is a secondary alcohol and the average degree of ethoxylation is from 3 to 4, and a water soluble electrolyte.

Description

The present invention relates to detergent compositions and especially to a nonionic detergent composition having an im-10 proved combination of sudsing behaviour and of cleaning performance,particularly with xegard to greasy and oily stains.
Detergent compositions presently finding wide-spread use normally contain a water-soluble organic anionic detergent as the principal soil-removal component~ Such detergent compositions find 15 utility in removing a wide range of stains. However, their ability to remove grease and oil stains is somewhat limited. Such a deficiency is especiaily apparent when polyester fabrics which have been soiled with various grease and oil stains are laundered in aqueous laundry baths. Attempts at formulating anionic deter-20 gent compositions containing specific grease and oil removaladditives, e.g. enzymes, have not been fully satisfactory.
Water-soluble organic nonionic detergents are known to be especially good at removing grease and oil stains. While these nonionic detergents perform reasonably well in this respect, 25 detergent compositions containing them as the major soil-removal ~osv375a agent have not been significantly commercialized. Various draw-backs relating to processing and performance have hindered the introduction of a nonionic detergent-based composition~ For example, certain nonionic organic detergents are composed of rela-5 tively volatile components; aqueous slurries containing such com-ponents in a significant amount create when spray-dried an unaccept-able stack-emission problem. Elaborate processing techniques such as the use of inorganic carriers for the nonionic organic deter-~ents eliminate the need for including the detergent in the spray-10 drying process; however, these processing techniques are not with-out their own special problems.
The suds pattern of a water-soluble organic nonionic deter-gent~containing detergent composition is also unacceptable under certa$n washing conditions, e.g. European conditions where drum 15 washing machines are used. As a general rule, a copious amount of suds is desired only when the detergent composition is used for washing by hand. For other uses, e.g. drum-machine washing in Europe, a small degree of sudsing throughout the washing process is desired. Modifying the suds pattern o~ a water-soluble organic 20 nonionic detergent-containing detergent composition has been an arduous task. This fact, together with the heretofore discussed problems associated with the water-soluble organic detergents, has A tended to offset the nonionic detergents primary attribute, i.e.
their good grease and oil stain removal property.
Heretofore, the nonionic organic detergents that have been used in detergent composit ons have been of the water-soluble type.
It has always been assumed that an organic detergent could pro-perly perform its soil-removal function only if in water solution.
The use of water-insoluble detergents has been mainly limited to 30 solvent-based compositions intended for use in the dry-cleaning industry. Water-insoluble organic nonionic detergents that have ~ 5037~
been used in detergent compositions haYe been used only in con-junction with relatively large amounts of a water-soluble anionic or nonionic detergent. For ex2mple r Bri~ish patent specification 716,641 discloses the use of a water-insoluble organic nonionic detergent as part of a mixture at a level of from 10% to 70~, 5 the remaining portion of the mixture being a water-solubie oxganic nonionic detergent. Canadian Patent No. 860,898 and German patent specification 2,109,892 also contain disclosure~ of the utility of water-insolub1e organic nonionic detergents in detergent - ~ompositions, but not as a major portion of the total detergent 10 System~
It has been discovered, as aisclosed in our copending Canadian application no. 218,740 filed January 27, 1975~ that a properly formulated detergent composition containing a water-insoluble organic nonionic ~etergent as the principal detergent 15 can be made. S~ch a co~position is especially adapted for remov-i~g grease and oil stains; additionally it is also feasihle to produce such a composition via a spray-~rying process.
The composition disclosed in Canadian application no. 218,740 is especially adapted for removal of grease and oil stains, and 20 compriSes - ~
(a) at least 6% of a water-insoluble polyalkoxy organic nonionic detergent having the formula R(OCXH2X~OH, wherein R represents an alkyl or alkenyl group having from 8 to 22 carbon atoms or an alkylated or alkenyla-ted phenyl group having from 6 to 12 carbon atoms in the alkyl or alkenyl group, x is 2 or 3 and n is from 1 to 8, and having an HIB (as hereinafter defined) of less than 10.0;

.

~,~s~3t~9 S~) a water-soluble electrolyte in an amount sufi~icient to ai~ in the action of the water-insoluble nonionic deter~ent;. and ~c) from 0 to 30%, by weight of the total organic deter-gent, of organic anionic,zwitterionic or ampholytic detergent~, - . - ' The aforesaid compositions may also contain a proportion of a watex-soluble nonionic detergent having an HLB greater than 10.0 providea that the HLB of the mixed nonionic detergent 10 sy-stem is less than 10Ø
It has now been discovered ~hat, provided that a special narrowly defined class of poorly water-soluble nonionic surfac-tants is employed, certain specified mixtures of water-soluble nonionic detergents with said poorly water-soluble surfactants, 15 even though the HLB of the mixtures is a little above 10.0, have especially advantageous~properties. These compositions have an improved combination of low sudsing in the wash - especially in the wash at temperatures from 60C, a~d more especially from 80 C, to the boil - and excellent cleaning both of average soiling 20 and of greasy or oily soiling. Thus they may clean as well as prior-art compositions and provide better suds control in the wash, or they may clean better and provide similar suds control, or they may both clean better and control suds better~ .
In particular, the present invention provides a detergent 25 composition comprising (A) a nonionic polyethoxy surfactant ha~ing an HLB, a~
hereindefined, in the range from 11 to 14.5;
SB) a compound of the general foxmula Rl ~CHCH20 (C~2CH2~) n (I) .

~ ' ' , .

~lO50379 wherein Rl is a .straight chained alkyl group, R2 is ~ or -CH3, the total n~nber of carbon atoms in ~1 and R2.is from lO.~o 13, R2 is C~3 in from 15%
to 30% by weight of the ullethoxylated alcohols having . the formula Rl .
CHC~2OH (II3 - 'R2 ' ,.
and the average degree of e~hoxylation n is from 3 to 4; and (C) a water-soluble electrolyte in an amount sufficient to aid in the action of th9 water-insoluble nonionic detergent;
there being present from 6% to. 30% by weight of components (A) and (B) together, the weight ratio of component (A) to component (B) beiDg from 20:80 to,45:55, the composition containing not 15 more than 1~% of anionic surfactant by weight of components (A) and (B) together.
Preferably the weight ratio of components (A) and (B) together to component -~C) is from 1:15 to 1:2, but when insoluble ~uilders as described hereinafter are employed, lower levels of 20 soluble electrolyte may be used extending the abo~e range to 2:1, and especially from 1:4 to 2:1.
It is surprising that the combination of a polyethoxy non-ionic surfactant with the particular branched-chain compounds (B), in the specif.ied proportions, has advantages over corresponding 25 compositions wherein the components (A) and (B) are present in different proportions, or wherein the component (B) i5 replaced by nonionic surfactants of slmilar ~LB but of different constitu-tion, such as ethoxylated linear primary or secondary alcohols.

A

105037~ -The polyethoxy ~onionic surfactants of component (A) of the compositiOn of the present invention have the formula Ro(c~2cH2o)mH tIII) wherein R is a hyarocarbyl group and m i5 such that the sur-5 factant has ~he specified HLB ~alue.
The hydrocarbyl portion of the above-described materials gives rise to their lipophilic characteristics; whereas the ethylene oxide portion determines their hydrophilic characteristic6.
The overall hydrophilic-lipophilic charactexistics for a given 10 hydrocarbyl-alkylene oxide condensate are reflected in the balance of these two factors~ i.e~ the hydrophilic-lipophilic balance (HLA). The HLB of the ethoxylated nonionics of this invention can be experimentally determined in known fashion or calculated.
They are calculatea in ~he manner set forth in Becker, nEmulsions, 15 Theory and Practice" Reinhold Publishing Co., pages 233 and 248.
For example, the èquation HLB = B/5 wherein B is the weight per-centage of oxyethylene content, i~ used to calculate the H~B
of the fatty ~lcohol ethoxylates employed herein.
All manner of hydrocarbyl materials, such as branched-chain and straight-chain alcohols and alkylphenols, primary, secondary and tertiary alcohols~ olefinic alcohols and the like, having the requisite number of carbon atoms may be used to prepare the ethoxylated detergents. Glycols and polyols may also be used, but monoh~dric alcoholic and monohydric alXyl phenolic ethoxy-25 lates are preferred The alkyl phenol ethoxylates most suitable are those having6 to 12~ preferably 8 or 9 carbon atoms in the alkyl group.
Though effective, the alkyl phenol derivatives are less readily biodegradable than the alkyl derivatives. The alkyl ethoxylates 30 may be derived from primary or secondary, branched or unbranched ~q ' , ~S~3'79 monohydric alcohols having lO to 20 carbon atoms. It is pre-erred that a major proportion, for instance over 60~ by weight, should have 13 to 15 carbon atoms, wit~h a low level particularly of C12 or lower alcohols. Primary alcohols, branched or un-branched, are generally preferred to secondary alcohols. Par-~icularly preferred are alkyl ethoxylates of the general formula R
1~ . .
~CH-CH20 (CH2~H20)m~

whexein Rl, R2 and m are as defined above. It is further pre-;: ferred that R2 be CH3 in from 20~ to 26% by weight o the unethuxy-lated alcohols. Comm~rcially available materials of this type aresold under the traae marks "Dobanoln (Shell Chemicals) and ~Lutensol" (BASF).
Examples of other polyeth~xY nonionic surfactants are the products of the condensation of the appropriate proportion of ethylene oxide, to obtain the proper HLB value, in linear pr-mary alcohols, such as those from natural fats, e.g. coconut oil, palm kernel oil, tallow and the like, or on linear primary alcohols derived synthetically, as by the Ziegler process. "Tergitols"
(trade mark), e.g. the "Tergitol 15-S!' series, are examples of ethoxylated linear secondary alcohols. Primary and secondary alkenyl alcohols, e.g. dodecenol or oleyl alcohol, may be used, and branched-chain saturated alcohols, optionally more highly branche~ than the most preferred group described above, for instance derived by the well known OXO process, are also suitable.
The ~Synperonics" (traae mark) marketed by I.C.I~ LLmited are of this class and are be~ieved to have the general formula (IV~ above wherein R2 ~s CH3 in from 4~ to 60% by weight of the unethoxylated alcohols.

. ' ' ~O~V37g The component-(B) of the compositions is already narrowly defined. Most preferred are compounds wherein R2 is C~3 in from 20 to ~6% by weight of the unethoxylat:ed alcohols, Rl and R2 together have 12 to 13 carbon atoms and n is about 4. The re-mainder of the alk~l groups should be linear, apart from thesmall amounts of more highly branched groups-to be expected in commercial products. A commercial source of suitable surfactants is found in the "Dobanols" (trade mark~ especially "Dobanol 45-E-4", marketed by Shell Chemicals ~t is preferred that the ratio, ~y weight, of component (A) to component (B) should be in the range of from 25:75 to 40:60, especially about 1:2.
It is generally preferred that the compositions should contain li~tle or no anionic (soap, or non-soap) surfactant, but often small guantities not over 15%, preferably not over 10% by - weight of the total nonionics components ~A) and (B) are added to facilitate m~ufacture of the compositions, as more fully de-scribed below. The amount of nonionic detergent ~A) plus ~B) is preferably from 10% to 20% by weight.
The electrolyte used in the composition of this invention may be any of several known compounds capable of dissociating into ions when added to water. Such compounds ara necessary for use wi~h the organic nonionic detergent mixture to obtain proper cleaning performance. It is theorized that the electrolyte (1)

2~ prevents a gel-like phase formation when the present compositions are added to water and/or (2) aids in dispersing the water-insoluble nonionic detergent in water, especially at low tempera-tures. Regardless of the mechanism by which the electrolyte aids in the proper perormance of the nonionic detergent, its presence is necessary. The electrolyte is also needed for the role it plays in the physical form of the detergent composition. That is, in ~5Q379 solid forms of the present compositions~ it provides a crystalline structure to absorb the liquid nonionic detergent. Suitable electrolytes are selected from the water-soluble alkali metal and alkaline earth metal phosphates, c:arbonates, carboxylates sulfates and chlorides. Examples of salts of this type are sodium tripolyphosphate, sodium carbonate, potassium carbonate, so~ium acetate, potassium acetate, so~ium citrate, so~ium pro-pionate, sodium nitrilotriacetate, sodium oleate, potassium chloride, sodium chloride, sodium sulfate, magnesium sulfate.
-10 and trisodium sulfosuccinate. It should be understood that the foregoing list is merely illustrative and not limiting of the elPctrolytes ~at are useful in the context of this inv~ntion.
Preferred compositions of the invention are the granule-type detergent compositions intended ~or heavy-duty laundering.
Such compositions generally contain a water-soluble alkaline detergency builder. It shoula be understood that certain of the above-mentioned electrolytes also possess builder properties.
These electrolytes are preferred when the composition is for-mulated for heavY-dUtY launary purpo~es. Such preferred heavy-dut~ detergent compositions have a content of electrolyte within the range of 10% to 80%, preferably 20~ to 50~. However, electrolytes not possessing builder properties may be used in heavy duty detergent compositions provided a builder is also included.
As is well known in the detergency art, builders are included in detergent compocitions for sequestering water hardness ions. The builder used in the heavy duty detergent compositions of this invention ma~ be any of several well known and commercially available organic and inorganic builder salts. Suitable alkaline, inorganic builder salts are alkali metal carbonates, aluminates, ~ ~ .

- ~05(:~37~
phosphates, polyphosphates and silicates. Specific examples of these salts are sodium or potassium tripolyphosphates, aluminates, carbonates, phosphates and hexametaphosphates, optionally in the presence of certain crystallization seeds, for 5 example forms of calcium carbonate, as described in Belgian patent specification 798,856. Suitable organic builder salts are the alkali metal, ammonium and substituted ammonium poly-phosphonates, polyacetates, and polycarboxylates.
The polyphosphonates specifically include the sodium 10 and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane-l-hydroxyrl,l-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphos-phonic acid. Other examples are the water-soluble salts le.g.
those with sodium, potassiulp, ammonium and substituted ammonium, 15 such as mono-, di-, and triethanolammonium, cations) of ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic ac~d, carbonyldiphosphonic acid, ethane-lOhydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,

3-tetraphosphonic acid, propane-1,1,2-3-tetraphosphonic acid, 20 Examples of these polyphosphonic compounds are disclosed in British patents 1,026,366; liO35,913; 1,129,687; 1,136,519 and 1,140,980.
Polyacetate builder salts suitable for use herein in-clude the sodium, potassium, lithium, ammonium, and substituted 25 ammonium salts of ethylenediaminetetraacetic acid, N-(2-hyrox-ethyl)-ethylenediaminetriacetic acid, N-(2-hydroxyethyl)-nitrilodiacetic acid, diethylenetriaminepentaacetic acid, 1,2-diaminocyclohexanetetraacetic acid and nitrilotriacetic acid.
The trisodium salts of the above acids are generally preferred.
The polycarboxylate builder salts suitable fs)r use herein consist of water-solub~sal~s of polymeric aliphatic polycarboxylic 5~37~

acids as, for example, described in U.S. Patent 3,308,067.
Other detergent builder salts for use in the composi-tions of the present invention include the water-soluble salts of (a) amino p~lycarboxylates; (2) ether polycarboxylates;
(3) citric acid; and ~4) aromatic polycarboxylates deri~ed from benzene.
The water-soluble amino polycarboxylate compounds have the general formula R - N

wherein R is selected from:

-CH2COOM; -CH2CH2OH; and R' wherein R' is ~QH2CH2OH; -CH2COOM; or ~CH2COOM
CH2CH2N~

and each M is hydrogen or a salt-forming cation.
These materials include the water-soluble aminopoly-carboxylates, e.g. sodium and potassium ethylenediaminetetra-~ acetates, nitrilotriacetates and N-(2-hydroxy-ethyl)-nitrilo-diacetates. Especially preferred are water-soluble salts of nitriloacetic acid.
The water-soluble "ether polycarboxylates" have the general formula:

~S~37~3 o/~l \R2 wherein Rl is selected from CH2COOM; -CEI2CH2COOM;
COOM~ COOM COOM COOM
- C~ - C - ; and - CH - CH - ;
and R2 is selected from:
-CH2COOM; -cH2cH2cooM; - CH - CH2 C OOM COOM
COOM COOM COOM COOM COOM
-CH ; - C - C - ; and -CH - CH - ;
COOM
whereby Rl and R2 form a closed ring structure in the ;e~eh.t~that~the~a~e~..s~lected from COOM COOM COOM COOM
10- C = C -; and~ - CH - CH - , and each M is hydrogen or a salt-forming cation.
Specific examples of this class of carboxylate ~uilders . include the water~soluble salts of oxydiacetic acid having the formula ~CH2COOM

~-oxydisuccinic acid having the formula COOM COOM
CH -~-~CH2 COOM COOM

3~S03~
carboxymeth~l oxysuccinic acid having the formula COOM COOM

; \ CH2 - COOM
furan tetracarboxylic acid of the formula COOM COOM
/C ~ C
O\
f c COOM COOM
and tetrahydrofuran tetracarboxylic acid having the formula COOM f OOM
CH - ICH

CH - H
COOM COOM
The salt-forming cation M can be, for example, an alkali metal cation such as potassium, lithium or sodium, or ammonium or - an ammonium derivative.
Water-soluble polycarboxylate builder salts derived from citric acid cons~t~e another class of a preferred builder for use hereinO Citric acid, also known as 2-hydroxy-propane-1,2,3-tricarboxylic acid, has the formula - CH2.COOH
f (OH) .COOH
CH2.COOH
Citric acid occurs in a free state in nature; large quantities of it are produced, for example, as a by-product of ~- sugar obtained from sugar beets. For use in the compositions of this invention, it can be desirable to use the acid and ``
105~379partially neutralized species whereby the neu~ralizing cation is preferably selected from alkali metal ions, such as sodium, potassium and lithium, ammonium and substituted ammonium.
~ Certain zeolites or aluminosil:;cates, which are insoluble S in water, can also be used as a builder.
- -One such aluminosilicate which is useful in the compositions of the invention is an amorphous water-insoluble hydrated compound of the formula Nax(xAlO2.ySiO2)-, wherein x has a value of from 1 to 1.2 and ~ is 1, saia amorphous material being further characterized by a Mg exchange capacity of from about 50 mg eq.
CaCO3/g to about 150 mg eq. CaCO3/g. This ion exchange builder is more fully described in Canadian patent application 204,480, B.L. Madison et al, filed July 10, 1974.
A second water-insoluble synthetic aluminosilicate ion exchange material useful herein has the formula Nazl~Alo2~z.(sio2)y]x~2o~
wherein z and ~ are integers of at lea~t 6; the molar ratio of z to ~ is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264; said aluminosilicate ion exchange material having a partic~e size diameter from about 0.1 micron to about 100 microns, preferably to about 15 microns, a calcium ion ex~hange capacity of at least about 200 mg eq/g; and a calcium ion exchange rate of at least about 2 grains/gallon/minute gram described in Belgian Patent 814,874 and in copending Canadian ~5 patent application l9g,507 filed May 10, 1974.
The above described aluminosilicates are ~mployed at levels of from about 1% to about 40%, preferably about 5% to about 25 ~y weight.
The ratio of organic nonionic ~etergent mixture, components (A) and (B), to electrolyte is from 1:15 to 1:2, preferably from 1:9 to 1:4 for a soli~-type product, e.g. granules and powder ~ ' ' ~

' ~0S~ 3~
when not containing water insoluble builders,,such as those described above.
The grease and oil stain-removal ability of the composi-tions of this invention is superior to that of known anionic detergent compositions. Aaditionally, it has been found that the compositions of this invention are super'ior to detergent composi~
tions containing conventional water soluble organic nonionic ' detergents at temperatures above'which a phase change occurs ~as more fully explained below) and equivalent to such compositions 0 at lower temperatureS in terms of grease and oil stain-removal.
The reason for effective cleaning performance of the nonionic detergent containing rompositions of this invention is not fully understood. It is theorized that at higher temperatures in the washing solution a separate phase containing the nonionic detergent is formed~ Above this temperature (which is dependent on the specific detergent ~ixture) a very distinct phase is observed.
It is believed that this very fluid detergent phase is responsible for the high stain removal performance. At lower temperatures, such a phase is not noticed. Instead, a cloudy suspension is observed.
However, satisfactory cleaning performance is observed at the lower temperatures also.
The detergent compositions may be manufactured by any known method. For example, the nonionic detergents may be simply mixed with the electrolyte, as by spraying thereon,,or ~hey may be sorbed on a carriex and thereafter mixed with the elec~rolyte.
One convenient method is to ~repare spray dried granules comprising some or all of the solid components o~ the composition, including the electrolyte, and to use these as a carrier for the nonio~ic mixture. Often it is aesirable to include a little anionic sur-factant in the slurry to be spray dried to facilitate the drying -15-~

~ ' ' , ' .

-11)5~3'~
process and to control the bulk density of the dried granules.
Alternatively the built heavy duty compositions of this invention may be produced by a spray drying process. An aqueous slurry of the water insoluble nonionic detergent, electrolyte and builder (if the electrolyte does not possess builder proper-ties~ is initially formed. Usually the aqueous slurry comprises from 20% to 45~ water with the remaind~r being the nonionic organic detergent, electrolyte, builder and optional components.
The temperature of the aqueous slurry may be from 40C to 100C.
Thereafter, the slurry is sprayed into a spray drying tower.
In one method of spray drying, the hot air, i.e. air having a temperature between 100C and 380~C, is introduced at the base of the tower. As the atomized particles contact the heated air, water is driven off and the dried granules are collected at the bottom of the towerO The water-laden air exits at the top of the tower. In another method of spray drying, the hot air is introduced along with the atomized droplets at the same end of the tower.
Preferably, the hydrophobic portion of the organic deter-gents used in such a drying process contains little Cl2 andlower carbon atom chains. These compounds are especially use-ful for processes wherein stack emission is a concern.
Other detergent composition additives can be included in the compositions of this invention; for example, brighteners, enzymes, soil suspending agents, perfumes and bleaches can be included in the present compositions in the customary amounts.
The compositions of this invention are used in a conven-tional laundering process. Thus, 30 to 200 grams of the compo-sition is generally added to the washing machine as well as the soiled laundry and from 15 litres to 80 litres of water. The g temperature of the washing process can vary from 20C to boiling. However, especially good stain removal performance from the compositions of this invention is observed at a temp-erature above which phase separation occurs and, for this reason, it is preferred that such a temperature be employed.
The invention is therefore particularly valuable in washing at from 80 to 95C.
The following examples illustrate the present inven-tion.
Examples 1 - 4 Detergent compositions were prepared of the general composition:

Surfactant mixture ("Active") as stated below Sodium tripolyphosphate 34-32 Sodium sil.icate 56-7 Sodium su~phate 12 Sodium perborate 26 Moisture 6.5 Miscellaneous minor components, and impurities 2.9 Enzyme (protease) ~resent Specific compositions tested had "active" surfactant mixtures as follows:

Composition A Linear dodecyl benzene sulphonate (LAS) 8.0 Nonionic (Tallow alkyl Ell) 3.1 Soap (C16-20) 4.0 Composition B "Dobanol 45-E-7" 3.9 "Dobanol 45-E-4" 7.8 Composition C "Dobanol 45-E-7" . 7.8 ~Dobanol 45-E-4" 3.9 I,~,S O . 9 Composition D "Dobanol 45-E-7" 7.8 "Dobanol 45-E-3" 3.9 I.AS o . g Composition E "Dobanol 45-E-7" 3.9 "Dobanol 45-E-5" 7.8 Composition F LAS
Soap (normal type) 7 Nonionic (C17 alkyl E14) (This was a ~ationally marketed heavy duty detergent composition, believed to differ from the compositions above significantly only in lacking enzyme, and in the above "active~ combination~.

~OS~37~
Composition G "Tergitol 15-S~3" 7.8 "Dobanol 45-E-7" 3.9 "Dobanols" (tra~e mark) are primary alcohols ha~ing 14-15 carbon atoms with about 25% 2-methyl branching, condensed with an average of the indicated number (3,4, 5 or 7) of ethoxy groups.
"Tergitol 15-S-3"* is a mixture of linear secondary alcohols having 11-15 carbon atoms condensed with an average of 3 ethoxy groups.
Example 1 These compositions were used to wash normal fabric loa~s containing stained test pieces as indicated below. The washing conditions were:
- Hoover Automatie Washing Machine (3236H) Temperature 85C (Cycle B3) Product concentration 0.83~ by weight Water 18 hard Load 8 lbs (Domestic soiled clothes) Test pieces were compared for soil removal by a panel of judgès using a paired comparison technique.
Cleaning comparisons were as follows:
Composition B A F

Fabric/Soil Polyester Cotton/Ballpoint ink Better 3 -equal *Trademark ~0;~7~
Cotton Towel/Oil (Dirty Motor) Better 4 - equal Polyester Cotton/Boot Polish Better 7 - equal Nylon/Boot Polish Better 1 - equal Cotton/Lipstick Better 3 - equal Polyester Cotton/Brown Eye Shadow Better 5 - equal Cotton/Brown Eye Shadow Better 5 - e~
Nylon/Brown Eye Shadow(Better)3/4 - e~ual Nylon/Lipstick Better 3 - equal Cotton/Boot Polish Better 5 - equal Nylon/Ballpoint Ink(Better)0.9 - equal Cotton/Ballpoint Ink - all equal Cotton Towel/Oil Better 5 - equal The ratings in brackets were just not significant at 95% con-fidence over the random error of the test.
The degree of preference is indicated by the figures given for the separation of the ratings divided by the least significant difference ("yard stick") at 95% confidence.
Example 2 In another series of tests, using the same washing con-ditions as in Example 1, except for a 0.43% product concentra-tion, the following results were obtained for Composition B
compar~d with Composition D. These two compositions had satis-factory sudsing beha~iour in the washing machine.
~ c~S~i Cleaning Rating Polyester Cotton/Oil (Dirty Motor) ~ Better) ~ -Cotton Towel/Oil Better 2~ -Terry Towel/Oil Better 2~ -Cotton/Boot Polish (Better) ~ -Polyester Cotton/Boot Polish equal Nylon/Boot Polish equal Cotton/Krefeld equal - -~L~5~37~
Cotton/sallpoint Ink equal - -Cotton/Lipstick Better 1 Polyester Cotton/Lipstick (Better)~ -Cotton/Brown Eye Shadow equ~
Polyester Cotton/Brown ~ye Shadow equal Example 3 In similar tests to the foregoing, using 0.43% product concentration in soft water (2 hard), the sudsing of Composi-tions B and C was compared.
Runs Oversudsing ~ Full Porthole ,. . _ ~ , . .
~ - - - (wltkout oversudsing) Composition B 12 0 0 Composition C 10 4 Composition E 6 3 Desirably there should be no occasion when oversudsing or even suds fully covering the porthole of the machine is observed.
Example 4 In similar tests to the foregoing using 0.43~ product concentration in 18 hard water, the following cleaning ratings 20 were obtained~ These compositions had satisfactory sudsing behaviour in the wash.
Composition B G
--, Fabric/Soil Cotton - Motor Oil Bet~er Polyester Cotton - Motor Oil "

Cotton- Red Lipstick "

Polyester Cotton Red Lipstick "

Nylon- Red Lipstick "

Cotton- Brown Eye Shadow lOS03~9 ~olyester Cotton - Brown Eye Shadow Nylon - Brown Eye Shadow n Cotton - "Pan~ Stik:n* n Polyester Cotton - "Pan Stik" n Nylon - "Pan Stik"
Cotton - Krefeld Notes: In the foregoing Examples, the soils were as follows:
Lipstick Rimmel "truly red"
"Pan Stik" Max Pactor "deep olive"
ln Brown Eye Shadow Miners brown Boot Polish "Kiwi"** black Ballpoint ink "Bic"***red/blue/green/black Krefeld soil contains kaolin 86%, lampblack 8.0~, iron oxide (316) 4.0~, and iron oxide (~20) 2.0%. Wool grease is added at a ratio of 7:1 wool grease: pigment and spread evenly on the fabric (3.4% of finished cloth weight is grease)~
*Trademark **Trademark ***Trademark ,~q, .

Claims (13)

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

1. A detergent composition comprising (A) a nonionic polyethoxy surfactant having an HLB, in the range from 11 to 14.15;

(B) a compound of the general formula.

(I) wherein R1 is a straight-chain alkyl group, R2 is H or -CH3, the total number of carbon atoms in R1 and R2 is from 10 to 13, R2 is CH3 in from 15%
to 30% by weight of the unethoxylated alcohols having the formula (II) and the average degree of ethoxylation n is from 30 to 4; and (C) a water soluble electrolyte in an amount sufficient to aid in the action of the water insoluble nonionic detergent;
there being present from 6% to 30% by weight of components (A) and (B together, the weight ratio of component (A) to component (B) being from 20:80 to 45:55, the composition containing not more than 15% of anionic surfactant by weight of components (A) and (B) together.

2. A composition according to Claim lwherein the HLB value of component (A) is from 11.5 to 13.

3. A composition according to Claim 1 wherein the surfactant of component (A) is an ethoxylated alcohol having 10 to 20 carbon atoms, at least 30% by weight thereof having 13 to 15 carbon atoms.

4. A composition according to Claim 1 or 2 wherein the surfactant of component (A) has the formula (IV) wherein R1 and R2 are as defined in Claim 1 and m is a number such that the HLB value is from 11 to 14.5.

5. A composition according to Claim 1 or 2 wherein R2 in component (B) is CH3 in from 20% to 26% of the unethoxylated alcohols.

6. A composition according to Claim 1 or 2 which contains from 10% to 20% by weight of components (A) plus (B).

7. A composition according to Claim 1 or 2 wherein the weight ratio of component (A) to component (B) is from 25:75 to 40:60.

8. A composition according to Claim 1 or 2 wherein the content of anionic surfactant is not more than 10% by weight of compo-nents (A) and (B) together.

9. A composition according to Claim 1 wherein the weight ratio of components (A) and (B) together to component (C) is from 1:15 to 1:2.

10. A composition according to Claim 9 wherein the weight ratio of components (A) and (B) together to component (C) is from 1:9 to 1:4.

11. A composition according to Claim 1 or 2 wherein component (C) comprises one or more water soluble inorganic or organic detergency builder salts.

12. A composition according to Claim 1 which contains from 1 to 40% by weight of a water soluble builder and wherein the weight ratio of components (A) and (B) together to component (C) is from 1:4 to 2:1.

13. A composition according to Claim 12 which contains from 5 to 25% by weight of said soluble builder.