CA1040962A - Monionic detergent composition - Google Patents

Abstract

DETERGENT COMPOSITION

Alain Lagasse Thomas Dean Storm Ronald Allen Perry ABSTRACT
This invention relates to a detergent composition.
More particularly, it relates to a nonionic detergent compo-sition especially adapted for removing grease and oil stains.

Description

BACKGROUND OF THE INVENTION
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 utility in removing a wide range of stains. However, their ability to remove grease and oil stains is somewhat limited. Such a deficiency is especially apparent when polyester fabrics which are soiled with various grease and oil stains are laundered in aqueous laundry baths.
` Attempts at formulating anionic detergent compositions con-taining specific grease and oil removal additives, e.g.
enzymes have not been fully satisfactory.
Water-soluble organic nonionic detergents are known to be effective at removing grease and oil stains.
While these nonionic detergents perform reasonably well in this respect, detergent compositions containing them as the major soil removal agent have not been significantly commercialized. Various drawbacks relating to processing ~ and performance have hindered the introduction of a nonionic `j detergent based composition. For example, certain nonionic ~ organic detergents are composed of relatively volatile ., I
.
7~
,~

~U4(~62 components; aqueous slurries containing such components in a significant amount when spray-dried create an unacceptable stack emission problem. Elaborate processing techniques such as the use of inorganic carriers for the nonionic organic detergents eliminate the need for including the detergent in the spray-drying process. These processing techniques, though, ; are not without their own special problems.
The suds pattern of a water-soluble organic nonionic detergent-containing detergent composition is also unacceptable under certain washing conditions, e.g. European conditions where drum wash machines are used. As a general rule, a copious amount of suds is desired only when the detergent composition is used for hand-washing purposes. For other uses, i.e. drum machine washing in Europe, a small degree of sudsing throughout the washing process is desired. Modifying the suds pattern of a water-soluble organic nonionic detergent-containing detergent composition has been an arduous task.
This fact as well as the heretofore discussed problems associated with the water-soluble organic detergents, have all 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 compositions have been of the water-soluble type. It has always been assumed that an organic detergent could properly perform its soil removal function only if in water solution. The use of water insoluble deter-gents has been mainly limited to solvent based compositions ~ intended for use in the dry-cleaning industry. Water-insoluble -~ organic nonionic detergents that have been used in detergent compositions have been used only in conjunction with relatively A

- 2 -. : .... . . ::

10~ 962 large amounts of a water-soluble anionic or nonionic deterqent.
(For example, see British patent specification 716,641 wherein a water-insoluble organic nonionic detergent is used as part of a mixture at a level of from 10% to 70~ with the remaining por-tion of the mixture being a water-soluble organic nonionic de-tergent.) Canadian patent specification 860,898 and German patent specification 2,10~,892 also contain disclosures of the utility of water-insoluble organic nonionic detergents in deter-`! gent compositions - but not as a major portion of the total detergent composition.
It has now been discovered that a properly formulated detergent composition containing a water-insoluble organic " nonionic detergent as the principal detergent can be made. Such~` a composition is especially adapted for removing grease and oil `
;~ stains; additionally, it is also feasible to produce such a composlt~on via a spray-drying process. `
i It is therefore, an object of this invention to produce a nonionic detergent composition especially adapted for the removal of grease and oil stains.
It is a further object of this invention to produce a spray-dried nonionic detergent composition that has satisfactory cleaning performance.
Tpese and other objects will become apparent from the following description and examples.
`~ As used herein, all percentages and ratios are by weight unless otherwise stated. Temperatures are in degrees centigrade ~ unless otherwise indicated.
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.

; .SUMMARY OF THE INVENTION
The present invention provides a detergent composi-tion especially adapted for removal of grease and oil stains consisting essentially of a) from 6~ to 70~ of a water-insoluble organic nonionic detergent having the formula RtOCXH2X)noH
wherein R represents an alkyl or alkenyl group having from 8 to 22 carbon atoms or an alkylated or alkenylated phenyl ~ group having from 6 to 12 carbon atoms in the alkyl or alkenyl 10 group, x is 2 or 3 and n ranges from 1 to 8,and having an HLB
of less than 10.0; b) a water-soluble electrolyte selected from the group consisting of alXali metal and alkaline earth metal phosphates, carbonates, carboxylates, sulfates and chlorides, the ratio of said water-insoluble nonionic detergent to said electrolyte being in the range of 100:1 to 1:15; and c) from about 0% to about 15% anionic, zwitterionic, or ;: .
~ ampholytic detergent based on the weight of the total organic ;~ detergent system.
~` DETAILED DESCRIPTION OF THE INVENTION
The water-insoluble organic nonionic detergent has ~. the formula 4~ R~CxH2x)nOH
~ wherein R represents an alkyl or alkenyl group having from .~i 8 to 22 carbon atoms or an alkylated or alkenylated phenol .~ wherein the alkyl or alkenyl group contains from 6 to 12 ;;~
carbon atoms, x is 2 or 3, and n is from 1 to 8.
.
The water-insoluble nonionic .-, .~ . .
I 30 -:;:

~i sB ~
j ~ ~

~r I .......

lOg~i~62 detergents have an HLB (as defined hereinbelow) of less than 10.0, preferably from 7.0 to 9.5. For purposes herein, all 'nonionic detergents having an HLB below 10.0 are considered to be water-insoluble.
The hydrocarbyl~portion of the above-described materials give rise to their lipophilic characteristics, whereas the alkylene oxide portion determines their hydrophilic charac-teristics. The overall hydrophilic-lipophilic characteristics for a given hydrocarbyl-alkylene oxide condensate are reflected in the balance of these two factors, i.e. the hydrophilic-lipophilic balance (HLB). The HLB of the alkoxylated nonionics of this invention are experimentally determined in known fashion or are calculated. They are calculated in the manner set forth in Becker, "Emulsions Theory and Practice", Reinhold Publishing 15 Co., pages.233 and 248. For example, the equation HLB = E/S .
wherein E is the weight percentage of oxyethylene content, is used to calculate the HLB of the normal fatty alcohol ethoxylates ; employed herein.
All manner of hydrocarbyl materials such as branched chain and straight chain alcohols and alkylphenols, primary, secondary and tertiary alcohols, olefinic alcohois and the like having the requisite number of carbon atoms as above discussed are used to prepare the alkoxylated detergents. -The alkoxylated nonionic detergents of the type used herein are prepared by methods well-known in the art.
ln general, the above-described hydrocarbyl material having at least one hydroxyl group is condensed with one or more moles -~
of an alkylene oxide, e.g. ethylene oxide or propylene oxide.
Mixed alkoxylates are formed by condensing the hydrocarbon com-30 pound with mixtures of alkylene oxides. ~-~
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B

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Specific examples of water-insoluble nonionic detergents are found in the succeeding paragraphs.

.
Straight chain, primary alcohol alkoxylates The alkoxylates of n-octanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, and n-eicosanol having from 1 to 8, preferably 3 to 5 alkylene oxide groups, are useful detergents in the context of this invention. The respective ethylene oxide condensates are the most preferred alkoxylates.
Preferred primary alcohol alkoxylates are the ethoxylates of `10C14 20 alcohols with from 1 to 7 ethylene oxide groups, i.e.

.

; R(oc2H4)noH
.
wherein R is from 14 to 20 and n is from 1 to 7. An especially preferred deterqent is the ethoxylated C14 15 alcohol (50:50 mixture) with an averaqe of 4 moles of ethylene oxide, i.e.
1 15 C14 15 ~EO)4. Exemplary alkoxylated primary alcohols are:

; 12( )1;
n-C14(PO)2; and n-C18(EO)3 - ~

: `'. .' '::

....

~ .
. ' . ~
~,h 6 -` 1(~4~962 Stxaight chain, secondary alcohol alkoxyiates . = . ~
The alkoxylates of 3-dodecanol, 2-dodecanol, 4-tridecanol nd 2-hexadecanol having from 1 to 8 alkylene oxide groups are also useful as detergents in the context of this invention.
The respective ethylene oxid~e condensates are the preferred secondary alcohol alkoxylates. Most preferred secondary ~ alcohol ethoxylates are those having from 14 to 20 carbon ; atoms in the alcohol radical and from 1 to 7 ethylene oxide groups. Examples of satisfactory straight chain secondary alcohol alkoxylates are:

12( )l;
2-C14(P0)3; and -C18(EO)6.

Alk~l phenolic alkoxylates .j . .
The alkoxylates of p-hexylphenol, m-octylphenoI, p-octylphenol, p-nonylphenol with an average of 1 to 7 alkylene ox~de groups are useful herein. Examples of such materials are: -~
. ' , .~j p-octylphenol (EO)2; , -p-nonylphenol 5EO)4; and p-octylphenol (E)2(P)2-'`;~ ' ' ~
Preferred alkyl phenolic alkoxylates are those containing from 8 to 12 carbon atoms in the alkyl radical and from 1 to ~ ~-5 ethylene groups.

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

104(~962 Olefinic alkoxylates The alkenyl alcohols, both primary and secondary, and alkenyl phenols corresponding to the saturated compounds immediately hereabove described are alkoxylated to an HLB below 10Ø Typical alkenyl alkoxylates are 2-n-dodecenol (EO)3;

3-n-tetradecenol (E0)4; p-(2-nonenyl)-phenol (EO)~; and 2-tetradecen-4-ol-(EO)2.
Branched chain alko~ylates Branched chain primary and secondary alcohols which are available by the well-known "OXO" process are alkoxylated and used herein. Examples of branched chain alkoxylates are as follows: 2-methyl-1-dodecanol-EO(3); 3-ethyl-2-tetradecanol-EO(2) and 2-methyl-1-tetradecanol-EO(l).
. . .
The foregoing alko~ylates are employed herein as the pure compounds or as mixtures. When prepared on a commercial scale, the alkoxylates are usually not the individual pure compounds listed, but rather comprise mixtures having an average degree of alkoxylation and average lipophilic hydrocarboncchain length corresponding to the ranges herein disclosed.
. .
The electrolyte used in the comppsition of this ~ :
invention is any of several known compounds capable-of dissoci-ating into ions when added to water. Such compounds are ~ -- . .:,.
necessary for ùse with the water-insoluble organic nonionic detergent to obtain proper cleaning performance. It is theorized., that the electrolyte (1) prevents a gel-like phase ~armation when the present compositions are added to water and/or . .
(2) aids in dispersing the water-insoluble non~onic detergent ~ in water- especially at low temperatures. Regardless of the ! mechanism by which the electrolyte aids in the proper per-, i , ' . ' . ~ .
".. . ,,, . , " . .. : . , ,, : -~ . .. ~ .... .... , . : , .

1(~4~2 formance of the nonionic detergent, its presence is necessary. -The electrolyte is needed as well for the role it plays in the physical form of the detergent composition. That is, in solid forms of the present compositions, it provides ~ crystal-5 line structure for the liqùid nonionic detergent to be sorbed -on. The electrolyte also contributes to the prevention of gel formation in the liquid forms of the present compositions.
Suitable electrolytes are selected from the group consisting of the water-soluble alkali~metal and alkaline earth metal phosphates, carbonates, carboxylates, sulfates and chlorides. Examples of salts of this type include sodium tri- `
polyphosphate, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium citrate, sodium propionate, ~ sodium NTA, sodium oleate, potassium chloride, sodium chloride, ;~ 15 sodium sulfate, magnesium sulfate, and trisodium sulfosuccinate.
It should be understood that the abo~e listing is merely illustra-tive and not limiting of the electrolytes that are useful in the context of this invention.
~` The ratio of water-insoluble organic nonionic deter-gent to electrolyte is from 1:15 to 1:2, preferably from 1:9 to 1:4 for a solid type product, e.g. granules and powder and from 100:1 to 3:1, preferably from 75:1 to 6:1 for a liquid product. At least 6% of the composition represents the water-insoluble organic nonionic detergent. Preferably, the amount of water-insoluble organic nonionic detergent ranges from 6% to 30%, most preferably 10% to 20% for a solid type . product and from 30% to 70%, most preferably 40% to 60% for a ;~ liquid product.
.~ :
The grease and oil stain removal ability of the compositions of this invention is superior to that of known ., , _ g _ - . .
`''~

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104~3962 anionic detergent compositions. Additionally, it has been found that the compositions of this invention are superior to deter- ;;
gent compositions 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 at Lower tempèratures in terms of grease and oil stain removal. The reason for effective cleaning performance of the water-insoluble nonionic detergent-containing composi-` tions of this invention is not fully understood. It is theo-rized that at higher temperatures in the washing solution a separate phase containing the water-insoluble nonionic detergent is formed. Above this temperature (which is dependent on the specific water-insoluble detergent) a very distinct phase is observed. It is believed that this very fluid detergent phase lS is responsible for the high stain removal performance. At i 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.
Detergent compositions of this invention may have included therewith water-soluble nonionic detergents provided the HLB of the mixed nonionic detergent system is less than 10.0, preferably from 7.0 to 9.5. The addition of the water-soluble organic nonionic detergent at the above-indicated level does not adverse~y influence the cleaning performance of the detergent composition. Processing and sudsing characteris-tics also are not substantially affected by such minor addi-) tions.
-~ Examples of satisfactory water-soluble nonionic deter-gents are the compounds sold under the trademark of "PLURONIC~.

~ These compound~ are formed by condensing ethylene oxide with .''' , ' ': '.
',"~ ' ~ -4B -lo-~O~C~6;~

a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. Other suitable water-soluble nonionic detergents include the polyethylene oxide condensates of alkyl phenols, e.g. the condensation products of alkyl phenols having an alkyl group containing.~ from about 6 to 12 carbon atoms in either a straight chain or branched configuration, with ethy-lene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
The water-soluble condensation products of aliphatic alcohols having from 8 to 22 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, J e.g. a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms, are also useful nonionic detergents herein. These preferred water-soluble nonionic d-ter~ents have the formula R (OC2H4)mOH

. ~ . .
wherein R' is an alkyl group havin~ from 8 to 22 carbon atoms ~" 20 and m is from 5 to 30.
~ Minor amounts of water-soluble organic anionic ;~ (soap as well as synthetic detergents), ampholytic, or zwit- -terionic detergents can also be included in the compositions of the subject invention. Amounts of such detergents up to 30% based on the total organic detergent system~preferably 15%, most preferably only up to 10% by weight based on the total ethoxylated nonionic present are added without experiencing sudsing problems. The nonionic detergent of the invention , ......................................... .
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11 ~

lQ4~`96;i~
may be sprayed onto a carrier granule comprising inorganic materials. If this is the case, small amounts of anionic detergents facilitate the spray-drying of the otherwise inorganic carrier granule.
Compositions of this invention are formulated in any of several forms, e.g. liquid, powder, granule, or tablets.
Depending on the physical form desired, various additives may be included in the ormulation. Preferred herein are the granule-type detergent compositions intended for heavy-duty laundering. Such compositions generally contain a water-soluble alkaline detergency builder. It should be understood that certain of the above-mentioned electrolytes also possess builder properties. These electrolytes are preferred when the composition is formulated for heavy duty laundry purposes. Such ,15 preferred heavy duty detergent compositions have a level of -~electrolyte within the ranges of 10% to 80~, preferably 20~
to 50%. However, electrolytes not possessing builder proper-ties may be used in heavy duty detergent compositions provided a builder is also included.
- 20 As well-known in the detergency art, builders are included in detergent compositions for sequestering or tieing-` up hardness mineral ions found in water. The builder used in the heavy duty detergent compositions of this invention is ~` any of several well-known and commercially available organic ~ ,~.. . . .
and/or inorganic builder salts. Suitable alkaline, inorganic builder salts include alkali metal carbonates, aluminates, ' ;~' phosphates, tripolyphosphates and silicates. Specific examples u of these salts are sodium or potassium tripolyphosphates, aluminates, carbonates, orthophosphates and hexametaphosphates.
. ., Suitable organic builder salts include the alkali metal, ,~ ammonium and substituted ammonium polyphosphonates, poly-acetates, and polycarboxylates.

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The polyp~osphonates specifically include the sodium and potassium salts of ethylene diphosphonic acid, sodium and potassium salts of ethane-l-hydroxy-l, l-diphosphonic acid and sodium and potassium salts of ethane-1,1,2-triphosphonic acid.
Other examples include thè~water-soluble lsodium, potassium, ammonium and substituted ammonium (substituted ammonium, as used herein, includes mono-, di-, and triethanol ammonium .
cations)~ salts of ethane-2-carboxy-1, l-diphosphonic acid, ~hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1, 1,2-triphosphonic acid, propane-1,1,3,i-tetraphosphonic acid, ' propane-1,1,2-3-tetraphosphonic acid. Examples of these poly-phosphonic compounds are disclosed in British patents 1,026,366, 1,035,913, 1,129,687, 1,136,619 and 1,140,980.
Polyacetate builder salts suitable for use herein include the sodium, potassium lithium, ammonium, and substi-tuted ammonium salts of the following acids; ethylenediamine-, triacetic acid N-(2-hydroxyethyl)-nitrilodiacetic acid, diethyl-`~ enetriaminepentaacetic acid, 1,2-diaminocyclohexanetetraacetic -acid and nitrilotriacetic acid. The trisodium salts of the ~' above acids are generally preferred.
A
The polycarboxylate builder salts suitable for use -herein consist of water-soluble salts of polymeric aliphatic ; polycarboxylic acids as, for example, described in U. S. patent ~-~ 25 3,308,067 to F. L. Diehl, patented March 7, 1967.
' .

Additional detergent builder salts for use in the compositions of the instant invention include the water-soluble salts of: (1) amino polycarboxylates; (2) ether polycarboxy-lates; (3) citric acid; and (4) aromatic polycarboxylates derived from benzene.

"
~ 13 -.. ,i, .

The water-soluble amino-polycarboxylate compounds have the structural formula .

' ~CH2COOM
R - N
C~2COoM
; ' . .
wherein R is selected from:

-CH2COOM; -CH2CH20H; and ~ ` ~ CH2COOM
2 2 ~ . ;
R' wherein R' is 0H; -CH2COOM; or ~ ~ .

. ,~
. ~ and each M is selected from hydrogen and a salt-forming cation.
: , . ` . ! `~

104(3~62 The water-soluble "ether polycarboxylatesn have the formula: .

.
~ 1 ~ .
.

wherein Rl is selected from -C~2COOM; -CH2CH2COOM; and .

~ COOM COOM COOM COOM
, ., C ~ C - ; and -CH - CH - ;

, 10 and R2 is selected from: .
. ~ .
--CH2COOM; --CH2CH2COOM: - CH -- CH2 ~`
`~ , COOM COOM
, . .
~5 ~' ' .

.;~ ~ COOM COOM COOM
- CH ; - C = C - ; and - COOM

.~ CIOOM COOH
-CH - CH - ;
~; .
~!

r, . " ~ ' .
.,j"
~ -- l 5 ~", 104~962 whereby Rl and R2 form a closed ring structure in the event .
said moieties are selected from C~OOM ~ OOM fOOM COOM
- C ~ C ~ ; and -CR - CH - ; and each N is selected from hydrogen and a salt-forming cation.
Specific examples of this class of carboxylate build-ers include the water-soluble salts of oxydiacetic acid having the formula . ~` ! . .
~ CR2COOM
~, 10 o , :, -,.
1 . . I
j~` oxydisuccinic acid having the formula . "

'~ . CtOOM FooM
~` , ~C~I CH2 :'i 15 0 ~ fH CH2 .~"j " ' :' . .~-~, ,.~, ...

,~, .
.~, .
'^" Z~
f,'., ~a - 16 -, 104(~6Z

carboxy methyl oxysuccinic acid having the formula COOM COOM

O ~ ~ C}~2 \ ~
CH2 -~ COOM

. furan tetracarboxylic acid of the formula : ICOOM 700M
-~ C. , C
~ I ..
~ 10 ~C ~ C
-COOM IOOM

, ` . .
- and tetrahydrofuran tetracarboxylic acid having the formula .

CIOOM COOM
~ ~ CH - CH
.,~ 15 ,, o\ I .
CH CH .
COOM ~OOM
$
't :
~, ' ::~-.' ~ .
';
. "~ : :

~ ~ - 17 -.

~09~ 62 The salt-forming cation M can be represented, for example, by alkali metal cations such as potassium, lithium and sodium and also ammonium and ammonium derivatives.
Water-soluble polycarboxylic builder salts derived from citric acid constitute another class of a preferred builder for use herein. Citric acid, also known as 2-hydroxy-propane-1,2,3-tricarboxylic acid, has the formula . . ` ' .

CH2 .COOM
C(OH).COOM
H2.COOM

~ Citric acid while it occurs in 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 composi-tions of this invention, it can be desirable to use the acid ~
and partially neutralized species whereby the neutralizing ~;
. cation is preferably selected from alkali metal ions such as sodium, potassium, lithium and from ammonium and substituted a nium. ~ `
Built heavy duty detergent compositions contain from 10% to 80%, preferably from 20~ to 50%, alkaline , detergency builder.
The detergent compositions of this invention may be formulated by any known method. For example, the water-insoluble nonionic detergent is simply admixed with the electrolyte by spraying thereon or is sorbed onto a carrier , and thereafter admixed with the electrolyte. Other additives ~ .
~ .B~ 18-; -... , , .. :

1(~ 62 may be admixed with the water-insoluble nonionic detergent and electrolyte or included therewith in a spray-drying process.
The built heavy duty compositions of this invention are preferably produced by a spray-drying process. An aqueous slurry of the water-insoluble nonionic detergent elec-trolyte and builder (if the electrolyte does not possess builder properties) is initially formed. Usually the aqueous slurry comprises from 20~ to 45% water with the remainder being ; the nonionic organic detergent, electrolyte, builder and optional components. The temperature of the aqueous slurry ranges from 40C to 100C. Thereafter, the slurry is sprayed into a spray-drying tower. In one method of spray-drying, the source of hot air, i.e. air having a temperature between 100C and 380C 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 tower. The water-laden air exits at the top of the tower.
In another method of spray-drying, the source of hot air is;-introduced`along with the atomized droplets at the same end ; 20 of the tower.
Preferably, the hydrophobic portion of the water-insoluble organic detergent used in such a drying process ~' contains at least 14 carbon atoms, preferably from 14 to 20 , carbon atoms. These compounds are especially useful for -processes wherein stack emission is a concern. Most prefer-~- ably, the primary alcohols containing from 14 to 20 carbon atoms ethoxylated with from 2 to 7 ethylene oxide units are used. Such detergents produce an especially low amount of ~ sudg in the wash solution. Thus, even under European washing .7 :.

.,~' ' -~"
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conditions where typical washing machines are built with high spin rinses (conducive to suds formation), these most preferred compositions do not exhibit objectional sudsing.
It is believed that the water-insolubility of the nonionic 5 detergent necessarily decreases its ability to produce unwante`d suds.
As discussed above, nonionic detergents which are commercially available are actually a mixture of compounds comprising a number of alcohol derivatives having varying 10 alkoxylate content. In addition to there being a wide range of alkylene oxide units present on the alcohol moiety, there is also a certain proportion of unreacted alcohol. The con-ventional designation of a number of alkylene oxide units pres-ent per molecule of alcohol al~oxylate is actually a designa-15 tion of an average number of alkylene oxide units per molecule `
of alcohol, there being proportions of alcohols present that -have a greater number and a lesser number of alkylene oxide units. ~It has been found that stripping of these commercial nonionic detergents to remove the unalkoxylated and low alkoxyl-20 ated compounds results in a mixture which can be better spray-dried in the ordinary manner. Because a stack emission prob-lem can result from spray-drying an aqueous slurry containing certain commercially available nonionic detergents, removal ~ -of the more volatile components from these nonionic detergent 25 mixtures can be desirable. This can be done with the aid of a conventional stripping technique, e.g. as described in U. S.
patent 3,682,849, assigned to Shell Oil Company, patented August 8, 1972.
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1(~4(~;~62 The stripping of the water-insoluble nonionics results in a shift in the alkoxylate distribution to the extent that the unalkoxylated and lower alkoxylated components are removed. Although the lower alkoxylated part of distribution (AOo to AO2) is changed, the majority o~ the distribution remains much the same.
Other detergent composition additives can be in-cluded in the compositions of this invention; for example, brighteners, enzymes, soil-suspending agents, perfumes and bleaches can be included in the subject compositions at known 10 levels. Liquid forms of the compositions of this invention -include from 10% to 60% water and, from 0% to 10% of a lower alcohol, e.g. ethanol. Suds suppressors are also used with certain of the water-insoluble nonionic detergents which are capable of producing copious amounts of suds. The nonionic detergents of the present invention may be combined with other synthetic detergents described in U. S. patent 3,852,211 issued to Ohren, December 3, 1974,` with the latter present within t~e previously stated limits.
suas suppressors are normally used herein in an amount from about 0.01% to about 4% depending upon the nature of a specific suds suppressor. Suitable suds suppressors regulators) for use in the composition of the instant inven-tion include all those which are known to be suitable for use -in detergent technology. Examples of the like suds suppres-sing agents include saturated long chain fatty acids, long chain alkyl phosphates, insoluble organic compounds and the like. Particularly preferred for use herein are silicone sud~
suppressing agents and mixtures of chemically or physically - ~
bound silicones and silica. In more detail the silicone-based ~ -, . ~. :
,''' ' ' ,"' ' .
~ - 21 -;2 Suds controlling agents which are suitable for use in the instant compositions can be represented by:
1) silicones. In industrial practice the term "silicone" has come to be a generic term covering all high molecular weight polymers containing siloxane units and organic groups, in which the siloxane unit -Si-O constitutes the continuing backbone.

The silicones useful in the present invention are high molecular weight linear or cyclic polymers, in which the -Si-O- unit constitutes the continuing backbone, and in which the organic substituents are saturated and unsaturated Cl_4 alkyl radicals, optionally substituted by a hydroxyl group, aryl radicals or mixtures thereof. Preferred are dimethyl, also called polydimethyl siloxanes, and methyl-phenyl, also called polymethylphenyl siloxanes, whereby the molecular weight ratio of the hydrocarbon radical to the atomic weight of the silicon atom varies between 0.5/1 ~ ~ and 6/1, most preferably between 1.8/1 and 2.2/1, having ,~t` a viscosity between 5 and 500,000 centistokes, preferably between 200 and 25,000 centistokes at 25C. The poly-3 siloxanes can contain solid particles consisting of high molecular weight matrixed polysiloxanes.
. ' ~.
The silicones useful herein optionally but preferably con-tain other siliceous material such as finely particulated inorganic silica, for example, in the form of a siliceous aerogel. The addition of up to 20%, preferably, from 3% to 10~, calculated on the wei~ht of the silicone, of sllica or .' .

, , . .. .. . . .. . . .

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silicon dioxide is recommendable to obtain excellent suds controlling results. The particle size of the silicon dioxide is normally below about 25 m~, preferably between 10 and 20 m~; the silicon dioxide in addition preferably has a specific surface area above about 50 m2/g. If desired, the silicon dioxide can be replaced, in whole or in part, by an equivalent amount of a solid oxide having physical characteristics similar to those of silicon d~ox-ide. Examples of the like solid oxides include dioxide and alumina.

2) silicone-silica compounds. The silicone-silica compounds ` useful in the present invention consist of silicones to ! ` which finely divided inorganic silica or silicon dioxide is bound chemically; thus the polymeric silicone consists of a continuing backbone of siloxane units which is inter-rupted by silicon dioxide particles, as for example described in U. S. patent 3,388,073. The weight ratio of silicone to silica in this chemically-bound silicone-~` silica suds regulating agent can vary between about 99:1 to about 70:30, preferably from about 94:6 to about 75:25.
Highly preferred for use in the compositions herein is a - , `~; chemically-bound silicone-silica compound having a weight ~ j ` ratio of silicone to silica from about 88:12 to about 80:20. `-. . `' 3) silanated silica. Silanated silica useful in the present 3 ~
invention can be made by reacting a silica, produced, for !'' ` '-'' example, by vapor-phase hydrolysis of silicon tetrachloride, ~ ~
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with, for instance, dimethyl dichlorosilane, or by physically affixing silica to a polysilicone as described .
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~C~ - 23 -1(~4(~62 in U.S. Patent 3,207,698.

The silanated silica to be used in the present invention preferably has a median particle size of from 10 m~ to 1~ , and a specific surface~area above 50 m /g. The very pre-ferred silanated silica has a median particle size between 10 and 50 m~, and a specific surface area above 100 m2/g.
Preferably the 1% by wt~ s~spension of the silanated silica in a 1:1 water-isopropyl alcohol mixture has a pH above about 7.

Preferred siliceous suds controlling agents are 3:1 to 1:2 mixtures by weight of silicones, preferably dimethyl- and methylphenyl silicones as defined under 1) and 2) herein-above having a viscosity of about 1,000 to about 5,000 centistokes at 25C and containing about 3% to 5% of finely divided silica, and silanated silica, as defined ~ ~under 3) hereinabove, preferably having a median particle -~
; size of 10 - 25 microns, and a specific surface area above -: .- ~.
200 m /g.
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`~ The silicones and mixtures thereof as described in the above are normally used in the compositions of this inven-tion in an amount from about 0.01% to 1.0%, preferably from about 0.05% to about 0.3%.
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~ The terminology "polysiloxane" and silicone" is used -,~ interchangeably and accordingly represents identical ~-materials.

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` : 104~'962 The compositions of this lnvention are used in a conventional laundering process. Thus, about 30 to 200 grams of the composition is added to the washing machine as well as the soiled laundry and from 15 liters to 80 liters of S water. The temperature of the washing process can vary from 20C to ~5C. However, especially good stain removal perform-ance from the compositions of this invention is observed at a ~emperature above which phase separation occurs and, for this reason, it is preferred that such a temperature be employed.
lQ The following examples are illustrative of this lnvention.

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104~6~
EXAMPLE I
The following detergent compositions are tested:

C alcohol ethoxylated with an 12 . ~%
av4erage of 7 moles of ethylene oxide (50:50 mixture of C14 and`C15 ethoxy-lated alcohols) C12 alcohol ethoxylated with an -3.7% 8.3%
average of 4 moles of ethylene oxide C14 alcohol ethoxylated with an -8.3% 3.7%
average of 4 moles of ethylene oxide Sodium tripolyphosphate 30.2~30.2h 30. 2%
Sodium silicate (SiO2:Na2) = 2.0)6.6%6.6% 6.6%
Sodium sulfate 18.3%18.3% 18.3%
Sodium carboxymethyl cellulose0.9% 0.9% 0.9%
Sodium ethylene diamine tetraacetate 0.2% 0.2% 0.2%
` Sodium perborate 22.0% 22,0% 22.~/o .
~ Proteolytic enzyme ~MAXATASE CP*)0.6% 0.6% 0.6%
;~ Water 7 ~% 7.~/o 7.0%
Miscellaneous (brightener, perfume,etc.) bal. - -100.0% 100.0% ~0~0%

The nonionic detergents, æodium perborate and enzyme ~
; are dry admixed with the remainder of the composition which - -has been prepared by spray-drying.
The HLB's of the nonionic detergents contained in Compositions A, B and C are 11.6, 10.3, and 9.7, respectively. -~! Thus, Composition.C is illustrative of the present invention.
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Each individual composition is tested under the same conditions. Thus, cotton fabrics are individually stained with a variety of greasy sta;ns; namely, spaghetti sauce, dirty motor oil, and cosmetics. These stained fabrics are added to naturally stained fabrics to make up a total washing load of 4 kilograms.
The fabrics are washed for 19 minutes with 120 grams of the detergent composition in 22 liters of water ~hardness 2 17.0 grains) having a maximum temper~ture of 39C. The same amount of detergent composition and water are used in the mainwash with a washing time of S5 minutes and 85C. water. The fabrics are rinsed a total of 5 times after ~ompletion of the washing cycles.
At the end of the last rinse, the fabrics are dried and visually graded for grease and oil removal. Using a scale of 0-5 (0 for no stain removal and 5 for complete stain removal~, the following results are obtained: `
5 , .
Composition A B C
~; Stain Removal 2.88 3.01 3.44 The least significant value at the 95% confidence level is 0.33 (LSDo5 ~ 0~33)~ - -These results indicate that the compesition of this invention, i.e. Composition C, significantly removes a greater amount of grease and oil stains than compositions outside the . . ,- .
scope of this invention, i.e. compositions A and B.

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104~3~62 EXAMPLE II
Example I is repeated using the same test procedure : and base detergent compositions except for the substitution at an equal level of nonionic detergents as indicated below for those contained in the compositions of Example I. The stains used for this test are dirty motor oil, cosmetics, and ball-point pen ink.

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Stain removal Composition A (6% 50:50 mixture 14 C alcohols ethoxylated with an avera~e of 7 moles of ethylene oxide, C 4-1 (E0) , and ~ 6% of the same alloho~s ethoxylated ; with an average of 4 moles ethylene 14-15(E)4~ ~r,R = 10.3) 3 44 Composition B (3.6% C (E0) 3.69 and 8-4% C14 15 (E)414 ~ = 9-~) .
: Composition C (12% C14_15 4 4.27 ,J . 20 The LsDo5 = 0-24 ~ The above results show the superior grease and .~ oil stain removal of the compositions of this invention ;, (Compositions B and C) compared to Composition A.
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1()4(~962 EXAMPLE III
A detergent composition having the follow~ng formula is made by a spray-drying process:

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Mixture o~ 50% C14, 30% C16. and 18.0%
20% C alcohols ethoxylated with ; an ave~age of 4 moles of ethylene oxide (HLB = 8.6) Sodium linear alkyl (C12) benzene 1.0%
` ~ulfonate , `~ 10 Sodium carbonate 20.0%
Calcium carbonate (0.01 to 0.255.0%
, microns crystallization seeds) Sodium silicate (SiO2:Na2O = 2.0) 7.0%
Sodium sulfate 35.0%
i 15 Sodium toluene sulfonate 1.0%
Water 11.0%
Miscellaneous ~brightener, etc.) balance .'~ .
~-Objectionable stack emissions are not observed during the spray-drying process~ The resultant spray-dried .20 granules clean well with a minimum of suds production.

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` 104(~62 EXAMPLE IV
A liquid detergent composition has the following formula:

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. 2-dodecanol ethoxylated with an average 40%
` of 3 moles of ethylene oxide ~HLB=8.3) `
Sodium acetate 25 Water 30~
Miscellaneous (brightener, perfume, dye) S%
100%
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;This composition provides excellent grease and oil stain .i~removal when used under hand wash or machine wash conditions.

.~ 10EXAMPLE V
A detergent composition produced by dry admixing ~:
all the ingredients has the following formula: `

~ ' '~ Nonyl phenol ethoxylated with an average 6%
of 4 moles of ethylene oxide (HLB=8.9) Sodium tripolyphosphate 60%
Sodium silicate (SiO2:Na2O = 2.0 9%
Sodium carboxymethyl cellulose 1%
Sodium sulfate 17~
:"~, . . Water 5%
Niscellaneous (perfume, dye, etc.) 2%
;~J . 3 0 100%

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``` 104(39~2 This composition cleans well with respect to grease and oil stain removal at all temperatures, especially at 45C, ~, ~
EXAMPLE VI
A water-insoluble nonionic detergent (being a 50:50 1 mixture of C14 and C15 alcohols ethoxylated with an average of 4 moles of ethylene oxide) has an ~LB = 8.9. When this material is stripped by 10% using conventional stripping equipment, a material results which has an HLB of 9.7. A
substantial part of the unethoxylated and monoethoxylated alcohols are removed. An aqueous detergent composition slurry containing the stripped nonionic detergent is spray-dried to produce a granular product having the formula in Example I (with the necessary substitution of nonionic detergents). Such a granular product is especially free ~i of a stack emission problem during its production, yet ~;
still shows excellent ability to remove grease and oil stains ~n a washing solution.
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Claims (21)

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

1. A detergent composition especially adapted for removal of grease and oil stains consisting essentially of (a) from 6% to 70% of a water-insoluble organic nonionic detergent having the formula R(OCxH2x)nOH
wherein R represents an alkyl or alkenyl group having from 8 to 22 carbon atoms or an alkylated or alkenylated phenyl group having from 6 to 12 carbon atoms in the alkyl or alkenyl group, x is 2 or 3 and n ranges from 1 to 8, and having an HLB of less than 10.0;
(b) a water-soluble electrolyte selected from the group consisting of alkali metal and alkaline earth metal phosphates, carbonates, carboxylates, sulfates and chlorides, in an amount sufficient to aid in the action of the water-insoluble nonionic detergent, the ratio of said water-insoluble nonionic detergent to said electrolyte being in the range of 100:1 to 1:15; and (c) from about 0% to about 30% anionic, zwitter-ionic or ampholytic detergent based on the weight of the total organic detergent system.

2. The detergent composition of claim 1, wherein the detergent composition is in the form of a solid and the water-insoluble organic nonionic detergent represents from about 6% to about 30% of the composition and the ratio of said detergent to electrolyte is from about 1:15 to about 1:2.

3. The detergent composition of claim 2, containing from about 10% to about 80% of an alkaline detergency builder.

4. The detergent composition of claim 2, wherein the electrolyte is a sequestering builder.

5. The detergent composition of claim 4, wherein the electrolyte represents from about 10% to about 80% of the composition.

6. The detergent composition of claim 5, wherein the water-insoluble organic nonionic detergent is R(OC2H4)nOH
wherein R is an alkyl group containing from 14 to 20 carbon atoms and n ranges from 1 to 7.

7. The detergent composition of claim 6, wherein the ratio of water-insoluble organic nonionic detergent to electrolyte is from about 1:9 to about 1:4.

8. The detergent composition of claim 7, wherein the water-insoluble organic nonionic detergent is present in the detergent composition at a level of from about 10% to about 20%.

9. The detergent composition of claim 8, wherein the HLB of the water-insoluble organic nonionic detergent is from 7.0 to 9.5.

10. The detergent composition of claim 9, in the form of spray-dried granules.

11. The detergent composition of claim 10, wherein the water-insoluble organic nonionic detergent is a mixture of alkoxylated C14 and C15 alcohols having an average of four ethylene oxide groups.

12. The detergent composition of claim 11, wherein the electrolyte is sodium tripolyphosphate.

13. The detergent composition of claim 2, addition-ally containing a water-soluble organic detergent in an amount such that the HLB of the mixed nonionic detergents is less than 10Ø

14. The detergent composition of claim 13, wherein the water-soluble organic nonionic detergent has the formula R'(OC2H4)mOH
wherein R' is an alkyl group having from 8 to 22 carbon atoms and m is from 5 to 30.

15. The detergent composition of claim 14, addition-ally containing up to about 15%, based on the weight of component (a), of a water-soluble organic anionic, ampholytic or zwitterionic detergent.

16. The detergent composition of claim 15, in the form of spray-dried granules.

17. The detergent composition of claim 1, wherein the detergent composition is in the form of a liquid and the water-insoluble organic nonionic detergent represents from about 30% to about 70% of the composition and the ratio of said detergent is from 100:1 to 3:1.

18. The detergent composition of claim 17, addition-ally containing from about 10% to about 60% water.

19. The detergent composition of claim 1, which, in addition, contains from about 0.01% to about 1% by weight of a silicone suds suppressing agent.

20. The detergent composition of claim 19, wherein said suds suppressing agent is selected from the group con-sisting of (a) a polysiloxane, having a viscosity in the range of from 200 to 25,000 centistokes at 25°C;
(b) a polysiloxane-silica mixture containing from 3% to 10% by weight calculated on the mixture of said poly-siloxane and said silica, of finely particulated silica;
(c) a chemically bound silicone-silica compound having a weight ratio of silicone to silica from 99:1 to 70:30;
(d) a mixture of polysiloxane as defined in (a) and (b) and silanated silica; and (e) mixtures thereof.

21. The detergent composition of claim 20, wherein said suds suppressing agent is a chemically bound silicone-silica compound having a weight ratio of silicone to silica in the range from about 88:12 to about 80:20 and which is used in an amount from about 0.05% to about 0.3% by weight.