CA1086178A - Liquid detergent composition - Google Patents

Abstract

LIQUID DETERGENT COMPOSITION

Jose Luis Arnau Christian Roland Barrat Jean Wevers ABSTRACT OF THE DISCLOSURE
The present invention relates to liquid, concentrated, homogeneous, stable, heavy duty detergent compositions. Such compositions contain a polyethoxylated nonionic detergent compound, a minor amount of a polyacid having at least one pK value of at least 5.0, and a liquid carrier, whereby the pH of the liquid composition has a pH in the range between 6.0 and 7.5. The compositions can also contain mixtures of polyethoxylated nonionic detergent compounds, additional amounts of synthetic, anionic detergent compounds, minor amounts of brighteners, suds-regulating and pH-regulating agents, perfumes, dyes and other usual liquid detergent compound additives. Such compositions show enhanced cleaning performance, particularly on bleach-sensitive stains, and have excelled stability on storage.

Description

l7~
i Field of the Invention The present invention relates to liquid, concentrated, homogeneous, stable, heavy duty de~ergen-t compositions.
Description of the Art To be satisfactory for washing or pre-treating and subsequent washing of heavily soiled abri~s, in particular cotton fabrics, liquid detergent compositions must contain ; an adequate concentration of detergent compounds. In addition, they must remain stable and homogeneous when subjected to various storage conditions and be designed for use in both horizontal ttumble drum type) and upright (vertical agitator type) washing machines and for topical application as well as for handwashing.
Liquid, heavy duty detergent compositions containing a synthetic organic detergent compound, which is generally anionic, nonionic or mixed anionic-nonionic in nature; an inorganic builder salt; and a solvent, are disclosed, for ; example, in US patents 2,551,634; 1,908,651;2,920,045;
~ 2,947,702; 3~239~468; 3,272,753; 3,393,154; 3,554,916; 3,697,451;
3,709,838; Belgian patents 613,165; 665,532; 794,713 and 817,267; British patents 759,877; 842,813. These compositions j .
frequently contain a hydrotrope or solubilizing agent to permit the addition of sufficient quantities of surfactants and usual builder salts to provide a reasonable volume usage/per-formance ratio. Others are substantially anhydrous liquid compositions containing an alkanolamine component (US patent 3,528,925). Still others contain a soap component (US pa~ents

2,875,153 and 2,543,744). -~, .

6~7Ei As can be seen from the foregoing, a substantial effort has been expended in developing built and builder-free detergent compositions in liquid form. Yet, there are several problems associated with the art-disclosed compositions which render them less optimal for wide scale use, undesirable Erom an ecological standpoint in improperly treated sewage, objec tionable from a performance point of view in cleaning bo~h natural and synthetic fibers and subject to instability under severe storage conditions.
It haslnow been found that superior detergency, in particular with respect to bleach-sensitive stains, is obtained if a mixture of a major amount of soluble ethoxylated nonionic surfactant and a minor amount of a p~lyacid having at least one pK value of at least 5~0 is combined in a liquid vehicle or carrier, whereby the p~ of the detergent composition is in the .
range of from 6.0 to 7.5.
It has also been found that liquid, concentrated, heavy duty detergent compositions containing a mixture of a major amount of the soluble ethoxylated nonionic surfactant . .`
and a minor amount of the polyacids, having a pH in the range of from 6.0 to 7.5, exhibit superior removal of bleach-sensitive stains by topical application and through-the-wash fabric cleaning.
In addition, it has been found that these liquid, concentrated, heavy duty detergent compositions exhibit good physical properties, remain homogeneous and stable under severe storage conditions and stand the addition of màny usual adju vantsO
It is, therefore, an object of this invention to provide liquid, concentrated, heavy duty detergent compositions which exhibit excellent cleaning and superior removal of bleach-sensitive stains by topical application and through-the-wash fabric cleaning.
It is another object herein to provide li~uid, con-centrated, heavy duty detergent compositions which remain stable and homogeneous under severe storage conditions.
It is still another objec~ herein to pxovide liquid, concentrated, homogeneous, stable, heavy du-ty detergent composi-tions acceptable from an ecological standpoint.

These and otller objects are obtained here:Ln, as will be seen Erom the followin~ disclosure.

5~RY OF THE INVENTION

The present invention encompasses a liquid, concentrated, homogeneous, stable, heavy duty detergent composition containing:

~: ~ (l) from about 20~ to about 70% by weight of a soluble ethoxylated nonionic surfactant;
'~

(2) from 0.10% to 1.25%.by weight of a polyacid having at least one pK
value of at least 5.0;

(3~ balance: liquid carrier;

the pH of ~he detergent composition being between 6.0 and 7.5.

In a preferred composition aspect, the liquid composition comprises a surfactant mixture containing different soluble ethoxylated nonionic surEactants and optionally but preferably synthetic anionic surfactants j 15 in amount up to 50% by weight cal.culated on the total nonionic sur~
: factant and synthetic anionic surEactant content.
. '' .
In another preferred embodi~.ent, the concentration of polyacid is between 0.25% and about l.O~ by ~elght.
;

In another preEerred embodiment, the pH of the composition is m the ~' 20 range between 6.0 and 7Ø
'~ ' .

., 4 ~86~

In still another preferred en~odiment, the polyacid has at least one pK value of at least 5.0 and preferably equal or above x-l, wherein x represents the pH of the liquid compo-sition.

DETAILED DESCRIPTION OF THE INVENTION
The properties of the compositions of the present invention are the result of a combination of different compo~
nents and factors which have to be properly selected and correlated as described in detail below.
The Ethoxylated ~onionic Surfactant The instant compositions contain as an essential component soluble ethoxylated nonionic surfactant.
Ethoxylated nonionic surfactants can be prepared by a variety of methods well known in the art. In general terms, such nonionic compounds are conventionally produced by condensing ethylene oxide, forming the hydrophilic moiety or ethenoxy chain, with a hydrocarbon having a reactive hydrogen atom, e.g., a hydrox~l-, carboxyl- or amino group, and forming the hydrophobic moiety, in the presence of acidic or basic catalysts. Such procedures result in the production o a product mixture comprising a number of nonionics of vary-ing ethoxylate content. Therefore, the conventional designation o the number of ethylene oxide units "m" present per molecule of nonionic compound as designated~ for example, in the general formula R-A(CEI2CEI2O)~IH, wherein R represents the hydrophobic moiety and A the group carrying the reactive hydrogen atom, is an indication of the average number of ethylene oxide units ; per molecule of nonionic compound according to a statistic ~ ;
distribution where the peak is situated around the "m" number.
` i ~ .

' ~, ~ ; .
_ 5 -.

.

6~7~

The properties of the ethoxylated nonionics depend to a considerable extent on the hydr~philic moiety or average number of ethylene oxide units present. Most commercially available ethoxylated nonionics are viscous liquids or soft pastes having in general from about ~ to about 20 to 24 ethylene oxide units in average.
The soluble ethoxylated nonionic surfactants useful in the compositions of the present invention include those compounds which are obtained by reacting an alcohol with ethylene oxide and which are soluble in the instant liquid compositions.
Ethoxylated nonionic compounds have a negative temperature coefficient of solubility in water, becoming less soluble at higher temperatures. Therefore, soluble in the instant liquid compositions means soluble at temperatures below about 35C.
Usually, the ethoxylated nonionic surfactants are considered to include only those compounds which are soluble in water. There is a large number of ethoxylated nonionic j compounds having detersive properties but which do not have i, enough hydrophilic character to be fully soluble in water but are dispersible in water. They can be solubilized in water, however, with the help of solubilizing agents such as lower aliphatic alcohols, by admixing highly soluble ethoxylated nonionic compounds or by hydrotropeis. Therefore, soluble in the instant liquid compositions means soluble per se in water or soluble in the instant liquid composition.

' . ~

.

~L01~ 78 i The hydrophobic moiety of the soluble ethoxylated nonionic surfactants useful in the composition of the present invention can be derived from primary and secondary, straight or branched, saturated or unsaturated aliphatic alcohols having from about 8 to about 24, preferably rom about 12 to about 20 carbon atoms. Another source is the alkylphenols wherein the alk~l group on groups have Erom 1 to a~out 12 carbon atoms, wherein at least one group has at least 6 carbon atoms and the total number of carbon atoms in the alkyl groups is at most about 15.
Primary alcohols can be derived from animal and vegetable oils and fats by, for example, hydrogenolysis of said oils,fats or corresponding fatty acids. They are sub-stantially straight-chain or linear alcohols.
Primary alcohols can also be obtained from synthetic sources by different processes. The usual raw materials are polymers of lower alkylenes or olefins. According to the type of polymers, olefins, processes and process conditions, alco-hols with a different degree of linearity or branching are obtained. The major part of the commercially available primary synthetic alcohols are prepared by either the "oXO"
or "Ziegler" process.
Secondary alcohols are mostly obtained from synthetic ; sources, e.g., from olefins, either by direct hydration at high temperatures and pressures or hydrolysis of thè intermediate sulfuric acid product; by oxidation of paraffins, etc.
:, . :

.
~, ~ - 7 - ~
: :`

6~71~

Alkylphenols are obtained by reacting a phenol with an olefin thermally preferably in the presence of a catalyst, e.g., boron trifluoride. Xylenol and cresol can also be used instead of phenol.
Preferred for the compositions of the present invention are soluble ethoxylated nonionic surfactants derived from primary and secondary aliphatic alcohols.
The hydrophilic moiety of thenonionic compounds useful in the composition of th~ present invention is an ethenoxy chain consisting of from 2 to about 24 e~hylene oxide units in average, ; depending upon hydrophobic character of the hydrocarbon group.
Preferred are those ethenoxy chains containing at least about " 4 ethylene oxide units.
; Suitable examples of soluble ethoxylated nonionic surfactants can, for example, be prepared from aliphatic primary alcohols containing from 12 to 20 carbon atoms condensed with from about 4 moles to about 14 moles of ethylene oxide per mole of alcohol and mixtures thereof. Non-limiting, specific examples of soluble ethoxylated nonionic surfactants derived from straigh~ chain primary aliphatic alcohols are:

12 25 (C2H4O) 6 H; C16H33__ (C2H4O) 9-H; C18H35__ (C2H4O) -H;
C H -O- ~C2H40) g-Hi C14H29-- tC2H4~) 9 H; C12 25 2 4 9 12 25 (C2H4~ 4 H; C16H33-- (C2H4~) 9-EI; tallow-O-(C2H4o)ll_H;

CllH23 (C2H4)4 H; C16H33-O(C2H4O)7-H; and mixtures thereof.
~, Non-limiting,specific examples of soluble ethoxylated nonionic surfactants derived from secondary aliphatic alcohols are:
12 25 4 9 ( 2 4 )9 ; 8 17 (C4 9) O (C2H4) 12 H;

7 15) 2CH (C2H4) 6-H; C17H35CH (CH3)--O- (C2H40) -H;
C H gCH ( C3H7 )--O--( C2H40) 9 H; Cl4 29 3 2 4 ; 30 and mixtures thereof. Non-limiting,specific examples of ~ .
' ~ ' :, s , , , : . .

l7~

soluble ethoxylated nonionic surfactants derived from branched primary aliphatic alcohols are: CloH21CH(CH3)CH2-0-(C2H40)9-H; C12H25-CH(CH3)CH -0-(C H 0) H; C H CH(CH )CH -0-(C H40)9-H; C13~27CH(CH3)CH2 CH2 C 2 2 4 9 C H CH(C2H5) CH2-0-(C2H40)9-H; (C7H15)2 2 2 4 12 9 19 8 17) 2 (C2H40)12-H; C13}I27CH(C4Hg)CH2-0-(C H 0) -~;

13 27 ( 3 7) 2 2 ~C2H40)9 H, and mixtures thereof.
Non-limiting,specific examples of soluble ethoxylated nonionic surfactants derived from alkylphenols are CgHlgC6H4~0~(C2H40)9-H;
10 C H C6H4-O-(c2H40)l2-H; (C9Hl9)(CH3)C6 3 2 4 12 12 25 3)2 6H2 (C2H40)11-H; C12H25C6H4-0-(C H o) -H;
and mixtures thereof. Non-limiting,specific examples of mixtures of soluble ethoxylated nonionic surfactants consisting -of slightly water-soluble and highly water-soluble compounds useful in the compositions of the present invention are: 1/2 mixture ~f C12H25-0-(C2H40)5-H and C12 25 2 4 12 1/1 mixture of C14H29~0-(C2H40)5-H and tallow-0-(C2H40)11-H;

2/1 miXture f C15H31-0-(C2H40)7-H an~ tall~w-o-(c2~4o)ll-H;

ClOH21 (C2H4)3-H and C13~I27CH(CH )CH -0-(C H 0) -H; 1/1/1 mixture of C8H17CH(C6H13) (C2 4 )6 Cl2H25cH(cH3)cH2-o-(c2H4o)4 and C18 37 2 4 15 ; mixture of CgHlgC~H4-O-(c2H40)g H; ClsH31 ( 2 4 5 ;~ Cl8H37-o-(c2H4o)l2-H; 2/1/1 mixture of (CH3)3C(CH2)8CH2-0-2 4 3 16 33CH~CH3)CH2-0-(C2H40~ll-H and C14H29CH(CH )~~
(C2H40)9-H (all ratios being by weight).

.

_ 9 _ `, 6~7~

A part:icularly pre~crrcd soluble ethoxylated nonion:ic surfactant ls represented by a m:ixture o[: (1) a primary al:Lphatic alcohol ethoxylate obtained fron~ an alcollol, the hydrocarby:L cha:in of which contains at least 65% branched-chaln structure and is obtained by hydro-formylation of random olefins and has from about 14 to about 22, especially from 16 to 19 carbon atoms in the hydrocarbyl chain, and 8 to 14 ~oles of ethylene oxide; and (2) an alcohol ethoxylate derived from a primary alcohol with preferably 40% branched-chain structure . and havin~ from 9 to 15~ especially from 12 to 15 carbon atoms in the 10 hydrocarbyl chain, and 3 ~o 7 moles of ethylene oxide.
., .
.

: I

.,, . . ., ..
.
., . ' .'.
' ,~' ~ - 9a -: ` :

... . . :
, 16~8 Adjunct Sur~actants The compositions herein can optionally contain various other adjunct surfactants, which can be used to perform specific cleaning, grease-emulsifying and suds-modifying functions.
Such optional adjunct surfac~ants include synthetic anionic surfactants of the sulfonate and/or sulfate type, semipolar surfactactive agents and fatty acid al~anol-a~ides known in the art.
Synthetic anionic surfactants of the sulfonate type useful herein include paraffin sulfonic acid and olefin sulfonic acid having from 6 to about 20 carbon atoms in the hydrocarbon group; alkylbenzene sulfonic acids having from 8 to about 15 carbon atoms in the alkyl group; mixtures thereof; and their water-soluble salts.
The preferred synthetic anionic surfactant component ~-~ useful in the instant detergent compositions is a water-soluble -i salt of an alkyl-benzene sulfonic acid, preferably an alkanol amine alkylbenzene sulfonate, having from about 12 to about 15 carbon atoms in the alkyl group. More specifically, the most preferred synthetic anionic surfactant herein consists of a mono-, di- or triethylamine salt of a straight chain alkylbenzene sulfonic acid in which the alkyl group contains in average about 12 carbon atoms. ~`
5pecific examples of alkylbenzene sulfonic acids and of the corresponding alkanolamine salts useful in the instant invention include decylbenzene sulfonic acid and triethanolamine -' decylbenzene sulfonate, triethanolamine dodecyl benzene ' sulfonate, diethanolamine undecyl benzene sulfonate, ;
tridecylbenzene sulfonic acid and monoethanolamine tridecyl- ~ -benzene sulfonate, triethanolamine tetradecylbenzene sulfonate-and tetradecylbenzene sulfonic acid, and mixtures thereof.
` Said mixtures of acids and salts can, if necessary, be adjusted to regulate the pH of the compositions.

l78 A partlcularl.y pre~erred surEactant mixture for use in the composltions of thls invention compr.ises a solub:le nonlonic surfactant whlch ls a mixture of: (1) a primary al:iphatic alcohol ethoxyla~e wherein the hydrocarbyl chain contains at least 65% branched chaln structure and has from about 14 to about 22, especially from 16 to 19, carbon atoms and containing 8 to 14 moles of ethylene oxide; and (2) an alcohol ethoxylate derived from a primary alcohol with preferably 40% branched-chain structure and havi.ng from 9 to 15, especiall.y from 12 to 15 carbon atoms in the hydrocarbyl chain 9 and 3 to 7 moles of ethylene oxide; and a synthetic anionic surfactant which is an ethanolamine alkylbenzene sulfonate having from about 9 to about 15 carbon atoms : in the alkyl chain.
' , :, ~' ' .~ ' . .

."
.1 . . . , -':
, ~L~86~7~

S The concentration of the adjunct synthetic anionlc surfactant of the sulfonate type useful in the instant compo-sition should be below 50~ by weight, preferably below 20~ by weight, calculated on the total amount of soluble ethoxylated nonionic surfactant and synthetic anionic surfactant taken to~ether.
Semi-polar surfactants useful herein include water-soluble amine oxides containing one alkyl moiety of from about 10 to 24 carbon atoms and two moieties selected ~rom the 10 group consisting of alkyl moieties and hydroxyalkyL moieties containing from 1 to about 3 carbon atoms. Specific examples of semi-polar surfactants are: dodecyldimethylamine oxide;
dodecyldiethylamine oxide; tetradecyldi(hydroxyethyl)amine . oxide; and mixtures thereof.
Alkyl sulfates useful herein are the water-soluble salts, in particular the ethanolamine salts of sulfated higher alcohols especially those ~btained by sulfating fatty alcohols containing from about 10 to 18 carbon atoms. Ethoxylated alkyl sulfates useful herein are the water-soluble salts, 20 preferably the ethanolamine salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol, e.g., tallow or coconut alcohols, most preferably lauryl, myristyl or palmityl alcohols, and 1 to about 15, preferably from about 1 to about 6 moles of ethylene oxide per mole of fatty alcohol.
.'.
. . . .
, .:
, ':
'~

~ - lla -~L0~

The concentration of the adjunct surfactants of the semi-polar type and the sulfate, incl~ding ethoxylated sulfate, type in the instant compositions can be up to 50% by weight ; calculated on the total amount of soluble ethoxylated nonionic and anionic surfactant compounds taken together. In certain compositions it may be desirable to incorporate below 10~, preferably below 5% by weight, calculated on the amounts of soluble ethoxylated nonionic surfactants, of these semi-polar, sulfate and ethoxylated sulfate types of adjunct surfactants.
10When adjunct surfactants are present in the composi-tions of this invention, the total amount of surfactant should not be more than 70% by weight of the total composition.
The Pol~acids The second essential component of the compositions of the present invention is a polyacid having at least one pK
value of 5.0 or higher.
An acid can be defined as a compound capable of accepting a pair of electrons to form a co-ordinate bond (G.N. Lewis definition), or as a compound furnishing a proton (Bronsted-Lowry definition), or simply as a hydrogen-containing substance which dissociates on solution in water producing one or more hydrogen ions~
Acids can be classified as monobasic, dibasic, tribasic, etc.,according to the number of hydrogen atoms contained in the compound, replaceable by bases or dissociable in water.

' :.

~ - 12 -`: ;

.: .

6~7~

AS acids dissociate on solution in water, they can be characterized by-~eir dissociation constant (~Jhich is to a certain degree depelldent upon the temperature of the solution medium or water). The practical dissociation constant, usually indi-~t cated as and represented by the symbol pK, is e~pressed as the negative logarlthm of the dissociation constant. Dibasic, tri-basic acids produce 2, respectively 3 protons on solution in water; hence, they can be characterized by their 2, respectively

3 pK values. Generally, said pK values are de-fined at ambient temperatures, i.e., 10-30C; but, since the changes in pK
values for a given acid hardly differ if measured either at 10 or 30C, the temperature at which the pK's are measured are of minor importance with respect to the present invention, . ., provided they are within said range of about 10 to about 30C.
; Thus, the second essential component of the composi- ~
tions of the present invention is a polyacid having at least ~;
one pK value of 5.0 or higher, if measured at a temperature within the range of from about 10 to about 30C.
~ The polyacids useful in the present invention can j; 20 be either organic, i.e~, containing carbon atoms in the molecule and having preferably a -COOH group as proton donor, or inorganic. Speoific non-limiting examples of '`

- 12a -, ~8~71~

useful polyacids having at least one pK value of 5.0 or higher are (between braekets the temperatures at whieh the dissoeia-tion constants are measured); see for example) Handbook of Chemistry and Physics, published by the Chemical Rubber Publish-ing Co., Cleveland, Ohio, 50th Edition, pp. 1753, etc.):

ascorbic acid~ pK: 4.10 and 11.79 (24, 16C);
aspar'cie aeidr pK: 3.86 and 9.82 (25C);
: eitric acid, pK: 3.08, 4.74 and 5.40 (18C);
eyelohexane-l,l-diearboxylie aeid, pK: 3.45 and 6.11 (25C);
eyelopropane~ diearboxylie aeid, pK: 1.82 and 7.43 (25C);
dimethylmalic aeid, pK: 3.17 and 6.06 (25C);
diglyeollie aeid, pK:3.4 and 5.11;
glutarie aeid, pK: 4.34 and 5.41 (25C);
o-hydroxybenzoie aeid, pK: 2.97 and 13.40 (19, 13C);
m-hydroxybenzoie aeid, pK: 4.06 and 9.92 (19C);
p-hydroxybenzoie aeid, pK: 4.48 and 9.32 (19C);
. itaeonie aeid, pK 3.85 and 5~45 (25C);

Lq8 ,, maleic acid, pK: 1.83 and 6.07 (25C);
malic acid, pK: 3.40 and 5.11 (2~C);
methylsuccinic acid, pK: 4.13 and 5.64 (25C);
o-phthalic acid, pK: 2.89 and 5.51 (25C);
succinic acid, pK: 4.16 and 5.61 (25C);
o-phosphoric acid, pK: 2.12, 7~21 and 12.67 (25C, 25C, 18C);
pyrophosphoric acid, pK: 0.85, 1.49, 5.77 and 8.22 (25C);
Na2H2P20~, pK: 0.86, 1.96, 6.68 and 9.39 (25C);
nitrilotriacetic acid, pK: 3.03, 3.07 and 10.7 (25C);
ethylene diamine tetraacetic acid, pK: 2.0, 2.7, 6.2 and 10.3;
ethylenediaminotetramethylenephosphonic acid, pK: -, -, 3, 5.2, 6.5, 8.1, 10.2 and 12.0 (25C).
and mixtures thereaf.
Preferred are polyacids whereby at least one pK value is at least 5.5 or, with reference to the pH of th~ compositions, have at least one pK value which is equal to or above x-l wherein x represents the pH of the liquid composition, thus whereby for a composition having a pH of 6.8, has a pK value of at least 6.8 - 1 = 5.8 or hi~her.

.
'.

;'' ' ~:' :

,1 ~ 14 -:
7i~
.., Most preferred polyacids are those having at least two pK values o~ 5.0 or higher and more particularly, with reference to the pH of the composition, have at least two pK
values of x-l or higher (x = pE~ of the composition), thus whereby for a composition having a pH of 6.5, they have at least two pK values of 6.5 - 1 = 5.5 or higher.
' Specific, non-limiting examples of preferred poly-acids useful in the composition of the present invention are diglycollic acid, ni~rilotriacetic acid and citric acid.
Specific non-limiting examples of most preferred polyacids useful in the composition of the present invention are s ~ Na2H2P207, pyrophosphoric acid, ort~ophosphoric acid and ethylene.~diamine tetraacetic acid. Another class of most , preferred polyacid species for use herein comprises organo-phosphonic acids, particularly alkylene polyamino polyalkylene phosphonic acids, inclusive of ethylene dianine tetramethylene phos-phonic acid; hexamethylene diamine tetramethylene phosphonic ' acidi diethylene triamine pentamethylene phosphonic acid; and ' ~ aminotrimethylene phosphonic acid. :
The polyacids can be added as such into the composi-tions of the present invention or in the form of their water s~luble salts or semi-salts, e.g., as H4P207, Na2H2P207, or Na4P207. It may be necessary, howevex, to add pH-regulating agents, well known in the art, to adjust the pH of the com-positions.
` Irhe pH
An essential condition of the present invention is that the compositions have a pH within the range of from 6.0 to 7.5f preferably between about 6.0 and 7Ø

- 14a -~36~78 '"

Compositions containing the essential components of the present invention, but having a pH below 6.0 become difficult to process and are unstable, particularly if they contain stilbene-type brighteners, in addition they become less attractive because unsafe for topical application.
Compositions containing the essential components ~-of the present invention but having a pH above 7.5 lose their effectiveness with respect to removal of bleach-sen-sitive stains.
Liquid Carrier As liquid carrier, water, organic solvents, and mixtures thereof, can be used.
Compositions containing the above-described essential surfactants, polyacids and water will remain liquid and stable under most circumstances, particularly if the soluble ethoxylated nonionic surfactant has a relatively long ethenoxy chain, i.e., wherein the number of ethoxy units is at least equal to or higher than half the number of carbon i~
atoms of the hydrophobic moiety.
The liquid carrier used in the instant compositions may comprise water and an organic solvent. The organic solvent may comprise up to about 50% of the total liquid carrier usëd I in the compositions.
The organic solvents, which should not chemically react with any of the components of the instant compositions, are selected from the group consisting of lower aliphatic alcohols having from 2 to 6 carbon atoms and 1 to 3 hydroxyl groups; ethers of diethylene glycol and lower aliphatic mono-alcohols having from 1 to 4 carbon atoms; and mixtures thereof.
' .... .
.

1~8~

Elydrotropes selected from t~e water-soluble salts of alkylbenzene sulfonic acids having up to 3 carbon atoms in the alkyl groups are also useful in compositions of this invention.
Suitable examples of lower aliphatic alcohols useful in the instant compositions are ethanol, n-propanol, isopropanol and butanol; 1,2-propanediol, 1,3-propanediol, and n-hexanol. Useful examples of glycol ethers are monomethyl-, -ethyl-, -propyl-, and monobutyl ethers of diethylene glycol;
and mixtures thereof. Other organic solvents having a relati-vely high hoiling point and low vapor pressure could alsobe used, provided they do not react with any of the other ingredients present.
Suitable examples of hydrotropes that can be used in the instant ~positions are thewater-soluble alkylaryl sulfon-ates having up to 3 carbon atoms in an alkyl group such as sodium, potassium, ammonium and ethanol amine salts of xylene-, toluene-, ethylbenzene-,and isopropylbenzene sulfonic acids.

They are preferably used in compositions containing, in addition, a synthetic, anionic surfactant of the sulfonate type. Hydro-tropes can conveniently be considered as part of the liquidcarrier of the composition since the hydrotrope will necessarily dissolve therein.

' ~

:
In the preferred compositions, the liquid carrier is an aqueous mixture, wherein the amount of organic solvent, preferably ethanol, prcpanol, isopropanol, sodium salt of cumene sulfonic acid, and mixtures thereof, is between 2% and ,~ 15~ by weight of the total composition.
Concentration and Ratios Heavy duty liquid detergent compositions, to be suit~d for the washing of the heavily soiled fabrics, require high COncentratiQnS of surfactants of powerful cleansing ; 10 effect. They must exhibit a high degree of stability upon - ~ storage over a period of months under different temperature conditions. They must be free-flowing from the receptacle as manufactured and after aging. They must be homogeneous in compositions at the time of use to ensure the addition of the proper amount and ratio of the components.
The physical and cleaning properties of the instant compositions are the result of mutual effect of the different components in proper ratios. Therefore, it is the key to stability, pourability, homogeneity and cleaning effectiveness, . . . .
that the essential surfactants be present in specific ratios and sufficient concentration.
The instant compositions are specifically designed J to provide optimum cleaning benefits when used either as pre-treatment agents, preferably applied in highly concen-trated form directly onto the fabric stains, in particular ~ onto bleach-sensitive stains, prior to washing, or as ; detergents for conventional through-the-wash fabric laundering operations. Hence, highly concentrated, ;, .

6~8 liquid, stable, homogeneous detergent compositions, which can be topically applied onto stains as such, and can be conveniently added to the washing liquors, provide a clear formulation advan-tage.
The instant compositions remain liquid, stable, homo-geneous with a surfactant content variable within the range of from about 20% to about 70~ by weight, with the balance being primarily the minor amount of polyacids and the liquid carrier.
Preferred compositions contain at least about 25%
by weight of soluble ethoxylated nonionic surfactant in order to ensure proper greasy stain removal performance in both pre-treatment or topical application and through-the-wash utilization of the instant compositions.
Most preferred are compositions containing at least about 25% by weight of soluble ethoxylated nonionic surfactant and up to 25% by weight of an synthetic anionic surfactant of the sulfonat~ type and wherein the total amount of surfactants -is below about 60% by weight~
The amount of polyacids present in the instant com- ~
20 positions is critical and must be, with reference to the acid ~`
form, within the range of from 0.10% to about 1.25~ by weight, ;calculated on the total weight of the composition. Preferably, the amounts of polyacids vary in the range between 0.25~ and 1.0% by weight, whereby, most preferably, the concentration is inversely related to the pK value or values that are above 5Ø
, ~6~

Compositions having the appropriate amount of soluble ethoxylated nonionic surfactant and a pH between 6.0 and 7.5, but having a c3ncentration of polyacids below 0.10~ by weight, hardly provide any detergency effect on bleach-sensitive stains.
f By increasing the concentration of polyacids beyond 1.25% by ` weight, no additional detergency effect via topical application ' ~ will be obtained, particularly on bleach-sensitive stains, while phase separation of the composition occurs and precipi-tation o~ some polyacids, particularly of inorganic acids, . 10 can take place.
Optional Components An optional component of the instant compositions is an alkanolamine compound. The free alkanolamine useful hereint in particular to adjust the pH of the comp~sitions, ' is selected from the group consisting of mono-, di- and tri-ethanolamine, and mixtures thereof; preferred is the trlethano-lamine. The amount of alkanolamine which can be added can be up to 5~ by weight, but is preferably below 2% by weight.
f;~ A desirable component for addition herein is a 20 suitable opacifier. An opacifier contributes to create a ` uniform appearance of the compositions of this invention.
Examples of suitable opacifiers include polystyrene commercial-ly sold under the trade marks LYTRON 621 and LYTRON 607 manu-factured by Monsanto Chemical Corporation. It has been found that the LYTRON opacifiers can be incorporated in the compositions of this invention only in presence of polyacid, i.e., the opacifier precipitates in the compositions herein which do not contain the polyacids.
Another optional component of the instant compositions 30 is an aliphatic carboxylic acid as suds-controlling agent, having from 12 to 24, preferably from 16 to 22 carbon atoms.

- 19 _ ~
.~ . ~. .

8~7~

Its concentrations should not exceed 2.5% by wei~ht and pref-erably be restricted to at most 1.5~ by weight, calculated on the total weight of the composition.
Another optional but preferred component is a sili-cone-based suds-controlling and regulating agent. A heavy duty liquid detergent composition desiyned for use in both horizontal and vertical washing machines must have acceptable sudsing prop-erties when used in either of these machines. The silicone-based suds-controlling and regulating agents useful herein can be alkylated polysiloxane materials of several types, in combination with solid materials such as solid silica, silica aerogels, xerogels and hydrophobic silicas of various types.
Suitable examples of alkylated polysiloxanes are dimethyl-polysiloxanes having a molecular weight of from about 200 to 200,0~0. Suitable examples of mixtures of alkylated siloxanes and solid silica have a siloxane/silica ratio of from 20:1 to 1 preferably 10:1 to 3:1. Concentrations of suds-controlling agents useful in the instant compositions can vary between 0.01% and 2%; preferably 0O05% and 0.2~.
A preferred suds-controlling agent herein comprises a mixture of (a) dimethylpolysiloxane and silica-aerogel in a 9:1 weight ratio emulsified in (b) a nonionic of the general formula R'COO-(C2H40)p-H, wherein R' is an aliphatic hydrocarbon chain having 10 to 22 carbon atoms and p is a number of 300 to 2,000, in a weight ratio of (a) to (b) of from about 1:4 to 1:1, preferably about 1:2. Due to the pre-emulsification of the siloxane and silica, the preferred suds-controlling agent is easily dispersed in the instant compositions, and shows an extraordinary storage stability and suds-controlling effective-ness irrespective of the aging. Concentrations of the preferred silicone-based suds-controlling agents, preferably present in the 6171~

instant compositions can be up to 0.5~ by weight, preferably between 0.05% and 0.2% by weight.
Still other optional components include brighteners, fluorescers, antimicrobial agents and enzymes. Such components preferably comprise not more than about 3~ by weight of the total compositions. One particular advantage of the instant compositions is that the hardly water-soluble brighteners and ~; fluorescers can be added either directly to the compositions, i.e., as such, or during any st~p of the formulation process.
TESTS AND EXAMPLES
,~
The Eollowing tests and examples illustrate the liquid detergent composition~ of the present invention. The figures mentioned in the examples refer to percentages by weight.

. ~ , .
The abbreviations for the nonionic surfactants employed, e.g., C12 15(EO)~, are standard for such materials and C12 15 describes the carbon atom content of the hydrophobic moiety o~ the molecule while (EO)4 indicates the ethylene oxide unit content of the hydrophilic moiety of the molecule.
The effectiveness of the instant compositions, par-ticularly with respect to bleach-sensitive stains, if compared to practically identical or commercially available detergent compositions, is illustrated below, whereby most tests have been carried out by means of a "Launder-Ometer" device and some have been duplicated under real washing conditions. The~"Launder-Ometer" device is described, for example, in "Detergency, Theory and Test Methods" ~y N. G. Cutler and R. C. Davis, part I, pages 415-417 (edition 1972, Marcel Dekker, Inc., New York).

~ - 21 -, ., In all tests, stalned swatches were used, prepared as follows:
(1) cotton swatches, swatches of new but p.rewashed cotton (5 x 5 cm) were stained with red wine and tea respectively, by moistening them with 5 drops - Pasteur pipette - of red wine or 5 drops oE tea obtained b~ boiling 15 gr. of tea or 5 minutes in 200 cc. of water, and aging for at least 24 hours at ambient temperature; (2) polyester/cotton swatches ` ~( 65/35; 5 x 5 cm), swatches of new but prewashed polyester/
cotton swatches were prepared in the same manner as the cotton swatches.

.

; ' :

: .
,:"
' ~:;

'' . ~`
~
,~
., .
.~
~ - 21a -'' ~
- . , :
, TEST A
The effectiveness on removal of bleach-sensitive stains by liquid compositions of the present invention, if compared to pract.ically identical liquid compositions but wlthout th2 essential polyacids,is illustrated by the follow-ing Test A.
A series of six liquid detergent compositions Al-A6 were prepared, consi.sting of:
Components: 1 A2 A3 A4 A5 A6 -triethanolamine salt of - - - 12 16 20 : linear alkylbènzene sulfonic acid wherein the alkyl chain has in average 11.l9 carbon atoms.
;. -C14_15(EO)4 15 20 25 - _ _ -tallow (EO)ll 15 20 25 ~C12_15(EO)4derived from a _ _ _ 6 8 10 primary alcohol with about 60~ by weight of branched 20 chain structure C16-19 (EO)ll derived from _ _ _ 12 16 20 a primary alcohol with about 72% by wt of branched chain . structure -optical brightener (stilbene 0.2 0.2 0.2 0.20.2 0.2 type) ~~thanol 15 15 15 10 10 10 -perume,dyes ~ minors -triethanolamine ~ to adjust pH -30 -water ~ u-balance - ~
pH of the compositions 7.0 7.0 7.0 7.0 7.0 7.0 .
Another series of six detergent compositions were ~.

. prepared identical to the ones of the previous series except ~ :

: that 0.35% by weight of ethylenediaminotetramethylenephosphonic acid (EDTMP) was added.

11 ~86,~

A jar of the "Launder-Ometerl' device was filled with 0.2 liter of water (hardness : 3.14 millimoles/liter as CaCO3) and about 1.6 gr. o the detergent product to be tested.
Two cotton swatches stained with red wine and two cotton swatches stained with tea were pretreated by topical applica~
tion of the product to be tested applied onto the stains (yielding a total amount of composition to be tested per jar of about 2.6 gr. or a concentration of about 1.3% by weight).
For each composition Al~A6, two jars were prepared as described.
The 12 jars were placed in the "Launder-Ometer" and the temperature raised up to 60C over a period of 40 minutes.
Subsequently, the swatches were rinsed ~or about 3 minutes under running tap water (temperature about 17C) and line-dried.
The line-dried swatches were then visually graded by two graders working independently, using a 0-5 scale tunder Northern standard daylight; 0 = no removal of the stain, 5 = complete removal). Thereafter, all the results of both graders were pooled. The results are given in Table I.

TABLE I
.;
o~poslti~, First series Second series with wi~hout ~DTMP 0.35~ EDT~P
_. . . ~ . . . _. _ _ . _ Al 2.85 4.2 A2 2.8 4.4 A3 2.65 4.2 A~ 4.1 4.75 A5 4.0 4.7 6 4.8 ' ' ' ' ~ -'~ :

~86~L7b~

Thus the bleach-sensitive stain removal performance of the compositions of the present invention, i.e., containing a small amount of a polyacid, is significally superior over practically identical compositions but containing no polyacid~
TEST B
A series of six liquid detergentcompositions were pre-pared consisting of:
Components 1 B2 B3 B4 B5 B6 `;

-triethanolamine salt of a 20 20 20 20 20 20 lO linear alkylbenzene sulfonic acid wherein the alkyl chain averages 11.9 carbon atoms in length -C14-15(E)7 30 30 30 30 30 30 -optical brightener (stilbene ~ -0.2 -; type) - -triethanolamine ~-to adjust pH - ~
-ethanol 15 15 15 15 15 15 -perfumes, dyes minors 20 -water balance -ethylenediaminotetramethylene- - - 0.35 0.35 phosphonic acid (EDTMP) x -citric acid - - - _ 0.5 0.5 pH 7.0 6.5 7 6.5 7.0 6.5 ' These compositions Bl-B6 were tested in exactly the same way and under the same conditions as the compositions Al-A6 described in Test A. Thé stained swatches were similar ; to those of Test A and they were graded in the same way too.

The pooled results are given in Table II.

~.:
., ~

- 2~ -~: .

7~

TABLE I I
~ _ _ _ ___ . .
Compositions Bl B2 B3 B4 B5 B6 gradings 1.8 2.3 4.0 4.5 2.6 3.45 .... . _ From Table II, follows: the superiority of compositions B3 B6 ormulated according to the present invention over the compositions Bl and B2; the correlation between the pH of the composition and the pK value of the acid which is ; above 5 but within one unit of the pH of the composition, i.e. for citric acid having pK values of 3.08, 4.74 and 5.40, the effectiveness is more pronounced with a composition having a pH of 6.5 (B6) than with a composition having a pH of 7 (B5);
and the effectiveness of polyacids as EDTMP having more than one pK value above 5. 0 (B3 and B4 are more effective than B5 or B6.) TEST C
The influence of the pK values of the polyacids on the bleach-sensitive stain removal per~ormance in correlation with the pH of the detergent composition is ~; illustrated by the following Test C.
A series of six liquid detergent compositions were prepared Cl-C6, identical to the composition A6, except that compositions C2-C6 contained in addition the following polyacids:
Cl = A6 (thus no polyacid) C2 = A6 + 1% by weight of Na2H2P207 ~(pK:0.86; 1-96, 6-68; 9-39) C3 - A6 + 1% " " ~I citric ~cid (pK : 3.08; 4.74; 5.40) C4 = A6 -~ 0-5% " " " nitrilotriacetic acid (pK : 3.03; 3.07;
10.7) 5 A6 + 0 5% " ~ " glycolic acid (pK : 3.83) -~;
6 A6 + 0~5% " " " adipic acid (pK : 4.43; 4.41).

The pH of all compositions was 7Ø

6~7~ , , I , Each of these compositlons Cl-C6 was tested under exactly the same conditions as the compositions Al-A6 in Test A.
The line-dried cotton swatches were grad~d by two graders independently and the results of all stains and all swatches were pooled. The bleach-sensitive stain removal performance of each composition is given in Table III.
TABLE III

- - ~ . .. _ __ . .. _ ~ _ ~ _ ~
: Compositions Cl C2 C3 C~ C5 C6 .~ . _ .. __ Gradings 1.25 3.90 2.75 3 25 l.00 0.75 , _.................................. .. .. .. .
!' 10 The superiority in bleach-sehsitive stain removal performance of compositions C2, C3 and C4, formulated according to the present invention, over compositions C5 and C6 containing similar amounts of a polyacid (C6) but with pK values below x-l, or a monoacid (C5), is evident.
TEST D
The present test shows the effectiveness of removal of bleach-sensitive stains (wine, tea) via topical application '~
by compositions of the instant invention containing no bleaching agents versus commercially available granular detergent compo-sitions.
A series of five detergent compositions Dl-D5 were prepared and tested, being:

:
. .
., ' .

~L~8~7E~

Dl : identical to composition A6 of Test A;
D2 : identical to Dl but containing 0O35% by weight of ethylenediaminotetramethylenephosphonic acid (EDT~IP);
D3 : identical to Dl but containing 1~ by weight of citric acid;
D4 and D5 : commercially available granular detergent compositions consisting of (in % by weight) , .
Components D4 5 -sodium salt of linear alkylbenzene 9.3 8.1 sulfonic acid wherein the alkyl chain has 11.9 carbon atoms in : average -tallow (EO)ll 3.4 0.8 -hydrogenated fatty acid derived from 3.4 1.7 fish oil having 16 to 22 carbon atoms - sodium tripolyphosphate 35.0 67.0 ~ ::

-sodium silicate (SiO/Na20) 6.0 - : ~ .

: -brightener (stilbene type) 0.2 0.25 , -sodium carboxymethyl cellulose (100%) 0.8 1.5 ~ -perfume 0.2 0.2 ; -ethylenediaminotetraacetic acid 0.2 0.2 sodium salts ~ ''' .
,' '' ,. '"
; ' :! . .
. ' ~ ' , .
., - ' " '' ' ' ' ' .

'' ' ' ' ' ' ~ ' ' - ' ! ~

~L~8~

a2 o4 13.5 6.0 -sodium perborate 25.0 -polyethyleneglycol condensate 0.2 0.2 (average molecular ~7eight about 400) -miscellaneous 1.0 1.0 -proteolytic enzyme * 0.2 0.2 -moisture ----- balance -~

* proteolytic enzyme: "ALCALASE" - Trade Mark - made by Novo Industri A/S, Copenhagen, Denmark, containing about 6% by weight of active enzyme material.
: Test D with compositions Dl-D5:is carried out in the "Launder-Ometer" device under exactly the same conditions as described in Test A, with the same number of wine- and tea stained cotton swatches, except that 2.6 gr. per jar of each granular detergent D4 respectively D5 is presolubilized in 0.2 liter of water just prior to the test tno topical application . ~ . .
with the presolubilized granular composition)~ The rinse and :. line-dried swatches are then graded by two graders as described in Test A and all the results pooled. The pooled results are given in Table IV.

~ ' ~.
: . - .

61'7~

TABLE IV
, .. .. __ _ .
Compositions Dl D2 D3 D4 D5 Gradings 2.45 4.85 3.604.90 3.50 ~,' TEST E
: Test E shows the effectiveness of compositions of the present invention under real washing conditions.
The following series of four detergent compositions El-E4 were prepared and tested:

El : identical to the granular composition D4; ; :
E2 : identical to composition A6 of Test A, but containing 0.5% by weight of citric acid and . having a pH of 6.5;
E3 : identical to composition A6 of Test A, but containing 0.35~ by weight of EDTMP (pH = 7);
E4 : identical to E2 but containing 1% by weight of Na2H2P2o7 instead of citric acid (pH 5.65~.
-` In addition, composition= E2, E3 and E~ contained ;~
about 0.9~ by weight o~ a fatty acid having 16 to 22 carbon atoms. With each of these.compositions El-E4, four loads of about 3 kg each of domestic soiled laundry were washed in a horizontal drum-type washing machine .
:- tMIELE 416S). ~ . :

.
,; .
~ 29 -~ :
.,. .. . . . ~ .

lq~B6i'78 Each load contained in addition two cotton and two polyester/cotton swatches (10 x 10 cm), stained with tea, coffee and red wine re~pectively (stalning~ by 5 drops - Pasteur pipette - of red wine on cotton swatches and 5 drops on polyester/cotton swatehes; with tea: 5 drops of a mixture obtained by boiling 15 grams of tea for 5 minutes ; in 200 cc. of water, on cotton swatehes and 5 drops on polyester/eotton swatches; with coffee: 5 drops o a mixture obtained by boiling 25 gr. of coffee for 5 minutes in 200 cc.
of water, on cotton swatches and 5 drops on polyester/cotton swatehes; aging: at least 24 hours at room temperature.
Each of the stains on the swatches (12 in total tested with compositions E2, E3 and E~) were each pretreated with about 1 gr. of the liquid eomposition to be tested (i,e., about 12 gr. in total per load) and about 108 gr. of the detergent compositions E2-E4 were added into the respective washing iiquors (resulting in a total concentration of about 0.60% by weight). The swatehes washed with test composition El were not pretreated but the total concentration of composition El was also 0.6% by weight.
These loads of domestie soiled laundry and swatehes were washed at onee. In the main wash eyele of the washing maehine in about 20 liters of water (hardness : 3.14 milli-moles/ liter as CaCO3). The temperature of the washing liquor was raised to about 60C over a period of 25 minutes ancl kept at that temperature for an additional 30 minutes.
After dilution of the washing liquor, evaeuation of the diluted liquor and rinsing of the load (five cyeles with about 10 litres of water; hardness of water : 3.14 millimoles/liter; temperature ; 30 19-16C; and spinning) all swatehes were removed, line-dried, and the dried swatches visually graded by two graders working independently, using a 0-5 seale (0 = no removal of the stain;

. .
-. . . ~ :

5 = complete removal). Thereafter, all results of the graders with respect to the stains on cotton and polyester/
cotton swatches were pooled. The results are given in Table V hereafter.
The same test was repeated with the compositions -E4, all conditions being identical, e~cept that none of the swatches were pretreated and 120 gr. of each of the compo-sitions E2-E4 tested were added directly into the washing liquor. The line-dried swatches were again graded as described previously but whereby the results with respect to the cotton swatches and polyester/cotton swatches were pooled separately. The results are given in Table V.
TABLE V

Washing ComposLtions Swatches Procedure _ _ El E2 E3 E4 polyester/ with pretreatment _ 4.63 4.79 4.66 cotton without pretreatment 4.30 3.64 4.53 3.95 ~
cotton with pretreatment _ 3.37 4.44 4.37 -~ without pretreatment 4.36 2.73 3.66 3.00 ~
, .
From this Table V, it follows that compositions of the present invention are - at the same concentration -:
as good on bleach-sensitive stain removal, without pretreatment, than a heavily built granular detergent compositions con-taining a considerable amount of bleaching agent, and have superlor effect on bleach-sensitive stain removal if -using the same total concentration of the detergent compositions - there is pretreatment by topical application.

''~ `' '' ~ - 31 -EXAr'l.PLES
II III IV . V VI VII VIII IX X
Monoethanolamine 16.2 ~ - 20 salt of linear alkylbenzene sulfonic acid having in ave-rage 11.9 car-bon aboms in 10 the alkyl group Triethanolamine - 15 20 25 20 20 20 20 - 20 salt of linear : alkylbenzène sulfonic acid having in ave-rage 11.9 car-bon atoms in .: the alkyl group C17-1g(E)ll - _ _ - 20 (about 25%
branched)*
16-l9(E)ll 20 15 20 25 - _ _ 20 (about 72%
: branched) }
Tallow (EO)ll - - _ _ _ 20 _15(Eo)ll _ _ _ _ _ _ 30 20 (about 50%
branched) ., C14-15(E)4 _ _ _ - 10 10 - - - - :-C12-15(E)4 10 5 10 15 - - - _ _ _ g-ll( )8 ~ - - 20 14-15 )7 ~ ~ ~ ~ ~ 30 12-l5(Eo~3 ~ - - - - _ _ 10 Ethanol 8.5 10 10 12 15 15 13 6 10 7 Brightener ---------------------0.2-~------------ ------------ .
' (Stilbene type) Perfume, ----------~~~~~~~~~~0 35---------------------------dyes .. .

7~

:[I III . IV . V . VI . .VI.I VIII. . IX X
.. . . . ~
: EDTMP ** - 0.35 - - 0.~ - 0.3 0.25 0.35 ~
Citric Acid 0.5 ~ - 0.3 0.1 - 0.75 EDTA *** - 0.5 - -0,75 Triethano- 0.75 0.78 0.51.2 1 l.S0 0.85 0.6 0.7 1.3 lamine Water- --------- ---------balance---~
pH of the6.5 7 6.2 6.75 7.3 6.7 7 7.2 6.8 6.9 composi-tion * 25~ branched = about 25~ of the alkyl chains are branched.
** EDTMP = ethylenediaminotetramehylenephosphonic acid.
***EDTA - ethylenediaminotetraacetic acid.

., ,, ,~ '" . ~

, ~' `'.''"
,, ~' ', ''`' ~, .

; ' ':
::.
,~ . ~

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

Claims (22)

WHAT WE CLAIM IS:

1. liquid, concentrated homogeneous stable heavy duty liquid detergent comprising:
(a) from about 20% to about 70% by weight of the composition of a soluble ethoxylated nonionic surfactant selected from the group consisting of ethoxylated alcohols containing from about 2 to about 24 moles of ethylene oxide wherein the alcohol is selected from the group consisting of:
(i) straight and branched chain primary and secondary, saturated and unsaturated, aliphatic alcohols having from about 8 to about 24 carbon atoms in the hydrocarbyl group thereof, and (ii) alkyl phenols wherein the alkyl group or groups have from about 1 to about 12 carbon atoms, wherein at least one alkyl group has at least 6 carbon atoms and wherein the total number of carbon atoms in the alkyl groups is at most about 15; and mixtures thereof;
(b) from about 0.10% to about 1.25% by weight of the composition of a polyacid having at least one pK value of 5.0 or higher;
and (c) the balance of the composition being a liquid carrier;
wherein the pH of the product is from 6.0 to 7.5.

2. A composition according to Claim 1 wherein said polyacid is from about 0.25% to about 1.0% by weight of the composition.

3. A composition according to Claim 2 wherein the pH of the product is from 6.0 to 7Ø

4. A composition according to Claim 2 wherein said polyacid has at least one pK value of x-1 or higher where x is the pH of the composition.

5. A composition according to Claim 2 wherein said polyacid has at least two pK values of 5.0 or higher.

6. A composition according to Claim 4 wherein said polyacid is selected from the group consisting of ethylene diamine tetramethylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid, diethylene triamine pentamethylene phosphonic acid, and amino trimethylene phosphonic acid.

7. A composition according to Claim 1 which also contains an adjunct surfactant selected from the group consisting of synthetic anionic surfactants of the sulfonate and sulfate type, semipolar surface active agents, fatty acid alkanolamides, their water soluble salts and mixtures thereof and wherein the amount of said adjunct surfactant is less than 50% by weight of the total of said soluble ethoxylated nonionic surfactant and said adjunct surfactant in the composition and wherein said total amount of surfactant in the composition is not more than 70% by weight of the total composition.

8. A composition according to Claim 7 wherein said polyacid is from about 0.25% to about 1.0% by weight of the composition.

9. A composition according to Claim 7 wherein the pH of the product is from 6.0 to 7Ø

10. A composition according to Claim 7 wherein said polyacid has at least one pK value of x-l or higher where x is the pH of the composition.

11. A composition according to Claim 7 wherein said synthetic anionic surfactant of the sulfonate type is selected from the group con-sisting of alkylbenzene sulfonic acid having from about 8 to about 15 carbon atoms in the alkyl group, n-paraffin sulfonic acids having from about 6 to about 20 carbon atoms, water soluble salts thereof, and mixtures thereof.

12. A composition according to Claim 11 wherein said water soluble salts are the mono-, di- and triethanilamine salts and mixtures thereof.

13. A composition according to Claim 12 wherein said soluble ethoxylated noniollic surfactant is prepared from primary aliphatic alcohols containing from 12 to 20 carbon atoms condensed with from about 4 moles to about 14 moles of ethylene oxide per mole of alcohol and mixtures thereof.

14. A composition according to Claim 13 wherein said polyacid has at least two pK values of 5.0 or higher.

15. A composition according to Claim 14 wherein said polyacid has at least two pK values of x-l or higher where x is the pH of the composition.

16. A composition according to Claim 14 wherein said liquid carrier is water and an organic solvent selected from the group consisting of lower aliphatic alcohols having from 2 to 6 carbon atomb and from 1 to 3 hydroxyl groups, ethers of diethylene glycol and lower aliphatic monoalcohols having from 1 to 4 carbon atoms and mixtures thereof.

17. A composition according to Claim 16 wherein said organic solvent is from about 2% to about 15% by weight of the total composition.

18. A composition according to Claim 17 wherein said polyacid is selected from the group consisting of ethylene diamine tetra-methylene phosphonic acid, hexamethylenediamine tetramethylene phosphonic acid, diethylene triamine pentamethylene phosphonic acid, and amino trimethylene phosphonic acid.

19 A liquid, concentrated homogeneous stable heavy duty liquid detergent comprising:
(a) from about 20% to about 70% by weight of the composition of a soluble ethoxylated nonionic surfactant selected from the group consisting of ethoxylated alcohols containing from about 2 to about 24 moles of ethylene oxide wherein the alcohol is selected from the group consisting of:
(i) straight and branched chain primary and secondary, saturated and unsaturated, aliphatic alcohols having from about 8 to about 24 carbon atoms in the hydrocarbyl group thereof, and (ii) alkyl phenols wherein the alkyl group or groups have from about 1 to about 12 carbon atoms, wherein at least one alkyl group has at least 6 carbon atoms and wherein the total number of carbon atoms in the alkyl groups is at most about 15; and mixtures thereof;
(b) from about 0.10% to about 1.25% by weight of the composition of a polyacid selected from the group consisting of: ethylenediamine tetramethylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid, diethylene triamine pentamethylene phosphonic acid and aminotrimethlylene phosphonic acid; and (c) the balance of the composition being a liquid carrier;
wherein the pH of the product is from 6.0 to 7.5.

20. A composition according to claim 19 which in addition comprises an anionic adjunct surfactant selected from the group consisting of an alkylbenzene sulfonic acid having from about 8 to about 15 carbon atoms in the alkyl group, a n-paraffin sulfonic acid having from about 6 to about 20 carbon atoms, water soluble salt of said sulfonic acids, and mixtures thereof, whereby the adjunct anionic surfac-tant represents below 50% by weight of the total of the soluble ethoxylated nonionic surfactant and the adjunct anionic surfactant.

21. A composition in accordance with claim 19 which in addition comprises from 0.01% to about 2% by weight of a silicone suds-regulating agent.

22. A composition in accordance with claim 19 wherein the ethoxylated nonionic surfactant is represented by a mixture of:
(1) a primary aliphatic alcohol ethoxylate obtained from an alcohol, the hydrocarbyl chain of which contains at least 65% branched-chain structure and has from about 16 to 19 carbon atoms, and from 8 to 14 moles of ethylene oxide;
(2) an alcohol ethoxylate derived from a primary alcohol having from 12 to 15 carbon atoms in the hydrocarbyl chain and from 3 to 7 moles of ethylene oxide.