O

Ulllt?d States Patent [19] [11] Patent Number: 4,919,839

Durbut et al. [45] Date of Patent: Apr. 24, 1990

[54] LIGHT DUTY MICROEMULSION LIQUID 944653 4/1974 Canada .

DETERGENT COMPOSITION CONTAINING 6055497 5/1981 Japan ................................. .. 252/545
AN ANIOCIC/CATIONIC COMPLEX 1238896 10/1986 Japan ........................ .. 252/DIG. 14
373214 11/1959 United Kingdom ............. .. 252/8.75
[75] Inventors: Patrick Durbut, Verviers, Belgium; 1116966 6/1968 United Kingdom ..... .. 252/DIG. 14
Ammanuel Mehreteab, Piscataway, 1232698 5/1971 United Kingdom ..... .. 252/DIG. l4
N'J'; Myriam Mandi!" Sewing; Guy Primaly Examiner—-Dennis Albrecht
gun?’ Grace'Honogne’ both of Assistant Examiner-J. Darland
elgmm Attorney, Agent, or Firm-Bernard Lieberman; Murray
[73] Assignee: Colgate Palmolive Co., Piscataway, M- Grill; Robert C- Sullivan
NJ- [57] ABSTRACT
[21] Appl' No‘: 313’664 A light duty microemulsion liquid detergent composi
[22] Filed: Feb. 21, 1989 tion, useful for removing greasy soils from surfaces with
_ _ both neat and dilute forms of the detergent composition,
[51] Int’ cl's """"""""""" 51111]? Isl/2% includes a moderately water soluble complex of anionic
[52] us. Cl. .................................. .. 252/153- 252/173~ and “a?” surfactants’ 1“ which °°mP1eXthe am°m°
252/547_ 252/548; 252/542; 252}DIG_ 14: and cationic moieties are in essentially equivalent or
zsz/Dlé 25; 252/171; 252/551; 252/552; equimolar proportions, an anionic detergent, a co-sur
252/554; 252/DIG_ 19; 8/137 factant, an organic solvent and water. Preferably, the
[58] Field of Search ........ .. 252/121, 174.25, DIG. 14, complex component is one in which the anionic and
252/DIG_ 5’ 110, 153’ 542’ 552, 555, 104, 548, cationic moieties include hydrophilic portions or sub
3_75’ 545, 173, 90, 546, 547, 171, 551, 554’ DIG. stituents, in addition to the complex forming portions
19 thereof, the anionic detergent is a mixture of higher
_ paraffin sulfonate and higher alkyl polyoxyethylene
[56] References cued sulfate, the co-surfactant is a polypropylene glycol
U.S. PATENT DOCUMENTS ether, a poly-lower alkylene glycol lower alkyl ether or
2,950,255 8/1960 Goff ............. .. 252/DIG. 5 ‘1 Poly-lower alkylene glycol 1°Wer alkahoyl ester and
3,044,962 7/1962 13mm et a] ________ " 252/110 the organic solvent is a non-polar oil, such as an isopar
3,711,414 1/1973 Hewitt ..... .. 252/DIG. 14 aff'm, or an oil having polar properties, such as a lower
3,882,038 5/1975 Clayton . . . . . . . . . . . . . . .. 252/153 fatty acid ester or a lower fatty alcohol ester,

gggg?lgt aL _ Also within the invention are the described complex,

4,176,080 11/1979 Wise et al. . . . . . . . . .. 252/104 Preferably one of equimolar proportions of sodium 012
4,1s0,472 12/1979 Mitchell et al. .... .. 252/104 14 alkyl diethoxy ether sulfate and 012-14 alkyl-bis(2
4,264,457 4/1981 Becks et a1. .... .. 252/548 hydroxyethyl) methylammonium halide, and processes
4,272,395 6/1931 wright ------------- -- 252/548 for manufacturing the liquid detergent composition and
331315;“ et a1‘ ' for removing grease from laundry and hard surfaces‘ by
4:576:729 3/1986 Puszek 252/173 use of such a liquid detergent composition, especially in
4,681,704 7/1987 Bemardino et al. 252/546 heat fOrm, in which latter Precess Signi?cantly im
4,786,422 11/1988 Kern ............................. .. 252/l74.25 Proved Cleaning results, compared to that Obtained
when using control detergent compositions.
FOREIGN PATENT DOCUMENTS
818419 7/1969 Canada . 6 Claims, No Drawings
 4,919,839
1 2
pectedly improves the softening of the laundry. How
LIGHT DUTY MICROEMULSION LIQUID ever, this patent does not disclose the presence of a
DETERGENT COMPOSITION CONTAINING AN complex in a light duty microemulsion liquid detergent
ANIOCIC/CATIONIC COMPLEX and does not disclose any improvements in cleaning
hard surfaces when such a composition is employed in
This application relates to a light duty microemulsion neat form. U.S. Pat. No. 4,264,457 discloses liquid deter
liquid detergent composition which is useful for remov gent compositions that contain ethoxylated anionic and
ing greasy soils from substrates. More particularly, the cationic surfactants with nonionic surfactant but these
invention relates to such a detergent composition which too are employed as fabric softeners and are not said to
contains a complex of anionic and cationic'surfactants, be in anionic-cationic complex form. U.S. patent appli
an anionic surfactant, a co-surfactant, an organic sol cation Ser. No. 06/916,067 discloses anionic/cationic
vent and water, and which is useful to remove greasy surfactant complexes and their use in microemulsions
deposits from surfaces, as from dishes, both in neat form for wash cycle fabric softening, and Ser. Nos.
and when diluted with water. 06/916,068 and 06/916,069 also describe such com
Synthetic organic dishwashing detergent composi plexes, but in particulate wash cycle fabric softening
tions have long been produced commercially and light additives. However, none of these patent applications
duty liquid detergent compositions of such type have describes or suggests applicants’ preferred complexes or
enjoyed considerable success for hand washing of their light duty microemulsion liquid dishwashing de
dishes. Such compositions are normally based on ani tergent compositions and none describes or suggests the
onic detergents and are unbuilt. Although they are 20 unexpectedly bene?cial removals of fatty soils resulting
useful in normal dilutions in dishwater, they have not when such compositions are used, especially in neat
been satisfactorily effective when employed in neat form.
form, as on a sponge, to remove heavy greasy deposits British patent speci?cation No. 2,190,681 and U.S.
from hard surfaces, or as pre-spotters for laundry. patent application Ser. Nos. 07/120,250 and 07/267,872
Comparatively recently it has been discovered how 25 disclose microemulsion cleaning compositions in con
microemulsions can be made and it was learned that centrated and dilute forms, which comprise anionic
microemulsion cleaning compositions, which contain a synthetic organic surfactant, hydrocarbon solvent, co
surfactant, a cosurfactant, a lipophilic solvent and water surfactant and water, and which are intended for re
are more effective cleaners than ordinary emulsions and moving greasy soil from hard surfaces. However, such
surfactant solutions. 30 speci?cation and applications do not disclose the pres
Complexes made by reacting anionic and cationic ence in such microemulsions of applicants’ complexes
surfactants have been suggested as components of built or other complexes of anionic and cationic surfactants,
and unbuilt synthetic detergent compositions. In some and do not disclose the unexpectedly bene?cial removal
cases such complexes were said to be useful components of fatty soils from both hard surfaced items and from
of particulate detergent compositions but they have also laundry by microemulsions containing such complexes.
been suggested for use in liquid preparations. The only prior art disclosure of anionic-cationic sur
Prior to the present invention applicants’ invented factant complexes being incorporated in any micro
complexes had not been employed in microemulsion emulsions that has come to the attention of applicants is
cleaners, and their desirable effects on such microemul that which is recited in an article by Bourrel, Bernard
sions, including improved cleaning of heavy greasy soils 40 and Graciaa, that appeared in Tenside Detergents, Vol.
from hard surfaces when used in neat form, as on a 21, starting at page 311, which was published in 1984.
sponge, had not been recognized. In accordance with That article does not suggest the presently disclosed
the present invention a light duty microemulsion liquid light duty microemulsion liquid detergent compositions
detergent composition which is useful for removal of and their unexpectedly improved results. Rather, it
greasy soils from substrates, both in neat form and when 45 appears to be an essentially theoretical study of the
diluted with water, comprises a complex of anionic and effect of an anionic-cationic surfactant reaction com
cationic surfactants, in which complex the anionic and plex on microemulsion characteristics, and from that
cationic moieties are in essentially equivalent molar study the present compositions would not be obvious.
proportions, an anionic surfactant, a co-s'urfactant, an Pseudo-nonionic complexes of anionic and cationic
organic solvent, and water. Also within the scope of surfactants are described in Vol. 125 (No. 2) Journal of
this invention are novel complexes, processes for manu Colloid and Interface Science, pages 602-609, which
facturing the light duty microemulsion liquid detergent refers to ethoxylated sulfate surfactant reactants form
compositions, and processes for use thereof, especially ing complexes with cationic surfactants, but the com
in neat form. Highly preferred complexes are those in plexes made are not disclosed in microemulsions.
which both the anionic and cationic surfactant reactants 55 The anionic surfactants and the cationic surfactants
include hydrophilic substituents or components which which are reactable to form the complexes utilized in
modify the solubility in water of the complex so that it the invented compositions may be any such suitable
is about 35%. The microemulsion detergent composi reactant materials, although it is highly preferred to
tions made with such complexes are of cleaning proper employ such surfactants which include one or more
ties that are signi?cantly superior to those of controls, 60 hydrophilic components other than the complex form
especially when used in neat form, as'on greasy dishes ing components thereof, so that the solubility in water
and utensils, or as laundry pre-spotter of the complex resulting will be in the range of 5 to
A search of selected prior art patents indicates that 70%, preferably 10 to 60%, more preferably 20 to 50%,
the present invention is novel and unobvious. U.S. Pat. e. g., about 35%. Descriptions of some operative anionic
No. 4,000,077 describes the use of anionic surfactant and 65 and cationic surfactants are found in U.S. patent appli
cationic fabric softening agent in rinse water for soften cation Ser. No. 07/916,067, which is incorporated
ing washed laundry, and it is reported in the patent that herein by reference. Also incorporated herein by refer
the presence of the anionic surfactant (detergent) unex ence is the disclosure of U.S. Pat. No. 4,000,077, in
 4,919,839
3 4
which anionic and cationic surfactant reactants that can may be directly bonded to the quaternary nitrogen
produce complexes are also described. Accordingly, instead of being bonded to it through the lower alkyl.
the descriptions of such surfactant materials in this spec In addition to the cationic compounds previously
i?cation may be somewhat abbreviated. mentioned, other suitable cationic surfactants include
The anionic surface active agents (or surfactants) will 5 the imidazolinium salts, such as Z-heptadecyl-l-methyl
preferably be detergents and will normally include a l-[(2-stearoylamido) ethyl]-imidazolinium chloride; the
lipophilic anionic moiety of relatively high molecular corresponding methyl sulfate compound; 2-methyl- 1-(2
weight, which lipophile will preferably be or will in hydroxyethyl)-l-benzyl imidazolinium chloride; 2
clude a long chain alkyl or alkenyl group of at least 10 coco-l-(2-hydroxyethyl)-l-octadecenyl imidazolinium
or 12 carbon atoms, such as 10 or 12 to 18 or 20 carbon chloride; Z-heptadecenyl-l-(2-hydroxyethyl)-l-(4
atoms. Such anionic detergent will also usually include chlorobutyl) imidazolinium chloride; and Z-heptadecyl
a sulfonic, sulfuric or carboxylic acidic group, which, l-(hydroxyethyl)-l-octadecyl imidazolinium ethyl sul
when neutralized, will be a sulfonate, sulfate or carbox fate. Generally, the imidazolinium salts of preference
ylate, with the cation thereof preferably being alkali will be halides (preferably chlorides) and lower alkyl
metal, ammonium or alkanolamine, such as sodium, 15 sulfates (alkosulfates), and will include hydroxy-lower
ammonium or triethanolamine. Although the higher alkyl substituents.
alkyls of such detergents may be of 10 to 20 carbon The various anionic and cationic surfactants that are
atoms, normally they will be of 12 to 18 carbon atoms, useful for making the novel and unexpectedly bene?cial
preferably 12 to 16 carbon atoms and more preferably complexes of this invention will include hydrophilic
moieties or substituents in one or both such surfactants
12 to 14 carbon atoms (which may be designated in this
speci?cation as C1244 alkyls). so that the complex made will be of a moderate water
Examples of operative anionic surfactants include solubility and of a desirable hydrophilic-lipophilic bal
ance. In other words, one or both of the anionic and
sodium dodecylbenzene sulfonate; sodium linear tride cationic surfactants should include sufficient hydro
cylbenzene sulfonate; potassium octadecylbenzene sul philic function, apart from the sulfate, sulfonate or car
fonate; sodium lauryl sulfate; triethanolamine lauryl boxylate of the anionic surfactant and apart from the
sulfate; ‘sodium palmityl sulfate; sodium cocoalkyl sul halide or lower alkosulfate of the cationic surfactant, so
fate; sodium tallowalkyl sulfate; sodium ethoxylated that the complex will have moderate hydrophilic prop
higher fatty alcohol sulfate, which will usually be of l erties. Thus, the complex will be hydrophilic enough to
to 20 ethylene oxide groups per mole, such as sodium form the desired microemulsions of the invention and
lauryl monoethoxy ether sulfate, sodium lauryl die yet, because it will not be excessively hydrophilic or
thoxy ether sulfate and sodium C1244 alkyl diethoxy. water, soluble, will still be lipophilic enough to promote
ether sulfate; sodium C14-17 Paraf?n sulfonate; sodium oil solubilization in the microemulsion, thereby improv
ole?n sulfonate (of 10 to 20 carbon atoms in the ole?n); ing the capability of such microemulsion for removing
sodium cocomonoglyceride sulfate; and sodium coco 35 heavy deposits of greasy soil from substrates.
tallow soap (1:4 cocoztallow ratio). Preferred anionic It has been experimentally determined that when the
detergents for complexing with the cationic surfactants solubility of the complex in water is in the range of 30 to
are the ethoxylated higher fatty alcohol sulfates, in 40% (30 to 40 g./ 100 g. of the aqueous solution), e.g.,
which the salt forming cation is preferably alkali metal, 35%, the microemulsions of this invention that are
more preferably sodium. made will have a significantly improved capability of
As with the anionic surfactants, the cationic surfac removing fatty soils from substrates. Broader ranges of .
tants useful to make the present complexes may be any operativeness are 20 to 50%, 10 to 60% and 5 to 70%.
suitable such compounds which react with the anionic It is considered that solubility in water of the complex is
surfactants to form the desired complexes. Preferable more closely related to greasy soil removing capability
among such cationic surfactants are quaternary ammo 45 than are hydrophilic-lipophilic balance numbers
nium salts, in which at least one higher molecular (HLB’s) of such complexes.
weight group and two or three lower molecular weight To obtain the desired water solubility of the invented
groups are linked to a common nitrogen atom to pro complex, hydrophilic moieties and hydrophilic substitu
duce a cation, and wherein the electrically balancing ents, such as ethylene oxide or glycols, glycosides and
anion is a halide, acetate, nitrite or lower alkosulfate, 50 hydroxy-lower alkyls may be present in both the surfacl
such as bromide, chloride or methosulfate. The higher tant reactants that form the complex (but will not be the
molecular weight substituent on the nitrogen is often a complex-forming groups or “heads” of such surfac
higher alkyl group, containing 10 or 12 to 18 or 20 tants). Preferably, such hydrophilic groups will be eth
carbon atoms and the lower molecular weight substitu ylene oxide, hydroxy-lower (C1-4) alkyl and/or hy
ents may be lower alkyl of l to 4 carbon atoms, such as 55 droxy, in both the anionic and cationic surfactants.
methyl and ethyl, which often are desirably substituted, Excellent results have been obtained with ethylene
as with hydroxy groups. One or more of said substitu oxide groups in the anionic surfactant and with hydrox
ents may include an aryl moiety or may be replaced by yethyl groups in the cationic surfactant, but good re
an aryl, such as benzyl or phenyl. Among the possible sults can also be obtained with only one of the surfac
lower molecular weight substituents are also lower 60 tants being of such “hydrophilized” type. The ethylene
alkyls of l to 4 carbon atoms, such as methyl and ethyl, oxide or ethylene glycol ether groups in the preferred
which are substituted by poly-lower alkoxy moieties, anionic surfactants are desirably located in the other
such as polyethoxy moieties bearing a hydroxyl end wise lipophilic chain of such surfactant, which is nor
group, and being of the general formula R(X),,OH mally a higher alkyl, and the hydroxyethyl groups are
wherein R is C1_4 alkyl bonded to the nitrogen, X is 65 on the quaternary nitrogen of the cationic surfactant.
CHZCHZO, CH(CH3)CH2O or CHzCH2CH2O, and n is Experimentation has established that excellent micro
from 1 to 20. Alternatively, one or two of such lower emulsion forming and grease removal are obtained
poly-lower alkoxy moieties, having terminal hydroxyls, when the total of ethylene oxide and hydroxy-lower
 4,919,839
5 6
alkyl (hydroxyethyl) groups in the complex is about 4. In the anionic detergent portion of the invented mi
Thus, such total is desirably in the range of 3 to 5 or 3 croemulsions, when such detergent is a mixture of so
to 7 and more preferably two or more of such groups dium C1447 paraf?n sulfonate and sodium higher alkyl
will be in each of the anionic and cationic moieties and diethoxy ether sulfate, the proportion of such paraf?n
often will be about equally divided between them. sulfonate to such ether sulfate will desirably be in the
However, in some instances all of the hydrophilic moi range of 3:2 to 5:1, preferably being in the range of 2:1
eties and substituents may be in either the anionic or the to 4:1 and most preferably being about 3:1. At such
cationic surfactant reactant, but not in both. The num ratios, especially the most preferred ratio, excellent
ber of hydrophilic substituents on the reactants can also microemulsions are obtained, which exhibit desired
be related to the number of carbon atoms in the hydro grease removing effects when employed in neat form;
philic chains of the reactants. Thus, four ethoxy groups when they are diluted in water such systems develop a
satisfactorily hydrophilize 26 carbon atoms in such desirable micellar structure and perform satisfactorily in
chains or the number of ethoxies may be about 15% of dishwashing applications.
the number of lipophile carbon atoms, and suitable The co-surfactant of the present microemulsions,
ranges are from 12 to 20% and 10 to 25%. A highly which signi?cantly aids in the formation of such micro
preferred complex is that of sodium lauryl diethox emulsions, will be a polypropylene glycol of 2 to 18
yether sulfate and cocoalkyl-bis(2-hydroxyethyl) me propoxy units, a monoalkyl ether of a lower glycol or
thylammonium chloride. Of course, similar combina polyalkylene glycol of the formula RO(X),,H, wherein
tions of surfactant reactants, such as sodium tetradecyl R is C1_4 alkyl, X is CHZCI-IZO, CH(CH3)CH2O or
tetraethoxy ether sulfate and lauryl (2-hydroxypropyl) CHZCHZO, and n is from 1 to 4, or a monoalkyl ester of
dimethylammonium chloride, and sodium linear tride the formula R1O(X),,H, wherein R1 is C2_4 acyl and X
cyl triethoxyether sulfate and myristyl-bis(2-hydrox and n are as immediately previously described.
ybutyl) ethylammoniurn chloride may also be em Representative members of the mentioned polypro
ployed. The main consideration is that the complex pylene glycol ethers include dipropylene glycol and
resulting should be of both hydrophilic and lipophilic 25 polypropylene glycol having a molecular weight of 200
properties so that it will be of moderate solubility in to 1,000, e.g., polypropylene glycol 400. Satisfactory
water, and will form a satisfactory microemulsion and
glycol ethers and other glycol derivatives include dieth
will effectively remove greasy soil from substrates
ylene glycol mono-n-butyl ether (butyl carbitol), dipro
when employed in neat form. pylene glycol mono-n-butyl ether, dipropylene glycol
The anionic synthetic organic detergent component
30 isobutyl ether, ethylene glycol monobutyl ether (butyl
of the present microemulsion is one which is satisfacto
cellosolve), triethylene glycol monobutyl ether, tetra
rily water soluble and stable in such microemulsions.
ethylene glycol monobutyl ether, propylene glycol
tertiary butyl ether, ethylene glycol monoacetate and
Preferably it is a salt of an anionic detergent acid, which dipropylene glycol propionate. Because it is capable of
salt may be an alkali metal, ammonium or substituted providing stable microemulsions over a broad range of
ammonium salt, such as a sodium, potassium, ammo temperatures, while avoiding any problems related to
nium or triethanolamine salt, or a mixture thereof. Such toxicity and/or environmental safety, another ether
anionic detergent will normally include an essentially based on dipropylene glycol that is particularly pre
lipophilic long chain moiety and an acid moiety. Of the ferred as a co-surfactant is dipropylene glycol mono
acids, sulfuric, sulfonic and carboxylic acids are pre methyl ether, which is commercially available.
ferred, and the long chain lipophile will normally be a The organic solvent component of the present micro
higher linear alkyl or higher linear alkylbenzene. A emulsions may include solvents that have polar proper
preferred anionic detergent is sodium paraffin sulfonate ties, often in minor proportions, but the preferred or
wherein the paraf?n is of 12 to 18 carbon atoms, prefer ganic solvent is a suitable oil, such as a non-polar oil,
ably 14 to 17 carbon atoms. Preferably, a mixture of 45 which is usually a hydrocarbon, of 6 to 16 carbon atom.
anionic detergents will be employed, with one being Such hydrocarbon is normally a normal paraf?n or an
substantially more hydrophilic than the other. At least a isoparaf?n, and of these those of 10 to 12 carbon atoms
portion of the total anionic detergent content will desir are preferred, and most preferred are the C1041 isopar
ably be a detergent having one or more hydrophiles in af?ns. Such materials are available commercially from
the chain thereof. The higher alkyl of such detergent 50 Exxon Corp. under the trade name Isopar H. In addi
will normally be of a carbon content in the range of 10 tion to such hydrocarbons, terpenes and similar per
to 20, preferably 12 to 18. The hydrophile in the chain fume materials may be employed, as described in British
will preferably be ethoxy and the salt forming cation patent speci?cation No. 2,190,681, which was referred
will preferably be sodium. Thus, sodium higher alkyl to earlier. Other useful hydrocarbons are heptane, oc
ethoxy ether sulfate wherein the number of ethoxy tane and nonane but also included are those of cyclic
groups present is in the range of l to 10, preferably 1 to structure, such as cyclohexane. Among other solvents
5, e.g., sodium C1244 alkyl diethoxy ether sulfate, is a that are useful are the C14, acyl esters of CH8 alcohols,
preferred anionic detergent, and is the same as the ani and/or the C743 acyl esters of CH; alcohols. Such com
onic surfactant reactant that forms the desired complex, pounds may be considered as representative of the
which appears to aid in production of stable and effec 60 groups of useful oils of polar properties, and are pre
tive microemulsions. Although the described combina ferred in such group because of their similarity in struc
tion of anionic detergents is highly preferred it is within ture to fats and oils that are intended to be removed
the invention to utilize others of the well known class of from substrates by the invented composition.
anionic detergents, and combinations thereof, including In addition to the recited components of the composi
sodium linear tridecylbenzene sulfonate, sodium cocoal 65 tions of the present invention there may also be present
kyl monoglyceride sulfate, triethanolamine lauryl sul adjuvant materials for dishwashing and other detergent
fate, potassium higher ole?n sulfonate, and potassium compositions, which materials may include foam en
cocate (soap), and hydrophilized modifications thereof. hancing agents, such as lauric myristic diethanolamide,
 4,919,839
7 8
foam suppressing agents(when desired), such as higher stability and cleaning action against greasy soils when
fatty acids and higher fatty acid soaps, preservatives applied in neat form. In diluted form, such ratios also
and antioxidants, such as formalin and 2,6-ditert. butyl result in improved performances. Also important for
p-cresol, pH adjusting agents, such as sulfuric acid and the same reasons is the proportion of total anionic deter
sodium hydroxide, perfumes, colorants, (dyes and pig gentzcomplex, which will normally be in the range of
ments) and opacifying or pearlescing agents, if desired. 2:1 to 25:1, preferably 4:1 to 10:1, and more preferably
Although sometimes small proportions of builder salts is 6:1. On a 100 parts basis, 75 to 95 parts of the anionic
may be added to the present compositions for their detergent mixture will be present with 5 to 25 parts of
building functions, normally such will be omitted be the complex, and a preferred composition will include
cause they tend to produce cloudy emulsions and can 85 to 15 parts, respectively.
interfere with desired oil solubilizing properties of the The solvent (oil) content will rarely exceed 10% but
microemulsion. In addition to the mentioned adjuvants, in some situations higher proportions can be incorpo
sometimes it may be desirable to include water soluble rated and the microemulsions made will be stable and
metal salts, such as chlorides and sulfates of magnesium useful, especially in neat form. The proportion of co
and aluminum, to react with the anionic detergent to surfactant to solvent is relevant to cleaning and stability
convert it to such a metal salt, which may improve of the invented microemulsions and it is desirable for
performance of the invented compositions. However, that ratio to be in the range of 1:4 to 4:1, preferably 1:2
such salts are not required components of such compo .to 2:1.
sition and normally work best at acidic or neutral pH’s, To make the invented microemulsions various tech
if employed. The bivalent or multi-valent metal salts 20 niques may be employed. However, in almost all of
will normally not be present in any substantial excesses these it is desirable to added the solvent component last,
over their stoichiometric proportions with respect to at which time the desired microemulsion will usually
the anionic detergent(s). form spontaneously at about room temperature (20° C.)
The proportions of the various components of the or at elevated temperature (usually up to 50‘ or 60° C.).
invented microemulsions will be chosen to obtain the 25 Any adjuvants that are present may be added before or
desired properties in such compositions. Thus, the pro after microemulsion formation, sometimes depending
portion of anionic detergent present will be a satisfac on their nature, but in many cases it will not matter
tory cleaning proportion, sufficient, especially when the when they are added, because the order of addition will
microemulsion is diluted, to release greasy (fatty) de have little effect on the microemulsion, which is ther
posits found on dishes. The proportion of complex will 30 modynamically stable. Desirably, to make the present
be that which helps to form the microemulsion and emulsions a solution will ?rst be made of the synthetic
which improves its capability for taking up a greasy detergent(s) in water and the co-surfactant will be dis
soil, especially when the composition is applied neat to solved in such solution. Following a different proce
surfaces to be cleaned. The co-surfactant signi?cantly dure, the co-surfactant may be added first, followed by
helps the anionic detergent, aqueous medium and or 35 the anionic detergent(s). The complex, which may have
ganic solvent to form a stable microemulsion. Water been made previously by reaction of the anionic and
acts as the continuous medium for the microemulsion, cationic surfactant, either in aqueous medium, or in
and the organic solvent, very preferably a hydrocarbon, molten state, may then be added and the organic sol
forms the dispersed phase of the microemulsion, which vent, preferably a hydrocarbon, may then be admixed
is in very finely divided form, and such oil effectively to form the microemulsion. Alternatively, the complex
assists in incorporation in such dispersed phase of the may be made in aqueous solution or by reacting the
greasy soil that the present compositions remove from surfactant components in molten state and may be ad
dishes. mixed with the water, anionic detergent(s) and co-sur
In percentages, the proportions of components for factant, followed by admixing in of the organic solvent.
the invented microemulsion will usually be 1 to 10% of 45 It is also possible and very often preferable to react the
the complex, 20 to 40% of the anionic detergent, l to cationic surfactant in formula amount of water with
5% of the co-surfactant, 1 to 5% of the organic solvent excess ethoxylated anionic detergent and then admix
and 30 to 70% of water, with preferred ranges being 2 the non-ethoxylated anionic detergent, co-surfactant
to 8%, 25 to 35%, 2 to 4%, 2 to 4% and 50 to 70%, and oil. It is not normally considered to be desirable to
respectively. A speci?c preferred formula includes 50 react the anionic and cationic surfactants in the pres
about 5% of the complex, about 28% of the anionic ence of other components of the final microemulsion
detergent, about 2.5% of the co-surfactant, about 2.5% composition, and the presence of any non-hydrophil
of the organic solvent and about 62% of water (when ized anionic detergent will especially be avoided.
no adjuvants are present). Any adjuvant(s) present will The microemulsions made and utilized in the present
normally not exceed 10%, preferably will be limited to 55 invention are of the oil-in-water type, in which a lipo
5%,and more preferably are held to 1 or 2%. philic liquid phase is dispersed in a continuous hydro
In the anionic detergent component(s) of the formula philic phase in the presence of the anionic surfactant,
it will normally be desirable to include a mixture of anionic-cationic complex and co-surfactant. The dis
different anionic detergents, one of which will include persed phase is in the form of droplets or particles with
hydrophilic moieties or substituents in/on the lipophilic 60 an average diameter no more than 3,200A, typically
chain thereof. Preferably, such “hydrophilized” anionic being between 100 and 1,000 angstroms. Some micro
detergent will be l/5 to 1/ 1 of the content of the other emulsions containing both lipophilic and hydrophilic
“non-hydrophilized” anionic detergent. In other words, components also can form mesomorphic arrangements,
the proportion of paraffin sulfonate or other such ani the order of which does not persist for longer distances
onic detergent to “hydrophilized” anionic detergent 65 than about 0.16 micron. When the elementary structural
will be in the range of 1:1 to 5:1, preferably 2:1 to 4:1 entities of the dispersed phase (swollen migelles) are of
and more preferably about 3:1, e.g., 3:1. Such ratios are an average diameter greater than 3,200A the liquid
desirable so that the ?nal microemulsion is of improved composition is no longer- a microemulsion but is an
 4,919,839
9 10
emulsion, which can often be turbid and thermodynami CaCOg). The concentration will preferably be in the
cally unstable (whereas the microemulsion is clear and range of 0.1 or 1 to 100%, more preferably 10 to 100%,
very often is thermodynamically stable). When such for pre-spotting of greasy stains on laundry, for remov
elementary strugtural entities of the dispersed phase are ing thick greasy deposits from dishes and other hard
below about 40A a true (but not necessarily ideal) solu surfaces by sponging, and for soaking baked-on greasy
tion is present. Thus, the dispersed phase in the present deposits and chars to remove them from hard surfaces.
microemulsions is one wherein the elementary struc For such various cleaning applications the temperature
tural entities are of an average diameter in the range of of the microemulsion or the dilute microemulsions will
40 to 3,20OA, typically 100 to 1,000A. normally be in the range of 15° to 90° C., preferably 20°
The present microemulsions are clear and stable in 10 to 70° C., and often will be in the range of 20°, 25° or 30°
neat form and are capable of being diluted with water to to 40° or 50° C., especially for hand dishwashing. To
normal dishwashing concentrations without impairing assist in cleaning of baked-on greasy deposits from
the micellar dispersion of the organic solvent. Because items, such as from roasting or frying pans, after soak
the microemulsion form increases the surface area of the ing, such items may be rubbed with plastic (nylon),
lipophilic constituent it is considered that it contributes metal mesh or steel wool scrubbing pads to speed re
signi?cantly to the utility of the present compositions in movals of the deposits from them.
neat form. It is also important that the micellar disper The advantages of the invention have been referred
sion form be maintained for use when diluted with wa to previously and some have been described in some
ter. The surfactant, co-surfactant, solvent and water are detail, but a fuller description follows. The present mi
important to produce a microemulsion. The presences 20 croemulsions include an anionic detergent as the pri
of the anionic surfactant or detergent (especially the mary detersive component but although such anionic
combination of ethoxylated and non-ethoxylated ani liquid detergent is an excellent dishwashing detergent in
onic detergents), moderately water soluble complex and dilute form, it had previously usually been ineffective in
co-surfactant all help to form and maintain a highly concentrated or neat form. However in the present
stable microemulsion. Additionally, the presence of the 25 compositions it is effective when employed as is. This is
complex signi?cantly improves the capability of the attributable to both its microemulsion form and the
microemulsion, in neat form, to remove fatty deposits presence of the anionic-cationic surfactant complex,
from substrates, whether such are hard surfaces, such as which, although essentially lipophilic in nature, is still
those of dishes, or soft surfaces, such as, those of laun hydrophilic enough (being of limited or moderate water
dry. All the recited components coact with each other solubility) not to signi?cantly adversely affect the deter
in the proportions mentioned to produce a microemul gency of the anionic detergent in the composition. The
sion composition of improved and desired properties. In presence of the complex, together with the co-surfact
such compositions the proportion of water is the great ant and solvent or oil, does signi?cantly improve the
est, followed by that of the anionic detergent (mixture) grease removing power of the invented microemulsion
and those of complex, co-surfactant and solvent, which liquid detergent when it is employed in concentrated
are less than that of the anionic detergent(s). form. The invented microemulsion composition also has
The present compositions may be successfully em a greater capacity for solubilizing greasy soils, such as
ployed without dilution to remove extremely heavy triolein (the standard test fat/oil), and dissolves them
deposits of greasy fats and oils from dishes, pans and faster than do the conventional anionic detergent of
other hard surfaces, before normal hand dishwashing in 40 equivalent active ingredient (A.I.) content.
a dishpan or sink, or they may be employed to “dis The preferred compositions of the invention are supe
solve” soils in pre-spotting treatments of laundry items rior in cleaning power to similar compositions in which
that have been stained with greasy soils. Previously, the anionic and cationic surfactants (like sodium lauryl
light duty liquid detergent compositions based on ani sulfate and cetyl trimethyl ammonium bromide) that
onic detergents were notably deficient as pre-spotting 45 react to form a complex are more hydrophobic or lipo
agents. Thus, the present microemulsions are the ?rst philic in nature. Although such “control” compositions
light duty liquid detergents that are useful in neat form can be of similar stability and properties with respect to
as cleaners for hard surfaces and as laundry pre-spot oil solubilization capacity and time for effecting such
ters, and are useful in diluted form for hand (non solubilization, in neat form, the microemulsions contain
machine) dishwashing. They can be applied in neat ing such more hydrophobic or lipophilic control com
form to extremely greasy dishes, roasting pans with plexes, which actually behave like oils, being structur
baked on greasy deposits and residues, ovens, greasy ally equivalent to larger hydrocarbon molecules, as a
kitchen range hoods and tiles, and greasy walls, to re first approximation, are less useful as cleaning agents
move greasy deposits from them. Applications may be when in diluted form (see Example 4).
by means of a sponge or cloth, or by soaking, for the To sum up, the invented compositions are better than
more adherent deposits. Dilute forms of the invented prior art and control compositions with respect to the
microemulsions may be employed and will still be mi sum of cleaning power in neat form, cleaning ability in
croemulsions, with that term indicating that the organic dilute form, and stability . Because the microemulsion
solvent remains disposed inside the micelles. In dilute state is important to the success of the invented compo
form one part of the invented microemulsion may be sitions as cleaning agents, better stability results in bet
diluted with about 1 to 1,000 parts of water so that the ter cleaning, in addition to the desirable effect on ap
concentration thereof will be in the range of 0.1 to 50%, pearance that is obtained by maintaining the composi
but preferably the concentration will be in the range of tions in microemulsion form.
0.1 to 10%, and more preferably 0.1 to 1% for ordinary The following examples illustrate but do not limit the
hand dishwashing, and excellent cleaning of dishes will 65 invention. Unless otherwise indicated all parts are by
be obtained, similar to that of commercial dishwashing weight and all temperatures are in °C. in such examples
detergent compositions. Such excellent cleaning of and elsewhere throughout this specification, and in the
dishes is even obtainable in hard water (300 p.p.m., as claims.
 4,919,839
11 12
(orl0.09 parts of Texapon N70) and 21.20 parts of the
EXAMPLE 1 paraffin sulfonate (35.33 parts of Marlon PS 60)are dis
solved in water and are mixed with the complex, includ
EXLMPQL ing the water from the reactant solutions, after which
Percent LII the co-surfactant, adjuvants and solvent are admixed, as
Components (by weight) in Example 1. The result is a light duty microemulsion
ETHOQUAD C/12 (Akzo Chemical Co.) 3.12 liquid detergent composition like that of Example 1,
coco-bis(2-hydroxyethyl) methylammonium with the same properties.
chloride (75% active ingredient [A.I.]) In one change in the manufacturing procedure, the
TEXAPON N70 (Henkel & Cie.) sodium lauryl ether 13.87
sulfate having 2 ethoxy units per mole cationic and anionic surfactant reactants are melted, in
(70% A1.) the presence of an ionizing proportion of water, and are
MARLON PS 60 (Huls AG) sodium C1447 paraffin 35.33 reacted in such molten state, after which the complex
sulfonate (60% Al.) made is mixed with the aqueous solution of anionic
DOWANOL DPM (Dow Chemical Corp.) 2.50
dipropylene glycol monomethyl ether (100% A.I.) detergents, which solution contains the formula propor
ISOPAR H (Exxon Corp.) C1041 isoparaf?n 2.50 15 tion of water, and the other components are subse
(100% A.l.) - ' quently admixed with the resulting solution.
Adjuvants (dye, perfume, preservative) q.s. When tested in the manner described for the micro
Water balance
100.00
emulsion of Example 1, similar results are obtained.
20 EXAMPLE 3
A light duty liquid detergent in microemulsion form (Comparative)
is made by dissolving the Ethoquad C/ 12 and the Texa
pon N70 in approximately equal proportions of the A control laboratory test was run, in which the in
water and then mixing such aqueous solutions at about vented light duty microemulsion liquid detergent com
room temperature (25° C.) to form the corresponding 25 position of Example 1 (that of Example 2 could be used
cationic-anionic surfactant complex in water containing interchangeably) was compared for fat solubilization
the excess of Texapon N70. (Both the Ethoquad C/l2 characteristics with a control light duty liquid detergent
and Texapon N70 are of similar higher alkyl groups, composition containing 24.94% (A.l. basis) of sodium
with the cocoalkyl of the Ethoquad C/ 12 and the “lau C14.” paraffin sulfonate and 8.31% (also on an A.I.
ryl” of the Texapon N70 being C1244 alkyls). The Mar 30 basis) of sodium C1244 alkyl diethoxy ether sulfate,
lon PS 60 is admixed with the complex and excess Texa which control is essentially like commercial dishwash
pon N70 (in water), followed by additions of the ing detergent compositions. The control detergent com
Dowanol DPM and the adjuvants (which are desirably position includes more of the mentioned anionic deter
pre-dissolved in small proportions of the water compo gents than the experimental composition to compensate
nent). Subsequently, the Isopar H is admixed and the 35 for the omission of the complex, and the co-surfactant
microemulsion is formed spontaneously. (The adju and solvent are omitted
vants, which will total less than 1% of the product, may In the test run incremental quantities of triolein, (gly
be admixed at any suitable time before the Isopar H, and col trioleate), a standard test fat, are added to the com
sometimes may be added afterward). The microemul positions being tested, which are at 25° C., with con
sion is clear. trolled agitation, until saturation thresholds are ob
The microemulsion formed is employed to remove served (when the solutions turn turbid). Times required
beef fat deposits from dishes, greasy and sooty deposits to solubilize each increment of triolein are recorded so
from painted walls, and oily stains from work clothes in that a “kinetic curye” can be drawn. However, because
prespotting operations, prior to normal automatic wash the differences between the solubilizing properties of
ing of laundry, and is found to be very satisfactory in such compositions are so great, such comparative
such applications, being unexpectedly better than aque curves will not be given here, it being considered suffr
ous control compositions of the same and even greater cient to state that 100 grams of the experimental compo
concentrations of anionic detergent, such as over 33%, sition solubilized 6.4 grams of triolein in 72 minutes
on an Al. basis. It is also effective in softening burnt-on whereas 100 grams of the control composition took
greasy soils on ovens and on roasting pans so that such 50 three hours to solubilize 1.8 grams of triolein. The ex
are more readily removed by rubbing with a cleaning perimental composition took only 12 minutes to solubi
pad. Furthermore, when the invented microemulsion is lize 1.8 grams of triolein, clearly establishing that the
diluted with water to a normal washing concentration experimental formula much more rapidly solubilizes the
of 1.25 g./l., it is found to be excellent for hand washing triolein and has a greater capacity for solubilizing it,
of dishes, being as effective as commercially successful 55 than does the control.
light duty liquid detergents in such applications. The laboratory data given above indicate that the
invented compositions will function much more effec
EXAMPLE 2 tively in neat form as pre-spotters to remove oily stains
The cationic/anionic complex of Example 1 is made from laundry, and as cleaners for walls, ovens, baking
by reacting aqueous solutions of the Example 1 surfac 60 pans and other hard surfaces which may contain depos
tant reactants, with the amounts of surfactants present its of fatty materials, compared to control light duty
being 2.34 parts and 2.65 parts, respectively, on a 100% liquid detergent compositions, when both are employed
Al. basis (or 3.12 parts and 3.79 parts, ‘respectively, on in neat form. Such laboratory results are confirmed by
an “as is” basis). The reaction is carried out at about 25° comparative testings of the experimental and control
C. and the product is a moderately water soluble com 65 compositions in the applications described above.
plex of the cationic and anionic surfactants which dis Comparative testings of the described experimental
solves to the extent of about 35% (35 g./ 100 g. of solu and control compositions to determine dishwashing
tion). 7.06 Parts of the sodium lauryl ether sulfate characteristics were also carried out. In such tests, a
 13
4,919,839
14
standardized greasy soil solution is sprayed uniformly vants were omitted. Such formulas are given below,
on test substrates (white Formica ® tiles) and allowed with all percentages being on an A.I. basis.
to dry at room temperature for 30 minutes, after which
they are tested, employing a Gardner® Testing Ma
chine, which applies a moistened sponge containing a Percent {by weight!
measured amount of light duty liquid detergent compo Components A B C D
sition to such tile, in reciprocating strokes. The strokes Coco-bis(2-hydroxyethyl) — 2.34 — 2.34
are counted until a path has been cleared by the sponge methylammonium chloride
through the soiled area on the tile. An oil soluble dye in Sodium lauryl diethoxy ether 8.31 9.71 8.31 9.71
sulfate
the greasy soil facilitates noting of such endpoint. Based 10 Sodium C1447 paraf?n 24.94 21.20 24.94 21.20
on testing experience a difference of ?ve strokes for sulfonate
compared detergent compositions is signi?cant. Dipropylene glycol mono- — — 5.00 5.00
In the test described the experimental formula cleared methyl ether
a path through the soiled area after seven strokes C10.“ isoparaf?n — —- 5.00 5.00
Water bal- bal- bal- bal
whereas the control composition required 18 strokes, ance ance ance ance
showing clear superiority in such dishwashing applica 100.00 100.00 100.00 100.00
tions for the experimental formula. Such result is con
?rmed by actual hand dishwashing comparisons by
experienced testers. In the formulas of Columns B and D the complexes
EXAMPLE 4 20 are made by the reaction of 2.34 parts of the cationic
surfactant with 2.65 parts of the sodium lauryl diethoxy
(Comparative) ether sulfate. Thus, the formula of Example 5B differs
This example compares hand dishwashing capabili from that of Example 5A by including applicants’ pre
ties of the preferred experimental light duty microemul ferred complex and Formula 5D differs from Formula
sion liquid detergent composition of Example 1 with a 25 SC in the same manner.
“control” composition which is like it in all respects In the laboratory the products of the four formulas
except that the complex is made from 2.65% of sodium were tested for oil holding capacity and it was found
lauryl sulfate and 2.34% of cetyl trimethyl ammonium that such capacities were 1.8, 1.3, 3.6 and 4.6 g./ 100 g.
bromide, both percentages being on an A.I. basis. The of neat liquid detergent composition, respectively.
microemulsions made are tested for dishwashing capa 30 These data show that in the invented microemulsions,
bility by a laboratory test that has been proven to be which contain the described complex, co-surfactant and
accurate. In such test the light duty liquid dishwashing solvent, the combination of components causes a sur
detergent composition is dissolved in water of 300 prising increase in soil solubilization by the neat deter
p.p.m., hardness, as CaCO3, to the extent of 1.25 g./l., gent compositions, which makes them more effective as
with the water being at a temperature of about 35° C. 35 pre-spotting agents and for removing heavy deposits of
The solution of dishwashing detergent is subjected to a fatty soils from hard surfaces. Note that the data indi
controlled mechanical action and such agitation is con cate that one would expect a diminution in oil holding
tinued throughout the test, while a standard greasy soil capacity because Formula 5B holds less oil than For
(Crisco ® shortening) is added to the “dishwater”. The mula 5A, but surprisingly, in the invented microemul
end point is that amount of such grease which causes 40 sion (of Formula 5D), the oil holding capacity is in
disappearance of the foam on the surface of the water. creased over that of the 5C formula. Such ability of the
Such amount is correlatable with the number of dishes neat microemulsion in the present invention to remove
(mini-plates) which can be satisfactorily washed by the fatty soils from surfaces can be veri?ed by actual com
detergent composition being tested. parative testing for pre-spotting and cleaning character
For the (experimental) microemulsion of Example 1 45 istics of the respective formulas.
this test indicates that 43 mini-plates can be washed
EXAMPLE 6
satisfactorily whereas the “control” microemulsion
containing the “control” complex can wash only 28 In variations of the formula of Example 1 different
mini-plates. Experience has indicated that a difference complexes within the invention, having 3 to 6 hydro
of about four mini~plates is signi?cant and therefore it is philizing groups, as described in this speci?cation, are
clear that the experimental microemulsion is signi? substituted for the Example 1 complex, other ethoxyl
cantly better for washing greasy deposits from dishes ated anionic detergents, described in this speci?cation,
than is the “control” composition. Such results are veri are employed in place of the sodium lauryl ether sulfate
?able by actual use testing and are attributed to the and other anionic detergents, described in this speci?ca
presence in the invented compositions of the complex, 55 tion, are substituted for the C14_17 paraf?n sulfonates,
which includes enough “hydrophilized” substituents or and essentially the same types of results are obtainable.
moieties so that it is moderately water soluble. Similar When proportions of the components are varied :10,
results are obtainable when other such moderately :20 and i30%, while remaining within the ranges
water soluble complexes are employed in the present given in this speci?cation, the resulting microemulsions
formulations, such as those of 3 or 5 hydroxyethyl or 60 will also have the desirable properties described for
oxyethyl groups in the complex, and wherein the total compositions like that of Example 1. Similarly, other
number of carbon atoms in the lipophilic groups is in the co-surfactants may be substituted and other solvents
range of 24 to 32. may be employed, as were described, and in the differ
EXAMPLE 5 ent proportions previously mentioned, and similar good
65 results are obtained. -
The fat solubilization characteristic test of Example 3 In further variations of the invention the solubility in
was run on four detergent compositions which are vari water of the complex may be adjusted by utilizing mix
ations of the Example 1 formula, but in all cases adju tures of complexes in the speci?cation, with some being
 4,919,839
15 16
more hydrophilic and some being more lipophilic than is in the range of 5 to 25 parts of complex to 75 to 95
that illustrated. In variations, although not preferred, parts of anionic detergent mixture.
the desired water solubility of the complex may be 3. A liquid detergent composition according to claim
obtained by mixing complexes which are of greater and 2 which comprises about 5% of the complex, about
lesser water solubilities than the desired complexes of 28% of the anionic detergent, which includes about
this invention, with some or all being too water soluble 21% of sodium C14_17 paraf?n sulfonate and about 7%
or not water soluble enough. Of course, in all such of sodium C12_14 alkyl diethoxy ether sulfate, about
instances one of skill in the art will understand how to 2.5% of dipropylene glycol monomethyl ether and
make the operative compositions within the present about 2.5% of C10_11isoparaf?n, with the balance being
invention, with their characteristics, and excessive ex water and adjuvants, if any.
perimentation is not required. 4. A process for manufacturing a light duty micro
In the foregoing description and claims when compo emulsion liquid'detergent composition which is useful
nents of the invented compositions are mentioned in the for removal of greasy soils from substrates, both in neat
singular it is to be considered that mixtures are within form and when diluted with water, which composition
such descriptions. comprises 1 to 10% of a complex of sodium C1243 alkyl
The invention has been described with respect to diethoxy ether sulfate and C1244 alkyl-bis(2-hydrox
various examples, illustrations and embodiments thereof yethyl) methylammonium halide, in which such anionic
but is not to be limited to these because it is evident thatand cationic surfactants are in essentially equivalent
one of skill in the art, with the present speci?cation proportions, 20 to 40% of an anionic detergent, which is
before him/her, will be able to utilizev substitutes and 20 a mixture of sodium C1248 paraf?n sulfonate and so
equivalents without departing from the invention. dium C1243 alkyl diethoxy ether sulfate, in which the
What is claimed is: proportion of such paraffin sulfonate to such alkyl die
1. A light duty microemulsion liquid detergent com thoxy ether sulfate is in the range of 2:1 to 4:1, 1 to 5%
position which is useful for removal of greasy soils from
of a co-solvent which is dipropylene‘ glycol mono
substrates, both in neat form and when diluted with 25
water, which comprises 1 to 10% of a complex of so methyl ether, 1 to 5% of an organic solvent which is a
dium C1243 alkyl diethoxy ether sulfate and C1244 C10_12isoparaf?n, and 30 to 70% of water, in which
alkyl-bis(2-hydroxyethyl) methylammonium halide, in composition the ratio of anionic detergent to complex is
which such anionic and cationic surfactants are in essen in the range of 2:1 to 2521, which process comprises
tially equivalent proportions, 20 to 40% of an anionic 30 reacting the anionic and cationic surfactants, in liquid
detergent, which is a mixture of sodium C1243 paraf?n state, to make the complex, after which the complex is
sulfonate and sodium C1243 alkyl diethoxy ether sulfate, mixed with the other components of the liquid deter
in which the proportion of such paraf?n sulfonate to gent composition, with the C1042 isoparaffm being
such alkyl diethoxy ether sulfate is in the range of 2:1 to added last to the mixture of the other such components.
4:1, 1 to 5% of a co-solvent which is dipropylene glycol 35 5. A process according to claim 4 wherein the reac
monomethyl ether, 1 to 5% of an organic solvent which tion of the anionic and cationic surfactants is conducted
is a C10_12isoparaf?n, and 30 to 70% of water, in which at a suitable temperature at which both such reactants
composition the ratio of anionic detergent to complex is are dissolved in water or are in melted form.
in the range of 2:1 to 25:1. 6. A process according to claim 4 wherein the anionic
2. A liquid detergent composition according to claim and cationic surfactants are dissolved in water when
1 wherein the complex is of sodium lauryl diethoxy they are reacted to form the complex, and the complex
ether sulfate and coalkyl-bis-(Z-hydroxyethyl) me so made, in such water solution, is mixed with the ani
thylammonium ammonium chloride, which complex is onic detergent, co-surfactant and solvent, with the sol
about 35% soluble in water, the anionic detergent is a vent being the last of the components to be mixed with
mixture of C14_17 paraf?n sulfonate and sodium C1244 45 the others, whereby the microemulsion forms spontane
alkyl diethoxy ether sulfate in about 3:1 proportion, and ously.
the proportion of complex to anionic detergent mixture. * * * * *

50

55

65