COMPOSITIONS DE MICRO-EMULSION POUR ELIMINER LA SALETE, ET METHODES DE PRODUCTION

SOIL-REMOVAL MICROEMULSION COMPOSITIONS AND METHODS FOR MAKING THEM AND USING THEM

Abrégé anglais

28
ABSTRACT OF THE DISCLOSURE
Disclosed are emulsions made by simple agitation of
about 99.9-20% water and about 0.1-80% progenitor solutions,
the latter containing at least one surfactant, at least one
solvent, and at least one emulsifier, the solvent being of
selected polarity and all the ingredients being of selected
refractive index. Also disclosed are methods of obtaining
emulsions of a desired cleaning ability (which may be targeted
to a specific cleaning task) and cost using a correlation
(polarity/refractive index function) between cleaning ability,
polarity of the solvent and refractive index of the solvent and
other additives.

Revendications

23
WHAT IS CLAIMED IS:
1. An emulsion comprising
(a) 0.1-80% of a progenitor solution comprising
the following ingredients:
(i) 60 to 98% of at least one solvent
(ii) 1 to 20% of at least one emulsifier
surfactant, and
(iii) 1 to 20% of at least one additional
surfactant; and
(b) the balance being 99.9-20% water;
said emulsion having been prepared by simple
addition of the progenitor solution to warm water with ordinary
agitation; said ingredients being selected to yield a polarity
index function (PIF) being defined as <IMG> having a value
at least equal to a previously established critical value
wherein ND is the collective refractive index of the progenitor
solution and P is the collective polarity of said at least one
solvent; said critical value being the PIF value of emulsions
that have an ability to clean at least 60% of a soil, when said
emulsions are subjected to Q-panel testing and containing 10%
of a progenitor solution.
2. A method for cleaning industrial soils from a
substrate comprising the steps of:
(a) applying to said substrate an emulsion having
been prepared by simple agitation of about 0.1-80% of a
progenitor solution and about 99.9-20% water, said progenitor
solution comprising the following ingredients:
(i) 60 to 98% weight of at least one solvent
(ii) 1 to 20% weight of at least one
emulsifier surfactant; and
(iii) 1 to 20% weight of at least one
additional surfactant,
said at least one solvent having collective polarity P
and said ingredients having collective refractive index ND and
said emulsion having a polarity index function (PIF) value

24
greater than a previously established critical value, said PIF
being defined as <IMG>; said critical value being the PIF
value of emulsions that would have the ability to clean at
least 60% of a soil when subjected to Q-panel testing and
containing 10% of a progenitor solution;
(b) contacting said emulsion with said soils for a
period of time sufficient to remove said soils from said
substrate; and
(c) removing the spent emulsion from said substrate.
3. The emulsion of claim 1, wherein said at least one
solvent has a collective polarity of at least about 2.0 and
said progenitor solution has a collective refractive index of
at least about 1.35.
4. The emulsion of claim 3, wherein:
said solvent is selected from the group consisting
of aliphatic, aromatic, terpenic, paraffinic, isoparaffinic and
olefinic hydrocarbons, alcohols and glycol ethers of the
formula CnO(EO)x(PO)yH wherein Cn is an alkyl radical having n
carbon atoms (n is from 1 to 6), EO is a -CH2-CH2O-
(x is an integer from 0 to 4), PO is -CH(CH3)-CH2-O- or
-CH2-CH(CH3)O- (y is an integer from 0 to 4), benzyl alcohol,
alkyloxoalcohol esters of lower aliphatic acids, substituted
glycols of the formula CnO(EO)xCn (with n and x as defined
above), glycols of the formula H(EO)xH and H(PO)yH (wherein EO,
PO, x and y have been defined above) and acetate esters of
glycol ethers and combinations of at least two thereof;
said emulsifier is selected from the group
consisting of cationic, nonionic and anionic emulsifier
surfactants and combinations of at least two thereof; and
said surfactant is selected from the group
consisting of nonionic, cationic, anionic, zwitterionic and
amphoteric surfactants and combinations of at least two
thereof.

5. The emulsion of claim 4, wherein said progenitor
solution comprises 5% of one of a nonionic emulsifier consist-
ing of a mixture of ethoxylated triglycerides with calcium aryl
alkyl sulfonate, an anionic emulsifier consisting of the sodium
salt of alkyl sulfonamido carboxylic acid and a nonionic
emulsifier comprising a fatty acid polyglycol ester.
6. The emulsion of claim 5, wherein said progenitor
solution comprises 7.5% of a cationic surfactant comprising
nonylphenoxy poly(ethylenoxy)ethanol and 7.5% of one of
nonionic surfactant comprising -N-alkyl(C12, C14, C16,)dimethyl
benzyl ammonium chloride and a nonionic surfactant comprising
nonylphenoxy polyethoxy ethanol.
7. The emulsion of claim 6, wherein said solvent
comprises 60% Solvesso 150, 10% butyl carbitol, and 10% Tabs D.
8. The emulsion of claim 6, wherein said solvent
comprises 60% Solvesso 150, 10% Tabs D and 10% benzyl alcohol
and said emulsifier is Emulsogen IT.
9. The emulsion of claim 6, wherein said solvent
comprises 60% Solvesso 150, 10% Tabs D, and 10% isopropyl
alcohol.
10. The emulsion of claim 6, wherein said solvent
comprises 50% Solvesso 150, 10% Tabs D, and 20% isopropyl
alcohol.
11. The emulsion of claim 6, wherein said solvent
comprises 60% Solvesso 150, 10% Tabs D, and 10% methyl car-
bitol.
12. The emulsion of claim 6, wherein said solvent
comprises 60% Solvesso 150, 10% Tabs D, and 10% carbitol.
13. The emulsion of claim 6, wherein said solvent
comprises 50% Solvesso 150, 10% Tabs D, and 20% carbitol.
14. The emulsion of claim 6, wherein said solvent
comprises 40% Solvesso 150, 10% Tabs D, and 30% carbitol.
15. The emulsion of claim 6, wherein said solvent
comprises 70% Solvesso 150, and 10% carbitol.
16. The emulsion of claim 6, wherein said solvent
comprises 60% Solvesso 150, and 20% carbitol.

26
17. The emulsion of claim 6, wherein said solvent
comprises 80% Tabs D.
18. The emulsion of claim 6, wherein said solvent
comprises 80% Solvesso 150.
19. The emulsion of claim 4, wherein said progenitor
solution comprises 5% Icomeen T-15 cationic emulsifier.
20. The emulsion of claim 19, wherein said progenitor
solution comprises 7.5% Hyamine 3500 cationic surfactant and
7.5% of one of Igepal CO-630 nonionic surfactant and Surfonic
N91-8 nonionic surfactant.
21. The emulsion of claim 20, wherein said solvent is
60% Solvesso 150, 10% butyl carbitol, and 10% Tabs D.
22. The emulsion of claim 20, wherein said solvent is
60% Solvesso 150, and 10% butyl carbitol.
23. The method of claim 2 wherein said critical value
is about 6.
24. The method of claim 23 wherein said soil is a
tarsand soil.
25. An emulsion comprising
(a) 0.1-80% of a progenitor solution comprising
the following ingredients:
(i) 60 to 98% of at least one solvent
(ii) 1 to 20% of at least one emulsifier
surfactant, and
(iii) 1 to 20% of at least one additional
surfactant; and
(b) the balance being 99.9-20% water;
said emulsion having been prepared by simple
addition of the progenitor solution to warm water with ordinary
agitation; said ingredients being selected to yield a polarity
index function (PIF) being defined as <IMG> having a value
at least equal to a previously established critical value
wherein ND is the collective refractive index of the progenitor
solution and P is the collective polarity of said at least one
solvent; said critical value being the PIF value of emulsions

27
that would have a substantially increased ability to clean a
soil compared to emulsions having a PIF below said critical
value.

Description

SOIL-REMOVAL ~ICRO~MU1SION COMæOSITIONS
AND M~T~ODS FOR MARING TERM AND ~SING TEEM
FI~LD OF T~E INV2NTION
This invention relates to novel soil-removal emulsion
or microemul~ion compositions of optimized cleaning power which
ar~ made by a method that is simpler than methods fo~ making
emulsion microemulsion or biliquid fo~m polyaphron compositions
currently known in the art. In another aspect, the invention
relates to a method for using such compositions for cleaning
(especially industrial cleaning) purposes.
BACRGROUND OF_T~E INVENTION
Biliquid foams consist of a water-insoluble liquid
"bubble" (or "globule" or "internal phase") trapped within a
film of an aqueous surfactant-containing solution ("external"
or "continuous phase"). Biliquid foams have very small "bub-
bles" (e.g., of a diameter in the order of a micron or even asubmicron). The foams have been recognized for use in cleaning
generally because such bubbles are said to be stable and to
have a relatively large surface/volume ratio.
U.S. Patent 4,486,333 issued December 4, 1984 to Sebba
discloses and claims a method for preparing such a biliquid
foam composition of the polyaphron type (Col. 1, lines 35-47~
for use inter alia in cleaning (Col. 6, lines 31-41) or in mak-
ing dispersions from concentrates of emulsified liquids (Col. 6
lines 23-31) to be used, e.g., in solvent extraction. The '333
polyaprhons have globules of 0.1-10 microns and a PVR (phase
volume ratio, i.e., ratio of volume of discontinuous phase to

volume of lamellar continuous phase) of up to about 50.
First, according to '333, an ordinary gas foam is
prepared using water and~or another hydrogen-bonded liquid such
as an alco~_i or glycol and a water-soluble surfactant;
intermittentiy, a limlted amount of a nonpolar water-immiscibLe
liquid is added and the mixture is agitated to cause the
nonpolar liquid to spread on the foam surface and to form
no~coalescing globules of nonpolar liquid dispersed in a
continuous phase of hydrogen-bonded liquid. Each globule is
encapsulated in a double-surfaced film of surfactant and water.
The nonpolar liquid and the surfactant are said to be selected
to have a spreading coefficient greater than or equal to zero
to permit the nonpolar liquid to initially spread as a thin
sheet on the surfactant-containing aqueous lamellae and then to
break up in-to fragments and globules (of 0.1-10 micron size)
(~ol. 2, lines 55-68).
The total amount of nonpolar liquid thus encapsulated
is between 40 and 98% by volume of the entire composition and
the PVR is at least 1.5 and up to 49 ('333, claim 1~.
The surfactant in '333 can be any anionic, cationic or
nonionic surfactant that would produce a good foam (as long as
it fulfills the above spreading coefficient relationship) and
it is used in an amount preferably at least about 0.3% by
weight of the water (Col. 4, lines 26-32).
The '333 nonpolar liquid also preferably contains a
small (up to 5% by weight) quantity of a soluble nonionic
surfactant that pe~mits the nonpolar liquid to spread on the
aqueous film (Col. 4, lines 50-62).
The '333 invention suffers from the disadvantage that
it is difficult to prepare. Also, there is no attempt to
tailor a particular polyaphron to a given cleaning task other
than as a fuel additive and as a foaming gel although cosmetic
applications are alluded to. See, e.g., '333 Example 4.
U.S. Patent No. 4,606,913 issued to Aronson on August
19, 1986 also concerns high-internal phase emulsions (i.e.,
emulsions in ~hich the internal phase constitutes 74-75% of the

total volume) (Col. 1, lines 9-16). Use in industrial cleaning
applications is disclosed ~Col. 1, line 30).
The '913 patent recogni~es that choice of the emul-
sifier affects the stability of these emulsions and further
proposes the incorporation of "an electrolyte' in the emulsion,
particularly in the aqueous phase to improve stability.
Although any type of electrolyte is said to be suita~le and
trivalent inorganic salts are said to be preferred, only
magnesium sulfate and potassium sulfate are claimed (Col. 9,
10line 9; Col. 10, line 60).
~he emulsifiers generally named in the '913 patent are
conventional, generally nonionic, emulsifiers usually having an
HLB (hydrophilic to lyophilic balance) between 1 and 7 and are
said to include comhinations of sorbitan trioleates; mono- and
15multi-phosphoric esters of oleic acid; polyoxyethylene sorbitol
hexastearate~, ethylene glycol fatty acid esters, glycerol
mono-180 stearates, and sorbitan monooleates; polyoxyethylene
2-oleyl ethers, glycerol/fatty alcohol ethers, esters of
polyalcohols, polyethoxylated 2-oleyl alcohols, synthetic
20primary alcohol ethylene oxide condensates; and mono- and di-
glycerides of fat-forming fatty acids (Col. 5, lines 34-67).
Emulsifiers are said to be present at 5-30% by weight of the
external phase.
The '913 emulsions are said to be prepared by incor-
25porating the emulsifier in the oil phase and the electrolyte in
the aqueous phase and adding the aqueous phase to the oil phase
in small aliquots (not more than 15% of the total oil phase at
a time).
U.S. Patent No. 3,976,582 issued to Douglas on August
3024, 1976 discloses a method for making and stabilizing micellar
systems including microemulsions having maximum zeta potential
for optimizing the recovery of petroleum from shale rock and
other subterraneous formations and minimizing the undesirable
adsorption of surfactant or rock formations.
35The micell~r systems are said to be made in accordance
with known techniques. They comprise 5-20% surfactants (which

can be anionic or cationic), 5-60% hydrocar~on solvent, 10-60
electrolyte-containing water and 1-3.5~ "co-surfactant'~.
Cosurfactants are co-solubilizers i.e., semipolar organic
compounds, prefe-dbly alcohols.
The ~5~2 invention involves measuri~g th~ zeta poten-
tial of a range of micellar systems (varying in aqueous phase
content) (the zeta potential is normalized to account for
differences in electric conductivity) and selecting as optimum
those compositions that have a maximum or near maximum systemic
zeta potential.
U.S. Patent No. 4,542,745 discloses an oil-in-water
emulsion for use in medical ultrasonic probes containing as the
aqueous phase water and alcohol, glycerol or lower alkylene
glycol. Th~ oil phase is silicone fluid and is in droplets of
0.15 microns to 1.5 microns in diameter.
U.S. Patent No. 3,813,345 issued to Urton on May 28,
1974 is directed to a method for reducing the micelle size of
an oil-in-water emulsion (wherein the oil phase contains an
organic solvent, a surfactant and an unsaturated organic
compound soluble in the solvent and the aqueous phase in water)
by adding to such an emulsion a water-soluble resin with a high
number of positive-ion accepting sites and equilibrating this
resin with a positive ion donor to cause it to have the same
sign of (surface) charge (positive or negative) as the micel-
les, there~y causing further subdivision of the micelles. The
disclosed use for such micellar systems is in insecticide
preparations.
U.S. Patent No. 4,472,291 issued to Rosano on September
18, 1984 discloses viscous oil-in-water microemulsions contain-
ing a surfactant, a co-surfactant (emulsifier~ and a secondary
surfactant which has the property of increasing the viscosity
of the microemulsion. The stated uses of such microemulsions
include hard surface cleaners, shampoos, lotions, salves or
creams, car waxes, window cleaners, anti~rust formulations and
floor polishes (col. 5, lines 35-40).

U.S. Patent No. 4,592,859 issued to Smith-Johannsen on
June 3, 1986 is directed to stable suspensions of oil and water
in which the droplets of the discontinuous phase are surrounded
by colloidal particles having a ~eta potential within the range
of +18 to -18 ~V. The suspensions are prepared by adding to
water a combination of surfactants (anionic and cationic) which
form colloidal particles with the requisite zeta potential.
The oil phase is then added. Disclosed uses include cleaning
and polishing compositions, paints, varnishes, impregnants ~or
porous surfaces, cosmetics, cement additives, industrial oils
and waxes. Pharmaceutical and agricultural uses are also
mentioned.
All of the foregoing prior art ~ystems entail compli-
cated and time-consuming formulation methods, and/or are not
suitable for industrial cleaning applications. They require
special equipment and/or calculations and/or sophisticated
additives (such as water soluble resins or electrolytes) as
well as specific methods of addition of the dispersed phase to
achieve the necessary stability and/or globule configuration
(si7e and type of the dispersed phase). As a result, the prior
art systems are expensive and, most important, their use is
confined to specialty applications and they lack the ver-
satility necessary for an industrial-type cleaning composikion.
SUMMARY OF T13E INVENTION
This invention is directed in one aspect to emulsions or
microemulsions prepared by simple agitation of water and
quantities of single-phase compositions thereafter "progenitor
solutions") which contain a combination of at least one
surfactant, at least one solvent and at least one emulsifier,
the solvent ~eing of selected polarity and all ingredients
being of selected refractive index. The resulting emul-
sion~microemulsions ~hereafter simply "emulsions") are highly
stable and have optimal cleaning ability for a variety of in-
dustrial cleaning applications. The foregoing emulsions
contain between about 0.1 and about 80% of progenitor solution.

In another aspect, the present invention provides a
convenient guide (more specifically a function of solvent
polarity and "collective refractive index"--defined below) for
varying any ingre~ient used in the foregoing progenitor
solutions and/or tile amount of such ingredient in a manner
which increases the cleanlng ability of emulsions formed using
the progenitor solutions. The emulsions of the present
invention can thus be optimized for cleaninq ability (and ca~
be targeted to a particular cleaning ta~k) and, if desired,
cost, without using expensive ingredients (such as exotic
surfactants or emulsifiers) without using electrolytes and
without using special equipment (e.g. equipment to measure zeta
potentials).
In yet a third aspect, the present invention is
directed to methods of using the foregoing progenitor solutions
and emulsions for particular industrial cleaning and soil-
removal applications including without limitation removal of
tar and/or oil or greases from sand, industrial equipment and
other inanimate objects, such as removing thick oils and other
soils from hard surfaces (metal, wood, glass concrete, etc.).
DBTAIL~D DE:SCRIPTION OF_TE~E INVENTION
The present invention involves first the formation of
stable "single-phase" progenitor solutions which contain
60 to 98% of an organic solvent (preferably 70 to 90%),
l to 20% of a surfactant or combination of surfactants
soluble in the solvent (preferably S to 20~); and
1 to 20~ of an emulsifier (preferably 2 to 8%)o
~he progenitor solutions are then used to prepare
stable emulsions or microemulsions (water-in-oil or preferably
oil-in-water) having powerful soil-removal capacity. Both the
progenitor solutions and the emulsions made from them can be
formulated to be particularly effective in one or more par-
ticular cleanlng applications. In fact, the emulsions of the
present invention even when produced from a small percentage of
progenitor solution (and containing therefore a small per-
centage of cleaning agents) are particularly effective soil

removal agents. Depending on the choice of solvents, surfac~
tants and emulsifiers, and on the extent of dilution either a
true emulsion or a microemulsion may form from the progenitor
solutions. Typically true emulsions, i.e. opaque milky liquids
result on dilution. ~owever, true microemulsions, i.e.
translucent or almost transparent liquids are also occasionally
observed.
It is well known in the art that in order to have
effective cleaning agents, the soil to be removed must be
penetrated, solvated and removed (sequestrated) from the
substrate and dispersed in a cleaning medium. Penetration and
dispersion are achieved by surfactants. Ionic surfactants
affect the electrostatic propertie~ of the surface to which
they adsorb (or film in which they are resident). Nonionic
surfactants by orienting their hydrophilic moiety into the so-
called Stern layer surrounding a wetted soil particle (assumirlg
the medium is aqueous) promote dispersion and inhibit ag-
glomeration.
Similar principles apply to stabilization of cleaning
emulsion compositions. Stability of an emulsion is promoted by
surfactants which act as emulsifiers. They should have good
solubility in both the agueous and the oil phase. Often,
combinations of surfactants are more effective as emulsifiers
than single compounds, as is well known in the art. See,
generally Surfactants and Interfacial Phenomena, M.J. Rosen,
Wil~y 1978.
The electrical properties of a film or surface are very
important in stability of cleaning emulsions and in effective-
ness of cleaning ability. The electrostatic surface charges
can be measured, but expensive equipment is necessary. A
simpler method for optimi~ing stability and cleaning perfor-
mance of emulsions is provided below by the present invention.
Refractive index and polarity of a liquid provide a
measure of the electrostatic properties of that liquid. The
present inventor was able to correlate the cleaning ability of
various emulsions to the polarity and refractive index of their

ingredients and corresponding concentration of each ingredient
in the progenitor solution. Stabili~ation of the resulting
emulsion is governed by the equilibrium of the surfactants
within the progenitor sol~tion i.e., surfactants/emulsifiexs
are added until they aTe _Dle to completely emulsify or suspend
particles of a liquid in a second immiscible liquid. Thi~ is
done by routine e~perimentation well within the skill of the
axt.
According to the present invention, an arbitrary
polarity scale is first established for various s~l~ents ~ased
on the physiochemical characteristics of each solvent. This
can be done by using , for example, Snyder's Yolarity Index,
incorporated by reference. See Snyder, I.R., J. Chromatoqraphy
Sci., 16:223, 1978. However, any other polarity scale could be
used to generate a polaritytindex function (defined infra).
Table 1 below contains nonlimiting examples of solvents
suitable for use in this invention and their assigned
polarities ton a scale from 1 to 10).
A collective polarity P can then be calculated for the
solvent components of a particular composition as the weighted
sum of the polarity of the solvents contained in a given
composition according to the formula:
P = (SiPi)
where i is an integer from 1 to n, n is the total number of
solvents in the composition; Si is the weight fraction of each
solvent based on the total composition of the progenitor
solution; and Pi is the polarity of that solvent.
Refractive index values for the emulsifiers, surfac-
tants and solvents are used to calculate a collective refrac-
tive index ND in the same manner
ND = ~ XiNi
151
wherein Xi is the weight fraction of a particular component
(surface active agent or solvent) and N is the refractive index
of the same component. Refractive indices for solvents are
~ .

readily available in the literature (see, e.g., The Merck
Index, 11th Fd. and the Handbook of Chemistry and Physics,
Chemical Rubber Publ. Co., Cleveland, Ohio) as are those for
surfactants.
The ability of each composition to clean a particular
type of soil is then measured and the results are correlated
with the following empirical polarity/refractive index function
(PIF): ~10.N
(10-P)
See Figures 1-3 by way of nonlimiting example.
In Figures 1~3 the ability of compositions within the
invention to remove tarsand soil when formulated into
emulsion containing 10% of a progenitor solution is plo-tted
against the polarity/Lndex function f~r each composition. (See
data points.) The three figures correspond to the data of
Table 3 for 3 types of emulsifier Emulsogen IT (Fig. 2~,
Emulsogen SHT (Fig. 1) and Emulsogen EL (Fig. 3). The straight
lines drawn through Fi~ures 1-3 represent the best straight-
line fit but the cleaning ability is assessed much more
accurately by reference to the critical PIF value. Critical
PIF value is a value of the polarity index function which when
matched or exceeded by variation of the content and chemical
identity of the constituents of a progenitor solution results
in formation of emulsions essentially all of which have
cleaning ability of 60% or more (when cleaning ability is
measured by the procedure of the Examples). Critical PIF is
thus a function of the particular cleaning task, and is
independent of the ingredients of the progenitor solution.
It transpires from Figures 1-3 that tarsand soil (to be
removed to a substantial extent, i.e. 60-100%) needs a cleaning
composition with a high polarity-index function (in the c~se of
Figs. 1-3 given the polarity scale used and the experimental
procedure and parameters for assessing cleaning ability the
critical PIF value is no less than about 6; in fact a substan-
tial increase in cleaning ability is almost universally
observed when the PIF is higher than the critical value). This

means that the best compositions for cleaning tarsands should
have both relatively high polarity and relatively high index of
refraction. Indeed, the preferred compositions exempliied
below have a collective rPfractive index ND f about 1.4 or
more and a collective so'~ent polarity of about 3.0 or more.
Thus, once the critical value of the polarity-index function
has been identified, it is possible to conveniently select
emulsions that will have a desired cleaning ability for a given
task by selecting a com~ination of ingredients and contents
which will yield an emulsion with a PIF value equalling or
exceeding the critical value. The selection can be refined
further ~if desired) using no more than routine experimentation
consistent with the present disclosure.
Similar empirical plots can be generated for other
1~ soils than tarsand using only routine experimentation. Thus,
the combination of the present invention can be optimized for
each cleaning use by identifying the critical polarity index
function value for a particular application. It should be
emphasized, however, that the cleaning compositions that are
most effective for tarsands are also generally effective for
other industrial cleaning tasks as tarsand removal is a
particularly difficult cleaning task. It is also possible to
develop straight-line models for the relationship between soil-
cleaning ability and Polarity/Index Function value for each
type of soil by using various statistical techniques such as
linear regression analysis applied to data such as those of
Table 3. In practice, however, this does not appear to be
necessary as it is nor~ally easy to identify the critical value
for the polarity-index function (which may or may not be
numerically the same for different cleaning applications).
It is envisioned that each progenitor solution within
the invention will contain at least one organic solvent suit-
able for removing the target soil(s), i.e., having sufficient
affinity to the soil to solvate it. Nonlimiting examples of
species and categories of suitable commercially available sol-
vents and their assigned polarities are set forth in Table 1.
.

TA~I,E 1
POLARITY OF S01VE NTS
SOLVENT GEN13RIC NA~ /CATEGORY POI~RITY
Sol~esso 150 aromatic hydrocarbons solvent 3
Butyl Carbitol diethylene glycol monobutyl ether 7
Exxate 600 alkyl oxo-alcohol esters 8
of acetic acid
Tabs D menthadiene solvent 5
~enzyl Alcohol phenyl carbinol 6
Isopropyl Alcohol 9.5
Methyl Carbitol diethylene glycol monomethyl ether 9
Carbitol di0thylene glycol monoethyl ether 8
Isopar K isoparaffinic hydrocarbon solvent 1.5
Xero K paraffinic hydrocarbon solvent 1.5
Nonaromatic solvents, especially those having a flash point
higher than 140F, are preferred for enviro~mental reasons.
~roadly, suitable solvents include without limitation
aliphatic, aromatic, terpenic, paraffinic, isoparaffinic and
olefinic hydrocarbons, alcohols and glycol ethers of the
formula CnO(E0)x(PO)yH wherein Cn is an alkyl radical having n
carbon atoms (n i5 from 1 to 6), E0 is a -CH2-CH20- (x is an
integer from 0 to 4), P0 is -C~(CH3)-CH2-0- or -CH2-C~(CH3)0-
(y is an integer from 0 to 4), benzyl alcohol, alkyloxoalcohol
esters of lower aliphatic acids, substituted glycols of the
formula CnO(E0)xCn (with n and x as defined a~ove), glycols of
the formula H(E0)xH and H(PO)yH (wherein E0, P0, x and y have
been defined above) and acetate esters of glycol ethers.
The progenitor solution will contain at least one
surfactant soluble in the solvent. The choice of surfactant
depends on the compatibility with the solvent and/or solvent
composition of the progenitor solution and the soil to be
removed. Compatibility of the surfactant with solvent and soil
is determined from supplier information or is within the
ordinary skill in the art including at times routine experimen-
tation. Preferably, the cleaning emulsion will contain at
least two surfactants which may be nonionic and/or cationic and
or amphoteric. Both (or all) surfactants are preferably incor-
porated in the progenitor solution. Anionic and zwitterionic

12
surfactants can also be used.
Suitable surfactants generally include without limita-
tion those disclosed, e.g., in Norris U.S. Patent No. 3,663,961
(5/23/72) incorporated by refP_ence and in Surfactants ~nd
5 Interfacial Phenomena by MiltcJ. Rosen, John Wiley ~ Sons,
1978, pp. 1-17, also incorporated by reference. Other suitable
surfactants include:
Suitable anionic surfactants generally include without
limitation water-soluble salts of alkylbenzene sulfonates,
alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin
sulfonates, alpha-olefin sulfonates, alpha-sulfocarboxylates
and their esters, alkyl glyceryl ether sulfonates, fatty acid
monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy
ether sulfates, 2-acryloxy-alkane-l-sulfonates, and beta-
alkyloxy alkane sulfonates. For more specific examples, see
U.S. Patent No. 4,414,128, col. 3, lines 60-68 & col. 4,
incorporated by reference.
Suitable nonionic surfactants include alkoxylated
compounds produced by the condensation of alkylene oxide groups
with an organic hydrophobic compound (aliphatic, aromatic or
arylaliphatic). The length of the polyoxy alkylene group
should be controlled (which can be accomplished in a manner
known per se) so that the resulting surfactant is liquid and,
where applicable, soluble in the solvent or solvent mixture
2S used for the progenitor solution. More specific examples of
these nonionic surfactants are disclosed, e.g., in U.S. Patent
No. 4,414,128, col. 5, lines 14-68 and col. 6, lines 1-14,
incorporated by reference.
Suitable cationic surfactants include without limita-
tion those disclosed in U.S. Patent No. 3,813,345, col. 8,
lines 42-53, incorporated by reference.
Amphoteric and zwitterionic surfactants include without
limitation those disclosed in U.S. Patent No. 4,414,128, col.
6, lines 31-66, incorporated by reference.
Preferred are surfactants such as nonionic ethoxylates
(e.g. Igepals, Surfonics) anionic surfactants (such as

Sulframin, Sulframin AOS) and cationic surfactants (such as
Bardacs, Hyamine, Genamin 8). All materials disclosed or
referenced herein are readily commercially available.
In general, the choice of emulsifier will depend on (a)
the desired stability of the emulsion; (b) whether an oil-in-
water or a water-in-oil emulsion is desired; and (c) the type
of soil to be removed. A hydrophilic emulsifier will best
stabili~e O/W emulsions while a liophilic emulsifier stabilize6
best W/O emulsions. A highly oxidized SOLl would require a
more hydrophobic emulsifier than a relatively unoxidized 80il~
In principle any emulsifier that contributes to the desired PIF
Yalue can be used, including without limitation those disclosed
in Aronson U.S. Patent No. 4,606,913.
Preferred examples of emulsifiers include the follow-
ing:
Table 2
Emulsifier Composition Supplier Example
_ _
Igepal Ca 420 Ethoxylated octyl phenol GAF
Brij 92 Ethoxylated (2) oleyl ether ICI
Span 80 Sorbitan monooleate ICI
Span 85 Sorbitan trioleate ICI
Atmos 300 Mono and di glycerides of
fat forming fatty acids ICI
Drewmulse GMO Glycerol monooleate PVO
Kessco Ester Glycerol monooleate ARMAK
Drewpole 10-4-0 Decaglycerol tetraoleate PVO
Liposorb SQO Sorbitan Sesquioleate Lipo Chemicals
Magnesium oleate Ethoxylated (3) oleyl ether Croda
Volpo 3
Bodag GMR Glycerol mono ricinoleate Hodag
Emulsogen E = Combination of fatty amine American
salts with alkyl aryl poly- Hoechst Corp.
glycol ethers

14
Emulsogen M = Fatty alcohol polyglycol ether '~
Emulsogen A = Fatty alcohol polyglycol ether
ester
Emulsogen B~ = Ami.ne salt of a7~vl sulfamide
carbonylic acid
Emulsogen D.G. Alkyl aryl polyglycol ether
~mulgin IT-60 Fatty acid polyglycol ~enkel Chem.
ester Corp.
Emulgin TL-55 Fatty acid polyglycol ester "
Icomeen T-15 Fatty amine ethoxylates BASF
Emulan FM Triethanolamine monooleic BASF
acid ester
Marlowet OFW Mixture of n-alkyl benzene Huls Canada,
sulfonate, carboxylic acid Inc.
polyglycol esters and alkyl
polyclycol ether
The incorporation of electrolytes is not necessary, but
if desired for a particular application, electrolytes could be
used as additional optional ingredients. Suitable electrolytes
include monovalent divalent and polyvalent inorganic salts such
as halides sulfates, carbonates and phosphates, of alkali
metals, alkaline earth metals and heavy metals and mixtures of
such salts. It is emphasized, however, that electrolytes are
not necessary.
The progenitor solutions of the present invention are
prepared by blending surfactants, emulsifiers and solvents (as
well as optional ingredients such as thickening agents, dyes,
perfumes, preservatives, anti-oxidants, etc.) in normal
conventional equipment commonly used in the chemical specialty
industry. For example, simple mixing or blending vessels such
as stainless steel tanks equipped with an agitator (e.g. a
Lightnin~ mixer) are sufficient. Solvents are added first into
the blending vessel. The agitation is started and the remain-
ing ingredients s~lrfactants, emulsifiers, etc. are added and

blended until the mixture is homogeneous. This may require
mixing at e.g. 50-200 rpm for several minutes to several hours
depending on tank volume and agitator si~e.
The emulsions of the present invention are prepared by
-- 5 simple dilution of the progenitor solution into water with
normal agitation. The water can be any temperature, e.g. as
required for the cleaning application, but it is preferably
warm (e~g. 50~C or above). Soft water is preferred.
The emulsions can contain from 0.1 to 80% of the
- 10progenitor ~olution. Generally, a 1-10% concentration is
~ufficient for most industrial cleaning jobs, and is pref~rred.
The in~ention is further illustrated below by reference
to specific non-limiting Examples.
Example 1: Soil Removal Assessment
15Standard tarsand soils were prepared by smearing 2.5 cm
x 2.5 cm x 0.3 cm tarsand (alternatively jesco grease or 80-10
mixtures of tarsand and jesco could have been similarly
prepared) on Q-panels (i.e., metal testing panels having a Q-
shaped hole) and baking the applied soil for 30 minutes at
20120~C. The panels were thereafter left to attain atmospheric
equilibrium for 24 hours. This procedure is referred to in the
claims as Q-panel testing.
Other test soils such as multi-use and automotive
greases, gear oils, or automotive under coatings could be
25prepared for assessment in the same manner.
Finally, test soils could be alternatively prepared as
follows: Roofing tars or soils containing plasticizers or any
type of soil com~ination (greases, oils, waxes, etc.) are
smeared on metal panels and exposed to the elements (e.g., on
30roofs or walls) for aging. The applied soil thickness is in
all cases controlled via an applicator gauge.
Example 2: Preparation of Progenitor
Solutions and Emulsions
To a 2000 ml beaker containing a magnetic stirring bar
35placed on a magnetic stirrer 100 g of Solvesso 150 were added
followed by 100 g Tabs D, 100 g methyl carbitol, 75 g of

16
Rexonic 91-8, 75 g Hyamine 3500 and finally 50 g of Icomeen T-
150 The final mixture was stirred for 30 minutes and then
stored for use. This resulted in progenitor solution 20.
Additional solutions were made in the ~ame manner with sub-
stitutions of various ingredients, In all cases the emulsifierwas added last to the mixture of solvent(s) and surfactant.
The ingredients and amounts for all the resulting
progenitor solutions of this Example 2 are set forth in Table
3. In each case only one emulsifier was used and thus Solution
No. l, for example, is really 3 different compositions: one
with Emulsogen IT, one with Emulsogen S~T and one with Emul-
sogen EL.

oooo I~
~ O ' O
l ou~ o ~ I I l o c~ ~ n ~ n
1000 I I I I I IQ~ 10 1`~
I I I I I I I OOvO I ~ n w
I ~ O O æ
I ~> o o I I I I I 'o l o l ao'~ I I ~ n ~n
I I I l o l l o- l ~ ~ I l ~ n a~
I~'o~o I I I l~ol l~olo `~-~I
go~o I I lol I I'olao' ~n~nl I~ n
loo~ I lol I I l~olo ~n~nl l~ n ._
I ` o ' I I o l I I I o I o I I ~ n o
lo~~o I lol I I I'olo ~ I I~ n
lulo~ I lol I I I I Io~ ~ I I~ n
O I I o l I I I I I -~-' I ~ n
IOOO IOIIIIIIII _1_11 I~11Ul~1 ~_ ~
I ~o g Co2 I I I I I I I o I I ~ I I ~ n ~ ~
~o~ IIIIIIII1~ v~ ~ C~ ~
l u1 o o l o l I I I I I I I~ ~ I l u~ n ~ ~
looo æl, 1 1 1 1 1 1 1 u~l I~ ~
c~l I I I I I I I I looao~ 1-'-' ~nl I I
~o ~, I l ' I 'o I I I o ~ ao` _J_l I ~ I I I o
I I * ~ I I I I I I ~ o -'`' I ~n l I I ~

18
Emulsions were made containing 10% of each progenitor
solution in about 50C water by introducing a 10% vol. aliquot
of progenitor solution into 90% vol. of water with agitation
until homogeneous.
As apparent from Table 3, the co~_entration of the
emulsifier was maintained at a constant level (5~) throughout
all systems tested (except for progenitor solution 21-1). The
same was done with the surfactant concentration (15%). This
was done to normalize the data and does not imply that the
emulsifiers and surfactants are limited to the amounts listed
in Table 3. Various solvents of high and low polarity were
used. The emulsions were transferred to a pump spray bottle
and hand-sprayed onto the tarsand spray panels for one minute.
(Thi~ is also part of the Q-panel testing procedure.)
The amount of tarsand removed was visually estimated
and recorded. The results are also set forth in Table 3. The
soil removal ability for various emulsions can be vastly
different even when the ingredients are present in the same
proportions. See in particular the systems that have identical
surfactants and solvents but different emulsifiers. See also
the systems that have the same surfactants and emulsifiers but
different solvents. The emulsion stability was tested at 4C,
35C and at ambient temperatures for those emulsions that gave
satisfactory cleaning performance. Stability testing involved
preparations of emulsions containing 10~ and 20% of a mother
solution in water and left to stand at 4C for three months;
ambient temperature for three months and 35~C for three months.
No coalescence was observed at this time; only occasionally
minimal "creaming" occurred at 35C.
Example 3: Correlation of Polarity Index
Function and Cleaninq Ability
The collective polarities for each solvent mixture of
each progenitor solution in Table 3 are set forth in Table 4
below:

19
TP.BLE: 4
COI,LE CTIVE POLARITI~:S FOR SOLVE~IT
Progenitor Solution of Solvent Polarity
1 ~.8
~ 2.9
3 3O0
4 3.0
2.9
6 3.25
~ 3.2
9 3.1
3.6
12 42 15
13 3.5
14 1.2
4.0
16 2.4
17 1.2
18 1.2
19 3.0
3.2
221-1 2.93
The collective refractive indices for the emulsions o~
Table 4 are set forth in Table 5 below:

-- 20 --
9 ~ ~ 3
_ I I I I I I g~ I I g} I ~ ;; ~ ~
~' ~ ~'
I I I I y I I
W I I I W I I I ~
_ I I ~ W
~ I I I I I I I I I h ~
I I I I I I I I I
o I I I I I I i
I I I I I I I I I I I I I I
_ I I I ~ I 1 8 ~,

Figures 1-3 represent a plot of the cleaning ability
for tarsand 50il removal against the polarity/index function
(PIF) of each composition of Table 3.
The critical PIF value of about 6 in Figs. 1-3 has been
use ul in determining the best cleaning emulsion for the
following soils:
: tarsand
tarsand-jesco grease
multi-use gr~ases
;- 10 gear oils
Thus the data points in Figs. 1-3 permit the selection
o~ the most effective progenitor solution to assess the optimum
efficacity for tarsand solid removal. Alternatively, they lend
themselves to utilizing and selecting a different solvent
and/or surface active agents to yield the desired polarity/in-
dex function (which should be at least equal to the critical
value)~ ~It should be noted that the index of water was not
used in computing the datapoints of Figures 1-3 ~ecause all the
emulsions had the same amount of water.) Ideally, the PIF OL
the progenitor solution should be as close to the critical
value as will yield the desired cleaning ability. Further
improvements in cleaning ability can be effected using no more
than routine experimentation.
Similar graphs can be generated in the manner disclosed
above for other emulsions of different ingredients and proper-
ties and for different cleaning tasks under different condi-
tions. For example, emulsions containing 10% of progenitor
solution #5 containing Emulsogen IT, and progenitor solution #3
containing Emulsogen SHT were effective against tarsand but not
jesco oil. However, all compositions that worked on jesco (a
tougher soil) also worked on tarsand. Particularly preferred
progenitor solutions are solutions #15 and #20 in Table 3.
Also the following are preferred:
1 2 3 4 5
Isopar K 68.3 39.3 6.0
d-limonene 25.0 12.9 8.0 87.0

22
methyl carbitol 68.4 40.2 45.0
butyl carbitol 35.0
Eco~een T 1.7 3.0
Emulsogen A 1.7 0.9 l.O 1.0 2.0
Emulsogen T 2.5
Comperlan VOD 0.8 1.0
Emulsogen ~15 4.9 4.5 4.5 1~0
1~
~yamine DMB 451 6.5 7.5 7.5
Igepal C0630 6.5 7.5 7.5
Also particularly preferred are emulsions containing
from about 0.5 to about 30% of one of the for~going preferred
progenitor solutions.