Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
W O 91/00337 PC~r/US90/03317
IMPROVED BUILDER-CONTAINING A~
CLEANER~DEGREASER MICROEMDLSION COMPOSITIONS
- Backqround of the Invention
This invention relates to cleaner/degreaser
compositions and, more particularly, to stable, aqueous,
builder-containing cleaner/degreaser compositions in the
form of true microemulsions which e~hibit enhanced cleaning
and degreasing capability
Heretofore, all of the conventional and available
ready to use and concentrated water soluble, dilutable
cleaner~degreaser compositions have e~pediently contained
infinitely or highly water soluble organic solvents such as
butyl cellosolve (ethylene glycol monobutyl ether), butyl
carbitol (diethylene glycol monobutyl ether), ethyl
carbitol, propylene glycol monomethyl ether, dipropylene
glycol monomethyl ether or isopropanol tog~ther with
anionic or nonionic surfactants and conventiohal adjuvants
such chelants, builders, perfumes, dyes, pH adjustors,
etc., these components falling generally within the
following compositional wt.% ranges:
2-10% Water soluble solvent(s)
1-3% Anionic or nonionic surfactant
0.1-3% Adjuvants
OS Water
100.0%
Such conventional compositions are generally deficient in
cleaning action and especially in heavy duty grease, oil,
wa~, etc. cutting action, often smell objectionably
strongly of volative solvent and can sometimes present
conbustability problems in concentrated form. They also
tend to be harsh on the hands and to defat the skin.
Further, heavy scrubbing, mopping or other mechanical
action is generally required to attain the desired
cleaning/degreasing action, especially where e~cessive
SUBSTITUTE SHEET
CA 020~7027 1998-12-30
-- 2
soilant buildup has occurred. Most, even in their
concentrated form, are ineffective in their capability to
remove graffiti or the like.
In U.S. Patent No. 5,080,831, I disclose stable,
aqueous cleaner/degreaser compositions which are formulated in
the form of totally water soluble solutions. Such
compositions comprise (a) at least one sparingly water soluble
organic solvent having certain defined characteristics; (b)
solubilizing additive consisting of from 0.1 to approximately
100 weight percent of a surfactant and from O to approximately
99.9 weight percent of a coupler, the solubilizing additive
being present in an amount not exceeding approximately tenfold
that required to completely solubilize the organic solvent;
and (c) water. While such compositions exhibit markedly
superior cleaning/degreasing efficacy over that achievable
with compositions containing infinitely water soluble organic
solvents, problems are encountered in incorporating builders
therein to further enhance their cleaning/degreasing
capability due to the "salting out" characteristics of
conventional builders.
There is a need, therefore, for improved builder-
containing, aqueous cleaner/degreaser compositions which
permit still further improvements in cleaner/degreasing
activity.
64725-537
.
CA 020~7027 1998-12-30
- 2a -
Summary of the Invention
Among the several objects of the invention may be
noted the provision of stable, aqueous cleaner/degreaser
compositions containing builders which boost the
cleaning/degreasing action of such compositions; the provision
of such compositions which are formulated in the form of
stable microemulsions; the provision of compositions of
64725-537
~o 570 27
thls type whlch lncorporate organlc solvent of lnherently
llmlted aqueous solublllty; the provlslon of such
composltlons whlch are nontoxlc, nonhazardous ln use and
exhlblt a low level of odor; the provlslon of such
composltlons whlch avold soll redeposltlon and lnhlblt metal
corroslon; and the provlslon of such lmproved bullder-
contalnlng composltlons whlch may be readlly formulated from
avallable components. Other ob~ects and features wlll be ln
part apparent and ln part polnted out herelnafter.
Brlefly, the present lnventlon ls dlrected to
stable, aqueous cleaner/degreaser composltlons whlch are
formulated ln the form of true mlcroemulslons. The
composltlons comprlse:
(a) at least one sparlngly water soluble organlc
solvent characterlzed by
(1) havlng a water solublllty ln the range
of approxlmately 0.2 to approxlmately 6
welght, percent;
(11) not belng a hydrocarbon or halocarbon;
(lil) havlng one or more slmllar or dlsslmllar
oxygen, nltrogen, sulfur or phosphorous
contalnlng functlonal groups;
(lv) belng a solvent for hydrophoblc sollants;
and
(v) belng present ln an amount exceedlng lts
aqueous solublllty.
A 64725-537
~0 57~27 ~
3a
~ b) from approxlmately 0.25 to 10.0 wt.%, based on
the total composition, of a builder;
(c) a solubillzlng additive consisting of from
approximately 0.1 to approxlmately 100 welght percent of a
surfactant and from 0 to approxlmately 99.9 weight percent of
a coupler, said solubilizing additive being present in an
amount not substantially exceeding the amount required
A 64725-537
W O 91/00337 PC~r/US90/03317
to transform the combination of said organic solvent and
said builder from the form of a true macroemulsion to the
form of a microemulsion and less than that reguired to form
a true solution; and
(d) water.
The compositions of the invention e~hibit improved cleaner/
degreaser efficacy over compositions which contain no
builder component.
Description of the Preferred Embodiments
In accordance with the present invention, it has
been found that improved builder-containing agueous
cleaner/ degreaser compositions can be formulated in the
form of stable microemulsions by combining at least one
sparingly water soluble organic solvent having certain
characteristics and being present in an amount e~ceeding
its aqueous solubility with a builder, a solubilizing
additive and water, the solubilizing additive beinq present
in an amount not substantially e~ding the amount
required to transform the combination of said organic
solvent and said builder from the form of a true
macroemulsion to the form of a microemulsion and less than
that required to form a true solution. Surprisingly, as
demonstrated by the e~perimental data presented
hereinafter, it has been discovered that the incorporation
of builders into such compositions formulated as
microemulsions boosts or enhances the cleaning~degreasing
efficacy as compared to compositions containing no builder
component. As indicated, it is essential to the formation
of microemulsion compositions in accordance with the
present invention that the solubilizing additive be present
in an amount not substantially e~ceeding that required to
transform the combination of the organic solvent and
builder from the form of a true macroemulsion to the form
of a microemulsion and less than that required to form a
SUBSTITUTE SHEET
W O 91/00337 PC~r/US90/03317
~ ~ ~ 7 ~ ~ ~ ' 5
microemulsions of the invention are clear and e~hibit the
Tyndall effect. It is believed that the aqueous phase of
the microemulsions contains the dissolved builder. Due to
the limited aqueous solubility of the organic solvents
employed in the practice of the invention, it is ~ln~ cLed
that true microemulsions are formed.
The incorporation of a builder component in the
microemulsion compositions of the invention provides
additional advantages not conferred by cleaning~degreasing
compositions which contain no builder component. Thus,
such microemulsions not only achieve an ~nhanred cleaning/
degreasing efficacy but, moreover, they avoid soil
redeposition and generally inhibit metal corrosion.
Accordingly, the compositions of the invention are
particularly useful for cleaning~degreasing metallic
surfaces. Further, such microemulsions are more cost
effective in their formulation since they generally contain
lower amounts of the organic solvent component than do
non-builder formulations. Also, the present invention
permits the practical and effective use of normally
hydrophobic (oliophilic) solvents in builder-containing
compositions, which solvents have great affinity for and
dissolving action against oleophilic soilants.
For use in the present invention, the sparingly
water soluble organic solvent must have the following
characteristics:
(a) it must have limited water solubility in the
range of appro~imately O.Z to 6 weight
percent;
(b) it must not be a hydrocarbon or halocarbon;
(c) it must have one or more similar or
dissimilar o~ygen, nitrogen, sulfur or
phosphorous containing functional groups;
(d) it must be a solvent for hydrophobic
soilants; and
(e) it must be present in an amount e~ceeding
SUBSTITUTE SHEET
W O 91/00337 PC~r/US90/03317
c~
~i
Organic solvents meeting these criteria provide superior
cleaning~degreasing action when formulated in accordance
with the invention.
The principal classes of organic solvents from
which useful organic solvents may be selected include
esters, alchohols, ketones, aldehydes, ethers and
nitriles. These will generally contain one or more of the
desired similar or dissimilar functional groups listed
above. Esamples of organic solvents containing similar
functional groups from among those listed above include
diethyl gluterate (2 ester groups), phenacyl acetone (2
~eto groups), diethylethyl phosphonate (2 phosphonate ester
groups), ethylenedipropionate (2 ester groups), decylene
glycol (2 hydro~yl groups), m-dimetho~ybenzene (2 ether
groups), adiponitrile (2 nitrile groups), ethylene glycol
dibutyl ether (2 ether groups), and diethyl-o-phthalate (2
ester groups). Among organic solvents containing
dissimilar functional groups from among those listed above
may be mentioned 2-phenosyethanol (h~drosy, ether groups),
1-pheno~y-2-propanol (hydrosy, ether groups), N-phenyl-
morpholine (amino, ether groups), isopropylacetoacetate
(keto, ester groups), _-metho~ybenzyl alcohol (ether,
hydro~y groups), 4~-methosyacetophenone (ether, ketone
groups), Q-nitrophenetole (nitro, ether groups),
2-heso~yethanol (hydrosy, ether groups), ethylcyano-
acetoacetate (cyano, keto, ester groups), p-anisaldehyde
(ether, aldehyde groups), polypropylene glycol 1200 (ether,
hydro~yl groups), n-buto~y acetate (ether, ester groups),
and 2-phenylthioethanol (thioether, hydrosyl groups).
In addition to the criteria listed above, it is
also desirable but not essential that the organic solvent
have a relatively low volatility or high flash point,
e~hibit a low level of odor, be chemically stable,
nonto~ic, nonhazardous and commercially available.
The sparingly water soluble organic solvents
which may be employed in the practice of the present
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W O 91/00337 PC~r/US90/03317
~ ~ ~ 7 ~ ~ ~ t
invention (and comprising some of the solvents listed
above) together with their aqueous ambient temperature
solubility in wt.% include 2-pheno~yethanol (2.3) (marketed
under the trade designation ~Dowanol EPh~), l-pheno~y-2-
propanol (1.1) (marketed under the trade designation~Dowanol PPh~), -phenylethanol (1.6), acetophenone (0.5),
benzyl alcohol (4.4), benzonitrile (1.0), n-butyl acetate
(0.7), n-amyl acetate (0.25), benzaldehyde (0.3), N,N-di-
ethylaniline (1.4), diethyl adipate (0.43), dimethyl-o-
phthalate (0.43), n-amyl alcohol ~2.7), N-~h~ lmorpholine
(1.0), n-buto~yethyl acetate (EB acetate) (1.1), cyclo-
he~anol (4.Z), polypropylene glycol 1200 (2), cyclohe~anone
(2.3), isophorone (1.2), methylisobutyl ketone (2.0),
methylisoamyl ketone (0.5), tri-n-butylphosphate (0.6),
l-nitropropane (1.4), nitroethane (4.5), dimethyl esters of
mi~ed succinic, glutaric and adipic acids (5.7) (mar~eted
under the trade designation ~DBE ester~ by DuPont), diethyl
glutarate (0.88), and diethyl malonate (2.08). As will be
apparent to those s~illed in the art, the above-listed
sparingly water soluble organic solvents are merely illus-
trative and various other solvents meeting the criteria set
out above may also be utilized in the practice of the inven-
tion. Because of their performance characteristics, lack
of odor, low volatility/high flash point, chemical stability
and availability, 2-pheno~yethanol and l-pheno y-2-propanol
are the preferred organic solvents of choice. N-buto~yethyl
acetate (EB acetate) and the dimethyl esters of mi~ed
succinic, glutaric and adipic acids are also among the pre-
ferred organic solvents.
As indicated, a number of otherwise potent organic
solvents having an aqueous solubility of less than appro~i-
mately 0.2 weight percent such as 2-(2-ethylhe~o~y)ethanol
(2-ethylhe~yl cellosolve) having an aqueous solubility of
only 0.095 wt.%, and 2,6-dimethyl -4-heptanone (diisobutyl
ketone) (aq. sol. 0.05 wt. %), and organic solvents having
SUBSTITUTE SHEET
WO91/00337 PCT/US90/03317
~an aqueous solubility in e~cess of appro~imately 6 weight
g~percent such as propylene glycol monomethyl ether acetate
(aq. sol. 16.5 wt.%), ethylene glycol diacetate (aq. sol.
14.3 wt.%), propylene carbonate (aq. sol. 19.6 wt.%) and
N-methyl pyrrolidone (infinite aq. sol.) are not useful in
the practice of the invention.
In formulating the stable, aqueous cleaner~
degreaser compositions of the invention in the form of
microemulsions, an organic solvent meeting the required
criteria is combined with a builder, a solubilizing
additive and water. As is ~nown to those skilled in the
art, a builder is a material that enhances or maintains the
cleaning efficiency of surfactants and functions by
inactivating water hardness, supplying al~alinity to assist
cleaning, providing buffering to maintain al~alinity, pre-
venting removed soil from redepositing during washing, and
emulsifying oily and greasy soils. Any of the conventional
builders known to the art may be used in the practice of
the invention. These include silicates such as alkali
metal silicates and metasilicates, alkali metal hydro~ides,
alkali metal carbonates, bicarbonates and sesquicarbonates,
phosphates such as alkali metal phosphates, pyrophosphates,
tripolyphosphates, he~ametaphosphates and tetraphosphates,
bora~ and alkali metal borates. Among specific builders
which may be used in the practice of the invention may be
mentioned sodium hydro~ide, sodium metasilicate, sodium
silicate (Na2O:2SiO2 or Na2O:3SiO2), sodium carbonate,
sodium sesquicarbonate, sodium bicarbonate, bora~, trisodium
phosphate, tetrasodium pyrophosphate, sodium tripolyphos-
phate, sodium he~ametaphosphate, sodium tetraphosphate, andsodium perborate. Other builders known to the art may also
be used~ The builder component will generally constitute
from appro~imately 0.25 to 10.0 wt.% of the total
composition.
35The solubilizing additive component of the
compositions of the invention consists of from
SUBST~TUTE SHEET
W O 91/00337 PC~r/US90/03317
appro~imately 0.1 to appro~imately 100 weight percent of a
surfactant and from 0 to appro~imately 99.9 weight percent
of a coupler and the solubilizing additive is present in
the formulated composition in an amount necessary to form a
microemulsion, i.e. an amount not substantially e~ceeding
the amount required to transform the combination of the
organic solvent and builder components from the form of a
true macroemulsion to the form of a microemulsion and less
than that l~quired to form a true solution. Preferably,
the amount of solubilizing additive employed is just suffi-
cient to form a microemulsion. The amount of solubilizing
additive (surfactants or surfactant plus coupler) required
to e~fect the formation of a microemulsion will vary
de~el.~ing upon the particular organic solvent and builder
employed and can readily be determined by simple e~peri-
mentation in each instance.
The solubilizing additive used in the practice of
the invention may consist of a surfactant or a surfactant
in combination with a coupler. As used herein, the term
~coupler~ is intended to mean a hydrotrope or a substance
that increases the solubility in water of another material
which is only partially water soluble, such as organic
solvents or surfactants. In some instances, the use ~of a
surfactant alone will suffice to render the organic solvent
component of the compositions just completely (microcolloid-
ally) soluble while in other instances the use of a surfac-
tant in combination with a coupler may be utilized to
achieve the desired microcolloidal solubilization of the
organic solvent, i.e. microcolloidal solubilization meaning
to transform the combination of the organic solvent and
builder from a true macroemulsion to the form of a
microemulsion. Whether or not a surfactant alone or the
combination of a surfactant and coupler is to be used is
dependent upon the particular organic solvent and
surfactant employed and can readily be determined in
each particular case by simple e~perimentation. The
SUBSTITUTE SHEE~
WO91/00337 PCT/US90/03317
hard surface cleaning/degreasing. Illustrative anionic
~' surfactants for use in the invention include dodecylbenzene
sulfonic acid, sodium dodecylbenzene sulfonate, potassium
dodecylbenzene sulfonate,triethanolamine dodecylbenzene
sulfonate, morpholinium dodecylbenzene sulfonate, ammonium
dodecylbenzene sulfonate, isopropylamine dodecylbenzene
sulfonate, sodium tridecylbenzene sulfonate, sodium
dinonylbenzene sulfonate, potassium didodecylbenzene
sulfonate, dodecyl diphenylo~ide disulfonic acid, sodium
dodecyl diphenyloside disulfonate, isopropylamine decyl
diphenylo~ide disulfonate, sodium hesadecylosypoly
(ethyleneo~y)(l0)ethyl sulfonate, potassium octylpheno~y-
poly(ethyleneo~y)(9)ethyl sulfonate, sodium alpha Cl2_l4
olefin sulfonate, sodium he~adecane-l sulfonate, sodium
ethyl oleate sulfonate, potassium octadecenylsuccinate,
sodium oleate, potassium laurate, triethanolamine myri-
state, morpholinium tallate, potassium tallate, sodium
lauryl sulfate, diethanolamine lauryl sulfate, sodium
laureth (3) sulfate, ammonium laureth (2) sulfate, sodium
nonylphenosypoly(ethyleneo~y)(4) sulfate, sodium diiso-
butylsulfosuccinate, disodium laurylsulfosuccinate,
tetrasodium N-laurylsulfosuccinimate, sodium decylo~ypoly-
(ethyleneosy(5)methyl)carbosylate, sodium octylpheno~ypoly-
(ethyleneosy(8)methyl)carbosylate, sodium mono decylo~ypoly-
(ethyleneo~y)(4)phosphate, sodium di decylosypoly-
(ethyleneosy)(6)phosphate, and potassium mono/di-octyl-
pheno~ypoly(ethyleneosy)(9)phosphate. Other anionic
surfactants known in the art may also be employed.
Among the useful nonionic surfactants which may
be employed may be mentioned octylphe~ ~oly(ethyleneo~y)-
(ll)ethanol, nonylphenosypoly(ethyleneosy)(13)ethanol,
dodecylphenosypoly(ethyleneo~y)(l0)ethanol, polyo~yethylene
(12) lauryl alcohol, polyo~yethylene (14) tridecyl alcohol,
laurylo~ypoly(ethyleneo~y)(l0)ethyl methyl ether, undecyl-
thiopoly(ethyleneosy)(l2)ethanol, metho~ypoly(o~yethylene-
(10)~(o~ypropylene(20))-2-propanol block copolymer,
SUBSTITUTE SHEET
WO91/00337 PCT/US90/03317
. ~ ~ .--. :Y~
nonylo~ypoly(propyleneo~y)(4)/(ethyleneo~y)(16)ethanol,
dodecyl polyglycoside, polyo~yethylene (9) monolaurate,
polyo~yethylene (8) monoundecanoate, polyo~y~thylene (20)
sorbitan monostearate, polyo~yethylene (18) sorbitol
monotallate, sucrose monolaurate, lauryldimethylamine
o~ide, myristyldimethylamine o~ide, lauramidopropyl
-N,N-dimethylamine o~ide, 1:1 lauric diethanolamide, 1:1
coconut diethanolamide, 1:1 mi~ed fatty acid diethanol-
amide, polyo~yethylene(6)1auramide, 1:1 soya diethanol-
amidopoly(ethyle~_J~)(8) ethanol, coconut diethanolamide,~modified~, and coconut diethanolamide, ~long chain
modified~. Other known nonionic surfactants may li~ewise
be used.
Illustrative useful cationic surfactants include
a mi~ture of n-al~yl (C12 50%, C14 30%~ C16 17~ 18
dimethyl ethylbenzyl ammonium chlorides, he~adecyltrimethyl-
ammonium methosulfate, didecyldimethylammonium bromide and
a mi~ture of n-al~yl (68% C12, 32% C14) dimethyl benzyl
ammonium chlorides. Similarly useful amphoteric surfactants
include cocamidopropyl betaine, sodium palmityloamphopro-
pionate, N-coco beta-aminopropionic acid, disodium N-lauryl-
iminodipropionate, sodium coco imidazoline amphoglycinate
and coco betaine. Other cationic and amphoteric surfactants
known to the art may also be utilized.
The preferred surfactants for general use in the
practice of the invention include dodecylbenzenesulfonic
acid and the sodium, potassium, triethanolamine, morpho-
linium, ammonium and isopropylamine salts thereof, and
morpholinium tallate.
The couplers which may be utilized in the practice
of the invention include sodium benzene sulfonate, sodium
toluene sulfonate, sodium ~ylene sulfonate, potassium
ethylbenzene sulfonate, sodium cumene sulfonate, sodium
octane-l-sulfonate, potassium dimethylnaphthalene sulfonate,
ammonium ~ylene sulfonate, sodium n-he~yl diphenyo~ide
disulfonate, sodium 2-et~ylhe~yl sulfate, ammonium
SUBSTITUTE SHEET
W O 91/00337 PC~r/US90/03317
- 12
.
r~
/".~, -
n-buto~yethyl sulfate, sodium 2-ethylhe~anoate, sodium
pelargonate, sodium n-buto~ymethyl carbo~ylate, potassium
mono/di pheno~yethyl phosphate, sodium mono/di n-buto~yethyl
phosphate, triethanolamine trimethylolpropane phosphate,
sodium capryloamphopropionate, disodium capryloiminodipro-
pionate, and sodium capro imidazoline amphoylycinate.
Certain water-soluble solvents known to the art as couplers
such as propylene glycol ethers (e.g. tripropyleneglycol
monomethyl ether) can be used in the practice of the
invention, but cannot be substituted for the sparingly water
soluble organic solvent component. Additional couplers or
hydrotropes known to the art may also be utilized.
In regard to the solubilizing additive component
of the compositions of the invention, it will be understood
that one or more surfactants from one or more compatible
classes of surfactants may be employed or utilized in a
mi~ed solubilizing surfactant system. For e~ample, a
combination of compatible anionic and nonionic surfactants
may be employed. Li~ewise, a combination of compatible
couplers may also be used as may a combination of one or
more compatible surfactants from different classes of
surfactants together with one or more couplers. Thus, one
may use a combination of blended surfactants and couplers to
achieve the desired minimal sol~ent solubilization. ~he
compatibility of the various surfactants and of the various
couplers with each other and in combination can be readily
determined by simple e~perimentation.
Similarly, but less preferably, a mi~ture of the
sparingly soluble organic solvents may be employed in
formulating the compositions of the invention. However, if
a mi~ture of solvents is to be used, each of the solvents
should have nearly the same appro~imate water solubility so
that they will solubilize in water at appro~imately the same
point upon addition of the solubilizing additive.
In addition to the organic solvent and solubiliz-
ing additive components of the compositions of the invention,
SUB~ I ~ I IJTE SHEE~
W O 91/00337 PC~r/US90/03317
~ ~ ~ f ~ 13
various optional adjuvants can be incorporated. These
include chelants such as the sodium salts of ethylenedi-
aminetetraacetic acid (Hampene 100 or Versene 100),
thickeners such as carbo~y acrylic polymers (Carbopol 940)
or acrylic acid/alkyl methacrylate copolymers (Acrysol
ICS-l), fragrances, dyes, pH adjustants, defoaming agents,
anti-corrosion additives and anti-rust additives. To
prevent flash rusting when the compositions are used to
clean and~or degrease metal surfaces, an anti flash-rusting
additive such as an alkanolamine (e.g., mono-, di- or
triethanolamine) may be incorporated.
In formulating the compositions of the invention,
the various components as brought together may first form an
oily suspension which becomes an emulsion upon the addition
of a surfactant/coupler, and is then finally transformed
into a microemulsion through the addition of the final
portion of the solubilizing coupler. For e~ample, 2.0 wt. %
sodium metasilicate, 7.5 wt. % 1-pheno~y-2-propanol, 2.5 wt.
% tripropyleneglycol monomethyl ether and 76.4 wt. % soft
water are stirred to form an oily suspension having a pH of
13.3. 2.4 wt. % dodecylbenzenesulfonic acid is added with
stirring to form a creamy white emulsion having a pH of
13.1 7.2 wt. % sodium ~ylene sulfonate (40~) is then added
with stirring whereupon some slight lightening of the
emulsion occurs. The addition of 1.8 wt. % sodium ~ylene
sulfonate (40%) causes the emulsion to become still lighter
but it remains opaque. Upon the final addition of 0.2 wt. %
sodium ~ylene sulfonate (40%) with stirring, the white
emulsion is transformed into a bluish microcolloidal
microemulsion having a pH of 13.05. The microemulsions of
the invention can also be formulated by combining the
various components together in different sequence to
transform any emulsion formed into a microemulsion. The
addition of an e~cess of the solubilizing additive to the
formulation will cause the microemulsion to be converted
SUBSTITUTE SHEET
W O 91/00337 PClr/US90/03317
14
into a solution and is to be avoided if optimum cleaning/
degreasing efficacy of the builder-containing formulations
is to be achieved.
The concentration of the aqueous cleaner~deqreaser
solution, as indicated by the terms ~total solids content~
and ~total actives content~ in the working e~amples provided
hereinafter refers, respectively, to the combined percentages
of nonvolatile components and to the sum total of nonaqueous
volatile and nonvolatile components.
The term ~cloud point' indicates the temperature
below which the composition e~ists as a clear, single phase
microemulsion and above which phase separation (hetero-
geneity) occurs. ~or practical reasons, a composition
should preferably have a cloud point in e~cess of, for
e~ample 50~C, to have a viably safe, storage-stable shelf
life under hot, summertime warehouse conditions.
As shown by the e~perimental degreasing test data
presented below, the compositions of the invention provide
enhanced cleaning/degreasing efficacy over that achievable
with compositions containing no builder or with available
builder-containing compositions formulated in the form of
total solutions.
The following e~amples illustrate the practice of
the invention.
E~ample 1
In the following e~amples of illustrative cleaner/
degreaser compositions of the present invention, the
compositions were subjected as indicated to the definitive,
semiquantitative degreasing test method described below in
order to measure their cleaning/degreasing efficacy.
A magnetic stirrer (Fisher Scientific Co., Catalog
No. 14-511-lA) provided with a vaned disc magnetic stir bar
(7~8- (diameter) ~ 5~8- (height), 22 mm ~ 15 mm, Fisher
Scientific Co., Catalog No. 14-511-98C) was used In each
instance, pre-cleaned, borosilicate glass microslides (3
SUBST~TUTE SHEET
WO91/00337 PCT/US90/03317
~ 15
1~, 1.0 mm thickness) were thinly smeared/rub-on coated with
Vaseline brand white petroleum jelly on one side only to a
distance of 1.0~ from the bottom edge to provide a 1.0~ ~
1.0~ coated area. The test cleaner~degreaser solutions were
employed at full strength unless otherwise indicated and in
an amount sufficient to fill a 50 ml Pyre~ he~r containing
the vaned disc magnetic stirrer bar to a level of 40 ml.
Each test solution and surrounding air were maintained at 21
+ 0.5~C and the test solution stirring rate was determined
by a setting of ~3~ on the stirrer dial of the magnetic
stirrer. The stirring disc was positioned off-center to
accomodate each microslide, touching neither the beaker
walls nor the microslide and rotating freely when in use.
The microslide, in each test, rested upright on the beaker
bottom, was allowed to lean against the lip of the beaker at
an appro~imately 75~ angle and was positioned with the
Vaseline coated face or area facing upward away from the
vaned disc magnetic stirrer bar.
For each test, the bea~er containing the stirrer
bar was filled to 40 ml. with the test cleaning/degreasing
solution at the indicated concentration, placed atop the
magnetic stirrer plate, and positioned off-center to accomo-
date the glass microslide, and yet allow the vaned disc
stirrer bar to rotate or spin freely. The stirrer was
turned on, the dial adjusted manually to the ~3~ stirring
rate setting and the Vaseline thin film coated glass micro-
slide was introduced into the test solution bath in such a
manner that the coated side faced upward and was positioned
away from the stirrer bar. The time ~0~ was noted
immediately on a wat~h or clock with a sweep second hand.
At appropriate time intervals, the glass
microslide was briefly removed from the cleaner~degreaser
solution bath and immediately ~read~ for ~% Vaseline removed
from the 1.0~ ~ 1.0~ treated area~, an objective determina-
tion, after which the microslide was immediately returned to
SUB~ ~ JTE SHEET
WO9l/00337 PCT/US90/03317
~ 16
i~ the stirred agueous cleaner/degreaser bath. The duration of
the degreasing test is determined by the time needed for
complete, 100% removal of the Vaseline film from the glass
microslide surface.
The accuracy of the above-described test method is
of the order of ~ 5% as determined by replicate run
averaging.
E~amPle 2
An aqueous, cleaner/degreaser formulation in the
form of a microemulsion was prepared having the following
composition:
Component Wt.
l-Pheno~y-2-propanol
(Dowanol PPh) 3.0
Monoethanolamine 1.8
Sodium metasilicate 1.5
Dodecylbenzenesulfonic acid 1.0
Soft H20 92.7
100 .0
The sodium metasilicate was dissolved in water with stirring.
The monoethanolamine, l-pheno~y-2-propanol and dodecyl-
benzenesulfonic acid were added and stirring of the resultant
emulsion/suspension was continued until the emulsion gradu-
ally cleared to produce an irridescent (blue) microemulsion.
The microemulsion had a pH of 12.65, a total solids content
of 2.5% and a total actives content of 7.3%. Upon heating,
the microemulsion remained irrides~ent to 50OC, then devel-
oped more turbidity up to 75~C and became a clear, colorless
aqueous solution above about 75~C. It e~hibited no cloud
point to 100~C.
The composition readily removed the following
soilant markin~s from alkyd enameled metal surfaces: black
SUBSTITUTE SHEET
WO 91/00337 PCI/US90/03317
17 ~- ~~ ~ r~ rl
Magic Marker, black and blue indelible ballpoint pen, #l
hardness pencil, red (wa~y) crayon, and automotive grease
smearings. Some trace smudge was left on the surface. The
composition readily removed four coats of floor finish
~trade designation ~Buckeye Citation~ by The Davies-Young
Company) from vinyl tile upon 5 minutes contact time at room
temperature, followed by swabbing action, a water rinse and
air drying.
This composition was subjected to the degreasing
test method of E~ample 1 with the following results:
1st attac~ on greased slide at 2-3 sec.
30% removal of grease at 30 sec.
60-65% removal of grease at 1.0 min.
100% removal of grease at 1.5 min.
E~amPle 3
E~ample 2 was repeated in formulating an aqueous
cleaner~degreaser microemulsion having the following
composition:
Comvonent Wt. %
1-Pheno~-2-propanol
(Dowanol PPh) 3.5
Monoethanolamine 0.5
Sodium Metasilicate 1.2
Dodecylbenzenesulfonic acid 1.2
Sodium ~lene sulfonate (40%) 5.0
Soft H2O 88.6
100 . 00
The composition was a bluish, irridescent microemulsion
having a pH of 12.5, a total solids content of 4.4% and a
total actives content of 8.4%. Upon heating, the composi-
tion remained an irridescent microemulsion to 48~C, became a
turbid emulsion between 48-59~C and a clear, colorless
solution above about 60~C.
SUBST~TUTE SHEET
W O 91/00337 PC~r/US90/03317
; 18
,
The composition effected 100% removal of the
markings set forth in E~ample 2 and also effected 100%
removal of four coats of ~Buckeye Citation~ floor finish as
in E~ample 2.
This composition was subjected to the degreasing
test method of E~ample 1 with the following results:
1st attack on greased slide at Z sec.
33% removal of grease at 15 sec.
60% removal of grease at 30 sec.
80-85% removal of grease at 45 sec.
100% removal of grease at 1.0 min.
E~ample 4
E~ample 2 was repeated in formulating an aqueous,
cleaner/degreaser microemulsion having the following
composition:
ComPonent Wt. %
l-Pheno~y-2-propanol
(Dowanol PPh) 3.5
Monoethanolamine 0.5
Sodium metasilicate 1.2
Dodecylbenzenesulfonic acid 1.2
Sodium cumene sulfonate (45%) 3.5
Soft H2O 90.1
100 . O
The composition was a bluish, irridescent microemulsion
haviny a pH of 12.6, a total solids content of 3.98% and a
total actives content of 7.98%. Upon heating, the
composition remained an irridescent microemulsion to 39~C
and became a clear, colorless solution above about 39~C. It
e~hibited no cloud point to 100~C.
SUBST~TUTE SHEET
~O91/00337 PCT/US90/03317
The composition effected 100% removal of the
markings set forth in E~ample 2 with no smudging, and also
effected 100% removal of four coats of ~Buckwye Citation~
floor finish as in E~ample 2.
This composition was subjected to the degreasing
test method of E~ample 1 with the following results:
10% removal of grease at 15 sec.
25% removal of grease at 30 sec.
45-50% removal of grease at 1.0 min.
70% removal of grease at 1.5 min.
85-90% removal of grease at 2.0 min.
100% removal of grease at 2.5 min.
E~amPle 5
E~ample 2 was repeated in formulating an aqueous,
cleaner/degreaser microemulsion having the following compo-
sitlon:
Component Wt.
l-Pheno~y-2-propanol
(Dowanol PPh) 3.5
Monoethanolamine 0.5
Sodium metasilicate 1.2
Dodecylbenzenesulfonic acid 1.2
Sodium Capryloamphopropionate,
50% Monateric CY-Na-50 2.0
Soft H2O 91.6
100.00
The composition was a pale yellow, irridescent microemulsion
having a pH of 12.5, a total solids content of 3.4% and a
total actives content of 7.4%. Upon heating, the composi-
tion remained an irridescent microemulsion to 50~C andbecame a clear solution at temperatures above 50~C. It
e~hibited no cloud point.
SUBSTITUTE SHEE~
W O 91/00337 PC~r/US90/03317
~,
The composition effected 100% removal of the
markings set forth in E~ample 2 with no to very slight
smudging, and also effected 95-100% removal of four coats of
~Bucke~e Citation~ floor finish as in E~ample 2.
This composition was subjected to the degreasing
test method of E~ample 1 with the following results:
1st attack on greased slide at 3 sec.
20-25% removal of grease at 15 sec.
50% removal of grease at 30 sec.
85-90% removal of grease at 45 sec.
100% removal of grease at 1.0 min.
E~ample 6
E~ample 2 was repeated in formulating an aqueous,
cleaner~degreaser microemulsion having the following
composition:
Comvonent Wt. %
l-Pheno~y-2-propanol
(Dowanol PPh) 4.0
Sodium metasilicate 1.0
20 Sodium hydro~ide (50%) 0.2
Dodecylbenzenesulfonic acid 1.5
Sodium ~ylene sulfonate (40%) 5.0
Monoethanolamine 0.5
Soft H2O 87.8
100.00
The composition was a bluish, irridescent microemulsion
having a pH of 12.65, a total solids content of 4.6% and a
total actives content of 9.1%. Upon heating, the
composition remained an irridescent microemulsion to 51.5~C,
was turbid in the range 50-60~C, and was a clear, colorless
solution above about 60~C.
SUBSTITUTE SHEE~
W O 91/00337 PC~r/US90/03317
~ ~ Il~ f,? r~J
2 ~ 7 ~ 21
, .
The composition effected 100~ removal of the
markings set forth in E~ample 2 with slight smudging and
also effected 100% removal of four coats of ~Buckeye
Citation~ floor finish as in E~ample 2.
The composition was subjected to the degreasing
test method of E~ample 1 with the following results:
20~ removal of grease at 30 sec.
35% removal of grease at 1.0 min.
60% removal of grease at 2.0 min.
90% removal of grease at 3.0 min.
100% removal of grease at 3.33 min.
E~am~le 7
A control composition was prepared by combining
the following components in the amounts indicated:
ComPonent Wt.
l-Pheno~y-l-propanol
(Dowanol PPh) 4.0
Dodecylbenzenesulfonic acid 1.7
Sodium hydro~ide (50%)0.5
Monoethanolamine 1.5
Soft H2O 92.~
100 . O
The composition was a clear, essentially colorless solution
containing no builder component. It had a pH of 11.7, a
total solids content of 1.844% and a total actives content
of 7.344%. It e~hibited no cloud point to 100~C.
The composition quite easily removed the following
percentages of the markings set forth in E~ample 2 from
alkyd enameled metal surfaces:
85-90% removal of black Magic Marker felt pen
80% removal of black indelible ballpoint pen
100% removal of blue indelible ballpoint pen
SUBSTITUTE SHEET
WO91/00337 PCT/US90/03317
22
~L
90% removal of #1 pencil
95% removal of red (wa~y) crayon
,,
100% removal of automobile grease smearings
There was slight smudging with the black Magic Marker and
black indelible ballpoint pen markings. The composition
also effected 100% removal of four coats of ~Buckeye
Citation~ floor finish as in E~ample 2.
The composition was subjected to the degreasing
test method of E~ample 1 with the following results:
10-15% removal of grease at 15 sec.
25% removal of grease at 30 sec.
45% removal of grease at 1.0 min.
70-75% removal of grease at 2.0 min.
90% removal of grease at 3.0 min.
100% removal of grease at 3.5 min.
E~am~le 8
An aqueous, cleaner/degreaser formulation in the
form of a microemulsion was prepared having the following
composition:
ComPonent Wt.
l-Pheno~y-2-propanol
(Dowanol PPh) 4.0
Dodecylbenzenesulfonic acid 1.7
Sodium hydro~ide (50%)0.4
Monoethanolamine 0.9
Soft H20 92.6
Sodium metasilicate 0.4
100 . O
All of the above components e~cept the sodium metasilicate
were stirred together to form an aqueous solution. The
sodium metasilicate was then added as granules and upon
dissolving in the solution, a microemulsion was formed
having a bluish, irridescent appearance. The microemulsion
SUBSTITUTE SHEET
W O 91/00337 PC~r/US90/03317
~ 7 ~ 23
had a pH of 12.1, a total solids content of 2.22% and a
total actives content of 7.12%. Upon heating, the
microemulsion remained irridescent to 37~C. and became a
clear, colorless solution above about 37~C. It e~hibited no
cloud point.
The composition effe~ted 100% removal of the
markings set forth in E~ample 2 with no smudging and also
effected 100% removal of four coats of ~Buckeye Citation~
floor finish as in Esample 2.
This composition was subjected to the degreasing
test method of E~ample 1 with the following results
33% removal of grease at 15 sec.
60% removal of grease at 30 sec.
85-90% removal of grease at 45 sec.
100% removal of grease at 1.0 min.
Esample 9
An aqueous, cleaner/degreaser formulation in the
form of a microemulsion was prepared having the following
composition:
ComPonent Wt. %
l-Pheno~y-2-propanol 4.0
(Dowanol PPh)
Dodecylbenzenesulfonic acid 1.7
Sodium Hydro~ide (50%) 0.5
Monoethanolamine 1.5
Soft H20 91.9
Sodium metasilicate0.4
100 . O
All of the above components e~cept the sodium metasilicate
3~ were stirred together to form a clear, aqueous solution.
The sodium metasilicate was then added as granules and upon
dissolving in the solution, a microemulsion was formed
SUB~ ~ JTE SHEE~
WO91/00337 PCT/US90/03317
-~ 24
~3
~, "o
~~ having a bluish, irridescent appearance. The microemulsion
had a pH of 12.3, a total solids content of 2.24% and a
total actives content of 7.74%. Upon heating, the micro-
emulsion remained irridescent to 41~C. Above about 41~C it
became a clear, colorless solution. It eshibited no cloud
point.
The composition effected 100% removal of the
markings set forth in Esample 2 with very slight tendency
to smudge and also effected 100% removal of four coats of
~Buc~eye Citation~ floor finish as in Esample 2.
This composition was subjected to the degreasing
test method of Esample 1 with the following results:
25-30% removal of grease at 15 sec.
60-65% removal of grease at 30 sec.
85-90% removal of grease at 45 sec.
100% removal of grease at 50 sec.
By comparison with the results set forth in
Esample 7, the above results show the enh~nced degreasing
activity achieved throught the incorporation of a builder.
E~am~le 10
Esamples 8 and 9 were repeated in preparing a
microemulsion cleaner~degreaser formulation having the
following composition:
Component Wt.%
1-Pheno~y-2-propanol 4.0
(Dowanol PPh)
Dodecylbenzenesulfonic acid 1.6
Soduim hydroside (50%)0.4
Monoethanolamine 1.5
Soft H2O 92.1
Sodium metasilicate 0.4
100 . O
SUBSTITUTE SHEET
WO91/00337 PCT/US90/03317
.J
The microemulsion had a bluish, irridescent appearance, a
pH of 12.3, a total solids content of 2.12% and a total
actives content of 7.62%. Upon heating, the microemulsion
remained irridescent to 44~C and above which it formed a
clear, colorless solution. It eshibited no cloud point.
The composition effected 100% removal of all
markings including auto grease as set forth in E~ample 2
and also effected 100% removal of four coats of ~Buckeye
Citation~ floor finish as in E~ample 2.
The composition was subjected to the degreasing
test method of E~amplel with the following results:
1st attack on greased slide at 1-2 sec.
40% removal of grease at 15 sec.
70-75% removal of grease at 30 sec.
100% removal of greease at 45 sec.
E~amPle 11
Esamples 8 and 9 were repeated in preparing a
microemulsion cleaner~degreaser formulation having the
following composition:
Component Wt. %
l-Pheno~y-2-propanol
(Dowanol PPh) 4.0
Dodecylbenzenesulfonic acid 1.6
Sodium hydroside (50%)0.4
Monoethanolamine 1.5
Soft H2O 92.0
Sodium metasilicate 0.5
100 . O
The microemulsion had a bluish, irridescent appearance, a pH
of 12.4, a total solids contents of 2.22% and a total actives
content of 7.72% Upon heating, the microemulsion remained
irridescent to 52.5~C and became a clear solution above
57.~~C I~ e~hibi~ed n~ cl~ud p~int
SUBSTITUTE SHEET
WO91/00337 PCT/US90/03317
26
.~ ~, , ~
f,~ The composition effected 100% removal of all
~u markings set forth in E~ample 2 with no smudging and also
;~ effected 100% removal of four coats of ~Buckeye Citation~
~f floor finish as in Esample 2.
This composition was subjected to the degreasing
test method of E~ample 1 with the following results:
20-25~ removal of grease at 15 sec.
50% removal of grease at 30 sec.
75% removal of grease at 1.0 min.
85-90% removal of grease at 1.5 min.
100% removal of grease at 2.0 min.
Esamp_e 12
An aqueous, cleaner/degreaser formulation in the
form of a microemulsion was prepared having the following
composition:
ComPonent Wt. %
l-Pheno~y-2-propanol
(Dowanol PPh) 4.0
Dodecylbenzenesulfonic acid 1.5
Sodium hydro~ide (50%)0.4
Soft H2O 93.7
Tetrapostassium pyrophosphate 0.4
100 . O
All of the above components e~cept tetrapotassium pyro-
phosphate were stirred together and the pH adjusted to 7.0
with a trace of sodium sesquicarbonate to obtain a clear,
colorless a~ueous solution. The tetrapotassium pyrophos-
phate was then added as granules and the solution immedi-
ately changed to a bluish, irridescent microemulsion. The
microemulsion had a pH of 9.11, a total solids content of
2.11% and a total actives content of 6.115%. Upon heating,
the microemulsion remained irridescent to 42~C. It
exhibited no cloud point to 100~C and no flash point.
SUBST~TUTE SHEET
W O 91/00337 PC~r/US90/03317
7 -~ 27
The composition effected 100%, easy and fast
removal of all markings set forth in E~ample 2.
This composition was subjectea to the degreasing
test method of E~ample 1 with the following results:
1st attack on greased slide at 2 sec.
45~ removal of grease at 15 sec.
90-95% reemoval of grease at 30 sec.
100% removal of grease at 35 sec.
E~ample 13
E~ample 12 was repeated in preparing a
microemulsion cleaner~degreaser formulation having
following composition:
ComPonent Wt. %
l-Pheno~y-2-propanol 4.0
Dodecylbenzenesulfonic acid 1.5
Sodium hydro~ide (50%)0.4
Soft H2O 93.7
Bora~ 0.4
100 . O
The microemulsion formed upon the addition of bora~
granules to the other components and the slow dissolution
of the bora~ produced a gradual change from a clear,
a~ueous solution to a bluish, irridescent microemulsion.
The microemulsion had a pH of 8.93, a total solids content
of 2.115% and a total actives content of 6.115%. Upon
heating, the microemulsion remained irridescent to 38~C,
clearing at 38.5~C and becoming a clear, colorless solution
above about 39~C. It e~hibited no cloud point to 100~C and
no flash point.
SUBSTITUTE SHEET
WO91/00337 PCT/US90/03317
28
~ ~ 3
~é~
The composition effected 100% facile removal of
all markings set forth in E~ample 2.
This composition was subjected to the degreasing
test method of E~ample 1 with the following results:
1st attack on greased slide at 1-2 sec.
50-55% removl of grease at 15 sec.
80% removal of grease at 30 sec.
100% removal of grease at 40 sec.
E~amDle 14
E~ample lZ was repeated in preparing a microemul-
sion cleaner/degreaser formulation having the following
composition:
Compon~nt Wt. %
l-Pheno~y-2-propanol 4.0
(Dowanol PPh)
~odecylbenzenesulfonic acid 1.5
Sodium hydro~ide (50%)0.4
Soft H20 93.6
Sodium carbonate 0.5
100.0
The addition of the sodium carbonate in powder form to a
clear, colorless agueous solution of the other components
produced the instantaneous development of a bluish,
irridescent microemulsion. The microemulsion had a pH of
10.75, a total solids content of 2.215% and a total actives
content of 6.215%. The microemulsion, unlike those of
E~amples 12 and 13, was slightly viscous and had a
Brookfield viscosity of 37 cps. at 21~C. Upon heating, the
microemulsion remained irridescent to 60.5~C and became a
clear, colorless aqueous solution above about 61~C. It
e~hibited no cloud point to 100~C.
The composition effected 100%, fast removal of
all markings set forth in E~ample 2.
SUBSTITUTE SHEE-r
W O 91/00337 PC~r/US90/03317 e~ 2 9 ~ ~ ~ ~s c-~ ~3 r ~
This composition was subjected to the degreasing
test method of E~ample 1 with the following result:
1st attack in greased slide at 2 sec.
30-35% removal of grease at 15 sec.
60% removal of grease at 30 sec.
85-90~ removal of grease at 40 sec.
100% removal of grease at 50 sec.
E~amDle 15
E~ample 2 was repeated in formulating an aqueous,
cleaner~degreaser microemulsion having the following compo-
sition:
ComPonent Wt. %
2-Pheno~yethanol 6.4
(Dowanol EPh)
Dodecylbenzenesulfonic acid 2.S
Anhydrous sodium 3.5
metasilicate
Chelating agent 2 ~ 0
(Hampene 100, 40%)
Sodium ~ylene sulfonate (40%) 7.5
Soft H20 78.1
100 . O
The composition was a faint bluish, microemulsion having a
pH of 12.86, a total solids content of 9.8% and a total
actives content of 16.2%. It e~hibited no cloud content of
point to 100~C and no flash point.
At a 1:5 dilution with water, the composition
effected 75% removal of black Magic Marker markings from an
alkyd enameled steel panel.
This composition at a 1:2 dilution with water
was sub~ected to the degreasing test method of E~ample 1
with the following results:
SUB~ 111 ~JTE SHEEl
W O 91/00337 PC-r/US9OtO3317
' 30
~ '~
1st attack on greased slide at 8 sec.
~' 10% removal of grease at 30 sec.
30% removal of grease at 1.0 min.
55% removal of grease at 2.0 min.
80-85% removal of grease at 4.0 min.
100% removal of grease at 6.0 min.
EsamPle 16
E~ample 2 was repeated in formulating an aqueous,
cleaner/degreaser microemulsion having the following
composition:
ComPonent Wt. %
Anhydrous sodium 3. 6
metasilicate
Dodecylbenzenesulfonic2.80
acid
Chelating Agent 2.00
(Hampene 100)
Propyleneglycol 2.00
monomethyl ether
Dipropyleneglycol 0.95
monomethyl ether
Tripropyleneglycol 0. 70
monomethyl ether
l-Pheno~y-2-propanol 6.35
(Dowanol PPh)
Sodium ~ylene sulfonate8.50
Soft H2O 73.l0
100 . 00
The composition was a faint, bluish, colloidal microemulsion
having a pH of 13.23, a total solids content of 10.6% and a
total actives content of 20.6%. It e~hibited no cloud
point and no flash point.
SUBSTITUTE SHEEl'
W O 91/00337 PC~r/US90/03317
J 31
At a 1:5 dilution with water, the composition
effected 90% removal of black Ma~ic Marker markings from an
al~yd enameled steel panel.
This composition at a 1:2 dilution with water was
subjected to the degreasing test method of E~ample 1 with
the following results:
1st attack on greased slide at 5 sec.
15% removal of grease at 30 sec.
35% removal of grease at 1.0 min.
70% removal of grease at 2.0 min.
90% removal of grease at 3.0 min.
100% removal of grease at 3.75 min.
E~amDle 17
E~ample 2 was repeated in formulating an aqueous
having the following composition:
ComPonent Wt. %
Anhydrous sodium 5.50
metasilicate
Dodecylbenzenesulfonic acid 5.00
Chelating agent 2.00
(Hampene 100)
Propyleneglycol 2.00
monomethyl ether
Dipropyleneglycol 0.95
monomethyl ether
Tripropyleneglycol 0.70
monomethyl ether
l-Pheno~y-2-propanol 6.35
(Dowanol PPh)
Sodium ~ylene sulfonate (40%) 8.5
Soft H20 69.0
100 . O
SUB~ 111 ~JTE SHEET
W O 91/00337 PC-r/~'S90/03317
32
The components formed a clear, aqueous solution rather than
a microemulsion because the composition included an e~cess
of solubilizing additive over that required to form a micro-
emulsion.
At a 1:5 dilution with water, the solution
effected 0% removal of black Magic ~ar~er markings from an
alkyd enameled steel panel.
The solution at a 1:2 dilution with water was
subjected to the degreasing test method of Esample 1 with
the following results:
1st attack on greased slide at 2.5 min.
10% removal of grease at 4.5 min.
20-25% removal of grease at 10 min.
50% removal of grease at 20 min.
70% removal of grease at 30 min.
90-95% removal of grease at 50 min.
100% removal of grease at 65 min.
E~ample 18
E~ample 2 was repeated in formulating an aqueous
microemulsion having the following composition:
ComPonent Wt. %
Anhydrous sodium 4.0
metasilicate
Dodecylbenzenesulfonic acid 2.0
Propylene glycol mono-t-butyl 9.5
ether (Arcosolve PTB)
Chelating agent ~Hampene 100) 3.0
Soft H20 81.5
100 . O
The organic solvent component, propylene glycol mono-t-
butuyl ether, has an aqueous solubility of 13.9 wt. % at
21~C. The composition was a very faint bluish,
SUBST~TUTE SHEET
WO91/00337 PCT/US90/03317
33 _~
f ~
colloidal microemulsion having a pH of 13.73, a total
solids content of 7.2% and a total actives content of
16.7%. It had a cloud point of 28~C.
At a 1:5 dilution with water, the composition
effected 60% removal of black Magic Mar~er markings from an
al~yd enameled steel surface.
This composition at a 1:2 dilution with water
became solution and was subjected to the degreasing test
method of E~ample 1 with the following results:
1st attack on greased slide at 7 sec.
20-25% removal of grease at 1.0 min.
33% removal of grease at 2.0 min.
40% removal of grease at 3.0 min.
45-50% removal of grease at 4.0 min.
60% removal of grease at 5.0 min.
65-70% removal of grease at 6.0 min.
75% removal of grease at 7.0 min.
80% removal of grease at 8.0 min.
85% removal of grease at 9.0 min.
90% removal of grease at 10.0 min.
95% removal of grease at 12.0 min.
100% removal of grease at 13.5 min.
E~amPle 19
E~ample 2 was repeated in formulating an aqueous,
cleaner~degreaser microemulsion having the following
composition:
Component Wt. %
Anhydrous sodium 2.0
metasilicate
Nonylphenol etho~ylate3.5
(T-Det N-14)
Chelating agent 2.0
(Hampene lOQ, 40%)
Dipropylenegycol 3.5
monometh~l ether
SUB~ 111 ~JTE SHEET
W O 91/00337 PC~r/US90/03317
~ 34
~' .
j*,.
'~ l-Pheno~y-2-propanol 6.5
(Dowanol PPh)
~~
Sodium ~ylene sulfonate (40%) 11.0
Soft H20 71.5
100.0
The composition was a slightly bluish, colloidal micro-
emulsion having a pH 13.62, a total solids content of 10.7%
and a total actives content of 20.7%. It had a cloud point
of 26~C and no flash point.
At a 1:5 dilution with water, the composition
effected 100~ removal of black Magic Marker markings from
an al~yd enameled steel panel.
This composition at a 1:2 dilution with water was
subjected to the degreasing test method of E~ample 1 with
the following results:
1st attack on greased slide at 5 sec.
25% removal of grease at 20 sec.
60% removal of grease at 40 sec.
85-90% removal of grease at 1.0 min.
100% removal of grease at 1.5 min.
EsamPle 2_
E~ample 2 was repeated in formulating an aqueous,
cleaner~degreaser microemulsion having the following
composition:
2 5 Com~onent Wt. %
Anhydrous sodium 2.0
metasilicate
Dodecylbenzenesulfonic acid 1.5
Chelating agent 5.0
(Hampene 100, 40%)
Benzyl acohol 9.0
Tripropyleneglycol 1.0
monomethyl ether
SUBSTITUTE SHEET
W O 91~00337 PC~r/US90/03317
~ ~ 6~ , '7 ', 35
Sodium ~ylene sulfonate (40%) 9. 5
Soft H20 7.2
100. 0
The composition was faint bluish microemulsion having a pH
of 13.19, a total solids content of 9. 3% and a total actives
content of 19.3%. It had a cloud point in escess of 100~C
and no flash point.
At a 1:5 dilution with water, the composition
effected 50% removal of black Magic Mar)~er markings from an
alkyd enameled steel panel.
This composition at a 1:2 dilution with water was
subjected to the degreasing test method of E~ample 1 with
the following results:
1st attack on greased slide at 4 sec.
35% removal of grease at 30 sec.
60% removal of grease at 1.0 min.
75-80% removal of grease at 1. 5 min.
85-90% removal of grease at 2.0 min.
95% removal of grease at 2. 5 min.
100% removal of grease at 2. 75 min.
E~ample 21
E~ample 2 was repeated in formulating an a~ueous,
cleaner/degreaser microemulsion having the following
composition:
ComPonent Wt.
Anhydrous sodium 2.0
metasilicate
Dodecylbenzenesulfonic acid 2. 5
Chelating agent 1. 5
(Hampene 100, 40%)
Tripropyleneglycol 2.5
monomethyl ether
l-Pheno~y-2-propanol 7.0
(Dowanol PPh)
SUBSTITUTE SHEET
W O 91/00337 PC~r/US90/03317
36
3~
,~ Sodium ~ylene sulfonate (40%) 9.O
Soft H20 75.5
10 0 ~ O
The composition was a faint bluish microemulsion having a
pH of 13.05 a total solids content of 8.7% and a total
actives content of 18.2%. It had a cloud point of appro~i-
mately 75~C and no flash point.
At a 1:5 dilution with water, the composition
effected appro~imately 95% of black Magic Marker markings
from an alkyd enameled steel panel.
This composition at a 1:2 dilution with water was
subjected to the degreasing test method of E~ample 1 with
the following results:
1st attack on greased slide at 4 sec.
45% removal of qrease at 30 sec.
65-70% removal of grease at 1.0 min.
80~ removal of grease at 1.5 min.
90% removal of grease at 2.0 min.
100% removal of grease at 2.5 min.
E~ample 22
E~ample 21 was repeated in formulating an aqueous
microemulsion containing no builder component and having
the following composition:
ComPonent Wt.
25 Dodecylbenzenesulfonic acid 2.5
Sodium hydro~ide (50%) 0.4
Chelating agent 1.5
(Hampene 100, 40%)
Tripropyleneglycol 2.5
monomethyl ether
l-~heno~y-2-propanol 7.0
(Dowanol PPh)
SUBSTITUTE SHEET
WO91/00337 PCT/US90/03317
~ 37
Sodium ~ylene sulfonate (40%) 6.5
Soft H2O 7.96
100.O
The small amount of sodium hydro~ide was included to
partially neutralize the dodecylbenzenesulfonic acid and
cause salt formation. The composition was a faint
opalescent microemulsion having a pH of 7.0, a total solids
content of 5.9% and a total actives content of 15.4%. It
had a cloud point in e~cess of 100~C and e~hibited no flash
point.
At a 1:5 dilution with water, the composition
effected only 0-5% removal of black Magic Marker markings
from an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was
subjected to the degreasing test method of E~ample 1 with
the following results:
1st attack on greased slide at 11 sec.
5-10% removal of grease at 30 sec.
30% removal of grease at 1.0 min.
55-60% removal of grease at 1.5 min.
70% removal of grease at 2.0 min.
85-90% removal of grease at 3.0 min
95% removal of grease at 4.0 min.
100% removal of grease at 4.5 min.
Thus, by comparison with the composition of Esample 21, the
composition of this e~ample containing no builder component
was less effective than the builder-containing composition
of E~ample 21.
E~amPle 23
E~ample 2 was repeated in formulating an aqueous,
cleanerfdegreaser microemulsion having the following
composition:
SUB~ I ~ I ~JTE SHEET
WO91/00337 PCT/US90/03317
38
~' .
~' ComPonent Wt. %
~"
Sodium tripolyphosphate 2.0
Dodecylbenzenesulfonic acid 2.5
Chelating agent
(Hampene 100, 40%) 1.5
Tripropyleneglycol
monomethyl ether 2.5
l-Pheno~y-2-propanol
(Dowanol PPh) 7.0
Sodium ~ylene sulfonate (40%) 7.5
Soft H2O 76.4
100.O
The composition was a bluish, opalescent microemulsion
having a pH of 11.27, a total solids content of 8.4% and a
total actives content of 17.9%. It had a cloud point in
e~cess of 100~C and e~hibited no flash point.
At a 1:5 dilution with water, the composition
effected 60% removal of black Magic Mar~er markings from an
al~yd enameled steel panel.
The composition at a 1:2 dilution with water was
subjected to the degreasing test method of E~ample 1 with
the following results:
1st attack on greased slide at 6 sec.
25% removal of grease at 30 sec.
40-45% removal of grease at 1.0 min.
65-70% removal of grease at 1.5 min.
80% removal of grease at 2.0 min.
90% removal of grease at 2.5 min.
100% removal of greast at 3.0 min.
E~ample 24
E~ample 2 was repeated in formulating an aqueous,
cleaner/degreaser microemulsion having the following
composition:
SUBSTITUTE SHEE~
W O 91/00337 PC~r/US90/03317
39 ~ .
ComPonent Wt. %
Anhydrous sodium metasilicate 2.2
Dodecylbenzenesulfonic acid 2.5
Polyglycol llZ-2(Dow) 10.0
Block ethylene o~ide/
propylene o~ide copolyol,
terminated by glycerol)
Soft H2O 85.3
100 . O
The composition was a very faint microemulsion having a pH
of 12.73, and a total solids and total acti~es content of
14.7%. It had a cloud point of 40~C and e~hibited no flash
point.
At a 1:5 dilution with water, the composition
effected 100% removal of black Magic Marker markings from
an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was
subjected to the degreasing test method of Esample 1 with
the following results:
1st attack on greased slide at 4 sec.
20% removal of grease at 30 sec.
55-60% removal of grease at 1.0 min.
80% removal of grease at 1.5 min.
100% removal of greast at 2.0 min.
E~amPle 25
E~ample 2 was repeated in preparing the following
composition containing a highly water soluble organic
solvent instead of a sparingly water soluble organic
solvent:
ComPonent Wt.
Anhydrous sodium metasilicate 2.0
Dodecylbenzenesulfonic acid 2.4
SUBSTITUTE SHEET
W091/00337 PCT/US90/03317
Ethylene glycol monobutyl
ether (Butyl Cellosolve) 10.0
~7 Soft H2O 85.6
100.0
The composition was a clear, very pale yellow solution
having a pH of 12.53, a total solids content of 4.4% and a
total actives content of 14.4%. It had a cloud point in
e~cess of 100~C.
At a 1:5 dilution with water, the composition
effected less than 5% removal of black Magic Marker mark-
ings from an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was
subjected to the degreasing test method of Esample 1 with
the following results:
1st attack on greased slide at 20 sec.
15% removal of grease at 1.0 min.
25-30% removal of grease at 20 min.
35-40% removal of grease at 3.0 min.
45% removal of grease at 4.0 min.
50-55% removal of grease at 6.0 min.
65% removal of grease at 10.0 min.
75% removal of grease at 15.0 min.
80% removal of grease at 20.0 min.
85% removal of grease at 25.0 min.
90% removal of grease at 30.0 min.
95% removal of grease at 35.0 min.
100% removal of grease at 39.0 min.
E~amPle 26
E~ample 2 was repeated in formulating an aqueous,
cleaner~degreaser microemulsion having the following
composition:
SUBSTITUTE SHEET
W O 91/00337 PC~r/US90/03317
7 ~;
ComPonent Wt. %
Anhydrous sodium metasilicate 2.3
Dodecylbenzenesulfonic acid 2.8
Tripropyleneglycol monomethyl
ether 5.0
Acetophenone 5.0
Soft H20 84.9
100.O
The composition was a bluish, irridescent microemulsion
having a pH of 12.61, a total solids content of 5.1% and a
total actives content of 15.1%. It had a cloud point in
e~cess of 100~C and eshibited no flash point.
At a 1:5 dilution with water, the composition
effected 100% removal of black Magic Mar~er markings from
an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was
subjected to the degreasing test method of Esample 1 with
the following results:
1st attack on greased slide at 5 sec.
25-30~ removal of grease at 30 sec.
70% removal of grease at 1.0 min.
100% removal of grease at 1.5 min.
E~ample 27
E~ample 2 was repeated in formulating an aqueous
Z5 cleaner~degreaser microemulsion having the following
composition:
ComPonent Wt. %
Anhydrous sodium metasilicate 2.0
Dodecylbenzenesulfonic acid 2.5
Cyclohe~anol 8.5
SUBSTITUTE SHEET
W O 91/00337 PC~r/US90/03317
42
g~
.
~G Tripropyleneglycol
monomethyl ether 1.5
Sodium ~ lene sulfonate ( 4096) 5. 4
Soft H20 80.1
100.0
The composition was a faint bluish microemulsion having a
pH of 12.74, a total solids content of 6.66% and a total
actives content of 16.66%. It had a cloud point of 65~C.
At a dilution of 1:5 with water, the composition
effected appro~imately 65~ removal of black Magic Mar~er
markings from an al~yd enameled steel panel.
The composition at a 1:2 dilution with water was
subjected to the degreasing test method of Esample 1 with
the following results:
1st attack on greased slide at 1.5 sec.
5-10% removal of grease at 30 sec.
15% removal of grease at 1.0 min.
20% removal of grease at 2.0 min.
30% removal of grease at 3.0 min.
40% removal of grease at 4.0 min.
50-55% removal of grease at 5.0 min.
70% removal of grease at 6.0 min.
85% removal of grease at 7.0 min.
100% removal of grease at 8.0 min.
E~ample 28
E~ample Z was repeated in formulating an aqueous,
cleaner~degreaser microemulsion having the following
compositlon:
Com~onent Wt. %
Anhydrous sodium metasilicate 2.0
2-Pheno~yethanol
(Dowanol EPh) 9.0
SUBSTITUTE SHEET
WO91/00337 PCT/US90/03317
43
Coco betaine (30%) 4.0
Sodium ~ylene sulfonate
(40%) 9.6
Soft H2O 75~4
lO0.0
The composition was a light bluish, irridescent micro-
emulsion having a pH of 13.42, a total solids content of
7.04 and a total actives content of 16.04%. It had a cloud
point above 100~C and no flash point.
At a dilution of l:5 with water, the composition
effected 100% removal of black Magic Marker markings from
an alkyd enameled steel panel.
The composition at a 1:2 dilution with water was
subjected to the degreasing test method of E~ample l with
l~ the following results:
1st attack on greased slide at 3 sec.
25-30% removal of greast at 30 sec.
65-70% removal of grease at l.0 min.
lO0~ removal of grease at l.5 min.
Z~ E~ample 29
An aqueous, cleaner/degreaser formulation in the
form of a microemulsion was prepared having the following
composition:
ComPonent Wt. %
Monoethanolamine 0.5
Sodium Metasilicate 2.0
l-Pheno~y-2-propanol 7.0
(D~wanol PPh)
Tripropyleneglycol monomethyl 3.0
ether
Doodecylbenzenesulfonic acid 3.0
Soft HzO 8Z.4
SUBSTITUTE SHEET
W O 91/00337 PC~r/US90/03317
~'
44
~,6
Isodecylo~ypropylimino- 2.0
dipropionic acid
(~Alkali Surfactant~, Tomah
Products, 35%)
Defoaming agent
(Atsurf F-12) 0.1
100.O
The sodium metasilicate was dissolved in water with
stirring The monoethanolamine was added followed by the
addition of the 1-pheno~y-2-propanol, tripropyleneglycol
monomethyl ether and dodecylbenzenesulfonic acid with
stirring Stirring was continued until a homogeneous
emulsion formed. The Alkali Surfactant was then added and
the emulsion was transformed into a microemulsion after
which the defoaming agent was added. The resulting micro-
emulsion had a slightly bluish, irridescent appearance, a
pH of 12.42, a total solids content of 5.7% and a total
actives content of 16.2%. It e~hibited a cloud point in
e~cess of 100~C.
The composition at a 1:2 dilution with water was
subjected to the degreasing test method of E~ample 1 with
the following results:
1st attack on greased slide at 1 sec.
40% removal of grease at 15 sec.
75% removal of grease at 30 sec.
100% removal of grease at 65 sec.
In view of the above, it will be seen that the
several objects of the invention are achieved and other
advantageous results attained.
As various changes could be made in the above
compositions without departing from the scope of the
invention, it is intended that all matter contained in the
above description or shown in the accompanying drawings
shall be interpreted as illustrative and not in a limiting
sense.
SUBSTlTUTE SHEET'
