Note: Descriptions are shown in the official language in which they were submitted.
~2~
FABRIC CLE~NI~G COMPOSITIONS YOR CLAY-BASED STAINS
Ivan H~TS
Ja~es P. JOHNS~N
John R. W~æR
Technical Field
The present invention relates to compositions and
processes for removing clay-based soils and stains from
fabrics. The compositions are particularly adapted for
removing cosmetic stains, which cornprise a mixture of clay-
based material and an oily or greasy binder material. Com-
positions which comprise a solvent ingredient to disperse
the binder and a polyamine material to disperse the clay are
provided. These compositions can be used in the form of a
simple fabric pre-spotter, or in fully-formulated laundry
detergents comprising a mixture of various ingredients de-
signed to remove a broad spectrum of stains and soils from
fabrics, with particularlv noteworthy benefits on stains
caused by cosmetics.
Background
Detergent formulators are faced with the task of
devising products to remove a broad spectrum pf soils and
stains from fabrics. Chemically and physico-chemically,
the varieties of soils and stains range the spectrum from
primarily oily, through proteinaceous and carbohydrate, to
inorganic, and detergent compositions have become more
complex as formulators attempt to provide products which
handle all types, concurrently. For example, protease en-
zymes are commonly used in detergents for blood and gravy
stains; amylase enzymes are used for carbohydrate stains;
-- 2
nonionic surfactants are used ~or hydrocarbon oils; and anio-
nic surfactants and b~lilders are~ used Eor particulate soil.
sleach is used to chemically degrade stains that are not
amenable to removal by less rigorous treatment.
One of the most difficult stains to remove frorn fabrics
is the cosme~ic stain, and from -time immemorial -the persis-
tent, telltale smudge of lipstick on a shirtcollar or hand-
kerchief has been the downfall of many a miscreant. More-
over, the remarkable ability of the modern cosmetic industry
to provide products which are more and more long-lasting on
the user's skin necessarily means that today's cosmetics are
increasingly persistent on fabrics to which they are unin-
tentionally applie~.
Chemically, many cosmetics comprise a clay base which
serves in part as a filler, thickener, carrier for color
bodies, and the like, blended with an oily material which
serves partially as a binder, gloss agent and emollient.
Cosmetics are typically manufactured with great care, such
that the clay and color bodies are in the form of very fine
particles, and are very thoroughly and completely mixed
with, and coated by, the oily material, which may be a hy-
drocarbon oil, silicone, lipid, or complex mixtures thereof.
While optimal from the standpoint of the cosmetic formulator,
the modern cosmetic product causes major problems for the
de-tergent formulator, since cosmetics constitute a mix of
widely divergent soil types (oily, particulate, clay~ all in
.intimate admixture and often brightly coloredO No single
detergent ingredient can reasonably be expected to handle
such a complex milieu.
The present invention employs oil-removal solvents and
clay-removal polyamines. The solvents dissolve the oil base
of the cosmetics, thereby exposing their clay component to
~he polyamine materials which disperse and remove it ~rom
fabrics.
The use of solvents of the type employed in this in-
vention as grease and oil removal ingredients in cleaners
-
~LZ3(~533
-- 3 -
of various types is well-known commercially and from
the patent literature. See, for example, U.S. Patent
2.073.464; EPO Applications 0 072 ~88 published ~ebruary
~3, 1983 and 0 040 882 published December 2, 1981; British
Patent 1.603.0~7.
~ Iowever, the use of such solvents in combination
with polyamine materials in the manner disclosed herein
is not believed to have been contemplated, heretoore.
Summary of the Invention
The present invention relates to compositions and
processes for removing cosmetic stains, and the like,
from fabrics, by means of a solvent (especially solvents
such as isoparaffinic hydrocarbons, kerosene, petroleum
fractions, d-limonene or mixed terpenes, fatty alcohols,
benzyl alcohol and mixtures thereo~) and an alkoxylated
polyamine (as described more fully hereinafter) at a
weight ratio of solvent:polyamine of 10~:1 to 1:20, pre-
ferably at least 2:1. The invention also encompasses
fully-formulated detergent compositions which comprise
conventional detergency ingredients such as detergency
builders, enzymes, detersive surfactants, and the like,
characterized in that such compositions contain at least
about 5% by weight of the aforesaid mixture of solvent
and polyamine. Preferably, such fully-formulated deter-
gent compositions contain at least 5~ of the solvent and
at least 0.2% of the polyamine~
Detailed Descrietion of the Invention
The essential solvent and polyamine components, as
well as the preferred surfactant components and other
optional ingredients used in the practice of the present
invention are described in more detail, hereinafter. All
percentages and ra-tios mentioned in this specification
are by weight, unless otherwise stated.
~L2~33
Solvent ~ The solvents employed herein can be any of the
well-known "degreasing" solvents com~only known Eor use in,
for example, the commercial laundry and drycleanin~ indus-
try, in the hard-surface cleaner industry and the metalwor-
king industry. Typically, such solvents comprise hydro-
carbon or halogenated hydrocarbon moie-tles of -the alkyl or
cycloalkyl type, and have a boiling point well above room
temperature.
The formulator of compositions of the present type will
be guided in the selection of solvent partly by the need to
provide good grease-cutting properties, and partly by aesthe-
tic considerations. For example, kerosene hydrocarbons
function quite well in the present compositions, bu-t can be
malodorous. Kerosene can be used in commercial laundries.
For home use, where malodors would not be tolerated, the
formulator would be more likely to select solvents which
have a relatively pleasant odor, or odors which can be reaso-
nably modified by perfuming. Such solvents include, for
example, the terpenes and terpenoid solvents obtainable from
citrus fruits, especially orange terpenes and d-limonene.
senzyl alcohol is another relatively pleasant smelling sol-
vent for use herein.
Excellent solvents for use herein are paraffins and
the mono- and bicyclic mono-terpenes, i.e., those of the
hydrocarbon class, which include, for example, the terpinenes,
limonenes and pinenes, and mixtures thereof. Highly preferred
materials of this type are d-limonene and the mixture of
terpene hydrocarbons obtained from the essence of oranges (e.g.
cold-pressed orange terpenes and orange terpene oil phase
ex fruit juice). Also useful are, for example, terpenes
such a dipentene, alpha-pinene, beta=-pinene and the mixture
of terpene hydrocarbons expressed from lemons and grape-
fruit.
The examples disclosed hereinafter describe various
other solvents which can be used herein.
~l2~ ;3~
- 5 --
Polyami~es - It is to be understood that the term "polyamines"
as used herein represents generically the alkoxylated polyami-
nes, both in their amine form and in their quaternized form.
Such materials can conveniently be represen-ted as molecules
of the empirical structures with repeating unLts:
t N - R tx Amine form
I
alkoxy
and
R
1? ~ X Ouaternarized
alkoxy
wherein R is a hydrocarbyl group, usually of 2-6 carbon
atoms; R may be a Cl-C20 hydrocarbon; the alkoxy groups
are polyethoxy, polypropoxy, and ~he like, with polyethoxy
having a degree of polymerization of 2-30, most preferably,
10 to 20; x is an integer of at least 2, preferably from
; 2-20, most preferably 3-5; and X~ is an anion such as
halide or methylsulfate, resulting from the quaternization
reaction.
The most hi~hly preerred polyamines for use herein are
the so-called ethoxylated polyethylene imines, i.e., the
polymerized reaction product of ethylene oxide with ethylene-
imine, having the general formula:
--~N - CH2-CH2 ~x
(E+O)y
wherein x is an integer of 3 to 5 and y is an integer of 10
to 20.
Surfactants - In addition to the solvent and polyamine, it
33
-- 6
is optional, but highly prcferred, that the compositions
herein contain organic sur~ace-active a~ents ("surfactants")
to provide the usual cleaning benefits associated wi-th the
use of such materials.
Water soluble detersive surfactants useful herein in-
clude well-known synthetic anionic, nonionic, amphoteric
and zwitterionic surfactants. Typical of these are the
alkyl benzene sulfonates, alkyl- and alkylether sulfates,
paraffin sulfonates, olefin sulfonates, alkoxylated (especially
ethoxylated) alcohols and alkyl phenols, amine oxides, ~-
sulfonates o~ fatty acids and of fatty acid esters, and the
like, which are well-known from the detergency art. In
general, such detersive surfactants contain an alkyl group in
the Cg-Cl8 range; the anionic detersive surfactants are most
commonly used in the form of their sodium, potassium or
triethanolammonium salts; the nonionics generally contain from
about 5 to about 17 ethylene oxide groups. U.S. Patents
4,111,855 and 3,995,669 contain detailed listings of such
typical detersive surfactants. Cll-Cl~ alkyl benzene sulfo-
nates, C12-C18 paraffin-sulfonates and alkyl sulfates, and the
ethoxylated alcohols and alkyl phenols are especially preferred
in the compositions of the present type.
The surfactant component can comprise as little as
1% of the compositions herein, but preferably the composi-
tions will contain 1~ to 40~, preferably 5% to 30%, of sur-
factant. Mixtures of the ethoxylated nonionics with anionics
such as the alkyl benzene sulfonates, alkyl sulfates and
paraffin sulfonates are preferred for through-the-wash
cleansing of a broad spectrum of soils and stains from fabrics.
Fatty Acid/Soap Ingredient - Fatty acids (generally C10-Cl8
chain length) and their water-soluble salts (i.e.,
common "soaps", especially alkali metal soaps) can be used
in the present compositions not only for their detersive-
surfactant properties, but also to provide an additional
. ~,~
fL~3~ 3
-- 7
detergency builder function by virtue oE their ability to
interact with water hardness cations. As will be described
more fully hereinafter, fat~y acids and soaps are particu-
larly useful when preparing fully-formulated, homogeneous
oil-in-water liquid detergents comprising the solvent and
polyamine in an aqueous carrier. Usage levels of 0.5 - 50
are typical.
Other Optional Ingredients - The compositions herein can
contain other ingredients which aid in their cleaning per-
~ormance. For example, it is highly preferred that through-
the-wash detergent compositions con~ain a detergent builder
and/or metal ion sequestrant. Compounds classifiable and
well-known in the art as detergent builders include the
nitrilotriacetates, polycarboxylates, citrates, water-
soluble phosphates such as tri-polyphosphate and sodium
ortho- and pyro-phosphates, silicates, and mixtures thereo~.
Metal ion sequestrants include all of the above, plus mate-
rials like ethylenediaminetetraacetate, the amino-polyphos-
phonates and phosphates (D~QUEST) and a wide variety of
other poly-functional organic acids and salts too numerous
to mention in detail here. See U.S. Patent 3,579,454 for
typical examples of the use of such materials in various
cleaning compositions. In general, the builder/sequestrant
will comprise about 0.5% to 15% of the composition. Citrate
is one of the most preferred builders since it is readily
soluble in the aqueous phase of heavy-duty liquid detergent
compositio~s.
The compositions herein also preferably contain enzymes
to enhance their through-the-wash cleaning performance on a
variety of soils and stains. Amylase and protease enzymes
suitable for use in detergents are well-known in the art and
in commercially available liquid and granular detergents.
Commercial detersive enzymes (preferably a rnixture of
amylase and protease) are typically used at levels of
0.001% to 2~, and higher, in the present compositions.
Ingredients such as propane diol and/or formate
.~'
~L~Z3~5i33
-- 8
and calcium can be added to help st~biliz~ the en~ymes in
well-known fashion, according to the desires of the formu-
lator.
Moreover, the compositions herein can contain, in addi-
tion to ingredients already mentioned, various other op-tio-
nal ingredients typically used ln commercial products to
provide aes-thetic or additional product performance benfits.
Typical ingredients include pH regulants, perfumes, dyes,
optical brighteners, soil suspending agents, hydrotropes
and gel control agents, freeze-thaw stabi.lizers, bactericide~,
preservati~es, suds control agents and the like.
Water-alcohol (e.g., ethanol, isopropanol, etc.)
mixtures can be used as the carrier vehicle in liquid
compositions, and alkylated polysaccharides can be used to
increase the stability and performance characteristics of the
compositions.
The compositions herein are preferably formulated in
; the neutral to alkaline pH range r generally in the range of
pH 6.5 - 9.0, preferably about 6.8 - 7.5~ Materials such as
sodium hydroxide, potassium hydroxide, the alkanol amines such
as triethanol-amines, or magnesium hydroxide, can be used to
adjust the pH, as desired. Preferred pH adjusting agents are
described hereinafter.
The preferred compositions herein are in liquid ~orm,
which can be prepared by simply blending the essential and
optional ingredients in a fluid (preferably aqueous) carrier.
As mentioned hereinabove, fatty acid or soap can be used in
such liquid compositions to provide clear, homogeneous
microemulsions of the solvent in an aqueous carrier. Solid
or granular compositions can be prepared by adsorbing the
solvent and polyamine in a suitable granular carrier, for
example, in a sodium sulfate, sodium perborate (bleach) or
spray-dried detergent granule carrier.
In one process aspect, the compositions herein in the
form of liquids or pastes can be used to pre-treat soiled
fabrics by rubbing a few milliliters o~ the compositon directly
onto and into the soiled area, followed by laundering in
standard fashion. In a through-the-wash mode, the compo-
~ r
,~ .
~LZ3~!~3~
si~ions are typically used at a concentrat:ion of at least500 ppm, preferably 0.1~ to l..5~ in an aqueous
laundry bath at pH 6.5 - 10 to launder fabrics. The
laundering can be carried out over the range erom 5C to the
boil, with excellent resul~s.
_ndustrial Application
The following examples describe a varie-ty of formula-
tions which can be prepared in the manner of the present
invention using the mixed solvent/polyamine ingredients.
The examples are given by way of illustration and are not
intended to be limiting of the scope of the invention. In
the formulations listed, the terms l'x1land llyl~ are stated
in parentheses to designate the degree of polymerization and
degree of alkoxylation of the polyamine. For some "polyami-
nesl', the designation R is also included~ thereby denotinga quaternarized polyamine. For such quaternarized materials,
the resultin~ anion ~ is of no consequence to cleaning
performance, and is not designated. In all examples, R is
-CH2-CH2- and alkoxyl is ethoxyl, unless otherwise specified.
Example I
Following the teachings of U.S. Patent 3,664,962, a
spot remover in stick form is prepared by blending the fol-
lowing ingredients, extruding the resulting mass through a
1.25 cm die, and packaging the resulting stick in an alumi-
num foil wrapper.
Ingredient Percent
Sodium stearate 22.0
d-Limonene 15.0
Benzyl alcohol 8.0
30 2-Propanol Z2.0
Polyamine (x=2; y=6avg.) 10.0
Sodium dodecyl benzene sulfonate3.5
Water to 100
~lZ~3~35~3
-- 10 ~
In use, the foil wrapper is peele~ away from a portion
of the stick, which is then rubbed briskly onto -the area
of a garment soiled with cosmetic, or the like, stains. The
garment is thereafter brushed, or optionally laundered, to
remove the stain, together with residues from the stick.
Example II
~ liquid fabric pre--treatmen~ and through-the-wash
detergency booster is prepared by blending the followincJ
ingredients.
IngredientParts by Weight
Paraffin oil (deodorized) 20
Polyamine (x=3; y=15 avg.) 7
Water 50
Ethoxylated sorbitan oleate 3
In a preferred method of use, a few (1-10) milliliters
of the composition of Example II are applied directly to an
area oE fabric stained with clay/grease soil and rubbed
briskly into the stained area. The fabric is thereafter
laundered with a commercial laundry detergent (e.g., VIZIR)
according to lable instructions.
In an alternate mode, the composition of Example II is
added directly to an aqueous laundry bath, generally at a
level of 500 - 5000 ppm, depending on the desires of the user
and the soil load, together with a commercial laundry deter-
gent, to enhance cleaning performance.
The composition of Example II can be diluted (1:1) with
water or water-ethanol and packaged in an aerosol or manual
pump dispenser for use as a spot remover.
Example III
A granular detergent composition comprising the solvent/
polyamine composi'cions of the present invention can be pre-
pared by blending the solvent/polyamine with a spray-dried
. ~
~23~33
-- 11
commercial laundry detergent. ~lowever, in a preferred mode,
the solvent/polyamine is admixed with non-neutralized anionic
surfactant, which is then admixed with alkaline detergency
builder and other optional detergency ingredients, whereby the
surfactant is neutralized _n situ in the product. This method
of formulating solvent-containing granular detergents is des-
cribed by A.Davidsohn in the report of the original lectures,
3rd International Congress of Surface Activity Cologne, payes
165 to 172 at 171 (1960).
Following the operating procedures suggested by David-
sohn, there is prepared a granular detergent of the formu-
lation:
Ingredient Percent
C121avg.)alkyl benzene sulfonate9.6 (acid form)
15 C12-15 alkyl ethoxylate(EO avg. 9) 1.4
- Sodium perborate.4H2O 22.0
Sodium tripolyphosphate 19.0
Orange terpene 10.0
Polyamine (x=3; y=16) 1.0
20 Sodium sulfate 20.0
C16-C18 hardened soap (suds control) 1.5
Enzymes (protease/amylase mix) 1.5
Carboxymethyl cellulose 2.0
water, optical brightener, minors to 100
The composition of Example III is used in standard fa-
shion to launder fabrics. In a preferred mode, ca. 2g.
of the compusition is admixed with ca. 5ml wate~ to form a
paste which is then rubbed into heavily soiled areas of
fabrics, prior to laundering with the composition.
Examples IV - IX
The following examples relate to compositions within the
scope of this invention with solvents which are particularly
suitable in industrial, heavy-duty laundry and cleaning
, ~
i3;:3
l.2 -
plants, and the like. It will bc appreci~ted by the formulator
that some of the solvents employed in such composit:ions may
be unsuitable for general home use, due to malodors, poten-
tial for skin irritation, low flash poin-ts, and the like.
However, such compositions are entirely suitable for use un-
der properly controlled conditions by professional operators
who take such matters i.nto consideration. In Examples IV-IX,
all ingredients are listed as parts by weigh-t.
INGREDIENT IV V VI VII VIII IX
10 Stoddard solvent 100 - - - - 250
Trichloroethylene - 10
Naphtha - - 30 - - -
Petrole~m Ether(b.p.80-85C)- - - 60 100
Mineral spirits . - ~ - 20
15 Benzyl alcohol - - - - 100
Butyl carb.itol (T.M.) - - - - - 50
Polyamine (A-F*) 5(A)10(B) 15(C)100(D) 20(E) 150(F)
Water 100 100200 - 250 350
Coconut soap - ~ 25
20 C alkyl benzene
12 sulfonate 50 5 - - 10 20
C alcohol ethoxylate
12-15 (EOAvg 9) 50 - - - - 20
C alkyl phenol
9 (ethoxylated (EOAvg 6) - 2 10 100 10
Mg~OH)2 to pH shown 7.0 7.17.5 - 7.7 8.1
*Polyamines A-F used in Examples IV-IX have the general formulae
disclosed hereinbefore and are as follows:
A x = 2; y = 2; R = ethylene; alkoxy = ethoxy
B x = 20; y = 30; R = propylene; alkoxy = propoxy
C x = 3; y = 15; R = ethylene; alkoxy = ethoxy; R = butyl
D x = 5; y = 9; R = butylene; aloxy = butoxy
E x = ~0; y = 10; R = hexylene; aloxy = ethoxy; R : dodecyl
F x = 3; y = 20; R = ethylene; alkoxy = ethoxy; R = eicosyl
- ~LZ:~S33
~leavy-~uty l,iquid Detergents
Having thus described a variety of compositions in
accordance with the invention, special attention is now
directed to highly preferred formulations which are particularly
useful as heavy duty liquid de-tergents -that are suitable for
laundering all manner of fabrics in a typi.cal home laundering
operation. The heavy duty liquid detergents disclosed herein-
after are formulated with a variety of detersive ingredients
to provide excellent cleaning of a wide variety soils and stains,
and wherein the solvent/polyam.ine contributes significantly to
the removal of clay/grease and dirty mo~or oil stains from
fabrics.
It is to be understood that, while such formulations can
be prepared as water-in-oil emulsions, they are preferably
prepared in the form of oil-in-water emulsions (wherein the
solvent is considered the "oil" phase) and are most preferably
.in the form of substantially clear, homogeneous oil-in~water
microemulsions. The formulator of heavy duty liquid detergents
will appreciate that using water as the carrier phase in such
compositions is a significant cost saving, and will further
appreciate that an aqueous carrier phase contributes importan~ly
to ease-of-formulation, since water-soluble detersive ingredients
can be more readily incorporated into oil-in-water emulsions
than in water-in-oil emulsions. Surprisingly, when used in a
pre-treatment mode, the oil-in-water emulsions herein are
comparable .n grease-cutting performance to water-in-oil
emulsions, which have much higher concentrations of solvent.
The compositions herein with high concentrations of surfactant
and fatty acid/soap may be packaged in high density polyethylene
bottles without solvent loss.
Example X
A heavy-duty liquid detergent in the form o~ a clear,
homogeneous oil-in water emulsion which shows excellent
performance with a wide variety of clay soil types of stain
is prepared as follows:
'~`
~2~S~3
- 14 -
INGREDIENT PARTS BY WEIGHT
Polyamine (x=5; y=15) 1.5
Ethanol 3.0
Potassium hydroxide (50% in water)8.0
5 Alkyl (Cll 8) benzene sulphonic acid 11.0
Alkyl (Cl~/15) ethoxylate (E07) 15.0
Potassium citrate monhydrate (63,5% in water) 2.4
Dequest* 2060 S (TM) . 1.2
Sodium formate (40% in water) 2.5
10 Ca as CaC12 6H2O 60 ppm
Orange Terpenes 10.0
Lauric / myristic acid (60/40) 12.5
Oleic acid 2.5
Maxatase** (TM) enzyme 0.71
15 Termamyl*** (TM) enzyme 0.10
Optical brightener (anionic) 0.23
Perfume 0.5
Dye 20 ppm
Water to 100
20 Product pH 7 3
* Diethylene triamine pentamethylene phosphonic acid
(Monsanto)
** KNGS, supplier
.*** NOVO, supplier
The above composition is prepared by blending the indicated
ingredients to provide a clear, stable microemulsion. In
laundry tests, particularly with a pre-treatment step, the
composition gives excellent performance on a wide variety of
stains, including cosmetics and dirty motor oil.
Preferred compositions of the foregoing microemulsion type
will generally contain 10-20% of the fatty acid mix and be
formulated at pH 6.6-7.3.
! ~ \
~2~0533
-- 15 --
EXAMPLE X I
The composition of Example X is modified slightly by using
0.6 parts by weight of magnesium hydroxide in place of 1.2 parts
of potassium hydroxide (50~) to adjust pH to 7Ø The resulting
product is a homogeneous microemulsion.
EXAMPLE X I I
The composition of Examples X and XI are modified by replacing
the orange terpene by a mixture of deodorized paraffin oil (iso-
C10-C12) (7.5~ of the total composition) and orange terpenes
(2.5% of the total composition). This change in the solvent
component in no way detracts from the performance attributes of
the compositions, but allows the perfumer more latitude for
introducing non-citrus perfume notes. Anionic optical
brightener (0.01 - 0.5~) may be added, as desired.
SOLVENT SELECTION
As disclosed hereinabove, final selection of the solvent
system for use in the present compositions will be dependant
upon soil type and load, aesthetics (odour) etc. However,
a number of criteria can be used to guide this selection.
For example, the solvent should be substantially water
immiscible; and, it should of course be capable of solubi-
lizing a broad range of problem greasy soils. In this latter
respect thermodynamic solubility parameters (Hansen Parameters)
are useful in making the solvent selection.
Any solvent can be described by the Hansen Parameters
~d ~p ~h ~d being the dispersion component; ~p the
polarity component; and ~h the hydrogen bonding component.
Likewise, key greasy problem soils can be described by "pseudo"
Hansen Parameters. In order to do this the solubility of
each greasy stain in a broad range of solvents of different
Hansen Parameters is first assessed. This can be done by
immersing the greasy stain on a range of different fabric
types (cotton, polyester cotton, acrylic) in each solvent
~LZ30~;33
- 16 -
in turn for a fixed time (say, 5 minutes) under fixed agita-
tion. On removal, excess solvent is drained-off and the st~ined
fabric is washed for 5 minutes in cool water containing 1%
concentration of a typical liquid laundry detergent. Following
final rinsing in cold water and drying, the stain removal
can be assessed visually or by any other suitable technique.
By proceeding in this way, those solvents giving best removal
of each problem greasy stain can be identified, and thereby
the range of each Hansen Parameter required for optimum
removal of that particular stain can be assessed. Thus, for
each stain a map of Hansen Parameters can be developed, and
solvent/solvent combinations can be selected on this basis
to give the target performance profile.
~lthough not intended to be limiting of the present
invention, the above technique indicates that mixed
solvent/solvent compositions with Hansen Parameters in the
range ~d ~7 to 9?, ~p (o to 4)~ ~h ( to 7) allow the
formulation of microemulsions with superior greasy stain
removal performance. The solvent combination can be targeted
against particular greasy stains, such as motor oil, where
the optimum Hansen Parameter range is ~d (7 to 9)~ ~h ( to 4)
~p (0 to 3) or marker ink, where the optimum range is
~d (769), ~h (2 to 11), ~p (2 to 7), or targeted more
broadly against mixed stains by selecting an intermediate
point in the range of Hansen Parameters.
Some preferred solvents and solvent mixtures herein,
especially: orange terpenes (d-limonene), paraffins (especially
iso-C10-C12); cyclohexane; kerosene; orange terpene/benzyl
alcohol; (60/40), n-paraffins (C12 15) / hexanol (50/50), fall
within the Hansen Parametexs, as stated.
These solvents and solvent mixtures are typically used
at concentrations of 5 - 20%, preferably 5 - 10%, in the
present compositions. Slightly polar solvents such as
benzyl alcohol or n-hexanol can be used with water-
immiscible solvents such as terpenes and paraffin oil atlevels of 0 - 10%. Various other solvent mixtures are
disclosed in Example XIX, hereinafter.
~230533
- 17 -
As can be seen from the foregoing, the present invention
encompasses a varietv of formulations in the form of stable,
solvent-containing emulsions. A superior heavy duty liquid
detergent composition can also be prepared using a solvent
system comprising diethyl phthalate (preferred) or dibutyl
phthalate in combination with the terpenes (preferably,
orange terpene) or dipentene, or paraffin oils, or
(most preferably) mixtures thereof. The following is a
representative example of such a composition.
EXAMPLE XIII
Ingredient Parts by weight
Polyamine (x=5;y=l5) l.5
Potassium Hydroxide (50 % Aq.) 8.0
Ethanol 3.0
Cll 8 Alkyl Benzene Sulphonic Acid ll.0
Cl4/l5 Alkyl Ethoxylate (E0 7) 15.0
Potassium Citrate (63.5 Aq.) 2.4
Deodorized Paraffin Oil *7.5
Orange Terpene 2.5
Dibutyl phthalate 3.0
Lauric/Myristic Acids (60/40) 12.5
Enzymes (per Ex. X) l.0
Water and minors with pH
adjusted with cyclohexvl amine
to 6.9 to l00
* Cl0-Cl2 Iso-paraffins
In Example XIII, the dibutyl phthalate can be replaced by
an equivalent amount of diethyl phthalate.
~12~533
- 18 -
It will be appreciated that many of the foregoing
compositions comprising the terpene hydrocarbons will ne-
cessarily have a rather strong citrus odor that may not be
entirely acceptable to all formulators of such compositions.
It has now been discovered that the C6-Cg alkyl aromatic
solvents, especially the C6-C~ alkyl benzenes, preferably
octyl benzene, exhibit excellent grease-removal properties
and have a low, pleasant odor~ Likewise, the olefin sol-
vents having a boiling point of at least about 1~0C, espe-
cially alpha-olefins, preferably l-decene cr l-dooecene, are
excellent grease-removal solvents.
The combinat~on of the aforesaid alkYl-aromatic or
olefin solvents with polar liquids such as benzyl alcohol,
n-hexanol, Butyl Carbitol (Trade Mark; 2-(2-butoxyethoxy)
ethanol) or the phthalic acid esters cons.itute additional
examples of preferred non-polar/polar solvents that are
preferred for use in the practice of this invention.
The following additional examples further illustrate
oil-in-water microemulsions. In Example ~VII, the use of
the quaternary ammonium compound to adjust the pH of the
formulation to a pH just barely below neutrality contributes
importantly to product performance while maintaining long-
term m1croemulslon stability.
,S:33
- 19 -
_XAMPLE YIV
Ingredient % By Weight
Cll 8 Alkyl benzene sulphonic acid lO.O
C1~/15 Alkyl ethoxylate (EO 7) 10.9
Coconut fatty acid (broad cut) 18,2
Oleic acid 2,3
Monomethyl ethanolamine 5,8
l-Decene 9.1
Ethanol (95~) 2,7
Dequest (50~)l l.09
Formic acid 0.18
K3 citrate. H2O (63.5% in H2O) 4,4
CaCl2 2H2 0-05
Maxatase enzyme (protease) 0.73
Termamyl enzyme (amylase) 0.10
Ethoxylated polyamine 2 1.73
Perfume/optional brightener/dye 0.5
Water Balance
Product pH 6.6
2~ l. Diethylene triamine pentamethylenephosphonic acid
2. Tetraethylene pentamine 105 EO units/molecule
The composition of Example XIV is a stable, oil-in-
water microemulsion suitable for use as a laundry detergent.
_XAMPLE XV
The composition of Example XIV is modified by replacing
the l-Decene by the same amount (9.1% total formulation)
of n-octyl benzene, Product pH "as is" : 6,6.
~230~33
-- 20 --
EXAMPLE XVI
The composition of Example XIV is modified by replacing
the l-Decene by any of the following solvent mixtures (per-
centages of total formulation being specified in parentheses):
l-Decene (6.1~)/D.iethylphthalate (3.0%); 1- Doc.ecene (5.9%)/
Benzyl alcohol (3.2%); n-octyl benzene (6.2~)/Diethyl
phthalate (2.9%); n-octyl benzene (5.0~)/ Butyl carbitol
(4-1~); Diethyl phthalate (6~)/liquidClo iso-paraffin(2
orange terpene(2%). Product pH's as is : 6.6.
_ AMPLE XVII
The compositions of Examples XIV, XV, and X~iI are
modified by adding sufficient cyclohexyl amine or dioctyl-
di~.ethyl am~onium chloride to ad~ust the "as is" ~ of the compositions from
6.6 to 6.94. The resulting compositions exhibit exceptional-
ly good fabric cleaning and whiteness maintenance.
EXAMPLE XVIII
An extra-heavy duty laundry additive composition is
as follows.
Ingredient Percent by ~eight
l-Decene 20
n-Octyl benzene 10
Diethyl phthalate 10
Polyamine (x=5 y=15) 10
Sodium tripolyphosphate to 100.
Another preferred olefin solvent herein b~ virtue of
its relatively low odor is the so-called "P-4" polymer,
available from a number of petrochemical suppliers to the
detergent industry as a raw material for branched a1kvl ben-
zene. P-4 is an isomer mix of the condensation product of
4-moles of propylene, i.e., C12 ~ranched olefins- P-4 is non
polar, and is preferably used in combination with a polar
solvent such as benzyl. alcohol,diethylphthate, Butyl Carbitol,
or the like .
~L2~0533
Otller useful polar solvents herein include the "cello-
solves" e.g. alkoxyl alkanols such as 2-bu-toxyethanol; C6-C12
alkanols (including benzyl alcohol) such as dodecanol, phe-
nethyl alcohol, diglycolether acetates,hexyl cellosolve and
hexyl carbitol, and the like.
22 ~Z30S33
EXAMPLE XIX
The following are additional examples of
grease-removal solvent mixtures which can be used with the
alkoxylated polyamines in the manner of this invention.
ComPosition Inqredient Percent
A Octyl benzene 70%
Diethyl phthalate 30%
B l-Decene 70%
Diethyl phthalate 30%
C Octyl benzene 80%
Benzyl alcohol 20%
D n-Octyl benzene 90%
Butyl carbitol 10%
E l-Decene 65%
Dibutyl phthalate 35%
F n-Octyl benzene 30%
l-Decene 40%
Benzyl alcohol 10%
Butyl carbitol 20%
G l-Decene 80%
n-Hexanol 20%
H l-Decene 60%
Diethyl phthalate 40%
I l-Dodecene 80%
Hexyl cellosolve 20%
J Mixed 1:1 nonyl/hexyl benzene 35%
2-Dodecene 35%
Dimethyl phthalate 30%
In a preferred method of use aspect, the compositions
herein are used in an aqueous laundering liquor at a
liquor pH of 6.5-8.0 (measured as 1% of composition in
water) to launder fabrics. Excellent cleaning is attained
by agitating fabrics in such liquors at this in-use pH
range~
23 _ 1230533
Nitroqen-functional Stabilizers/pH Requlants - As
disclosed in Examples XIII and XVII, above, various alkyl
and cyclo-alkyl amines, quaternary ammonium compounds, as
well as amine oxides, constitute a highly preferred class
of pH regulants and stabilizers in the oil-in-water
microemulsion detergent compositions of the present type.
Apparently, such materials may somehow associate with the
fatty acid or anionic surfactants to form a complex which
stabilizes the microemulsified oil (solvent). While the
nitrogen functional compounds do not boost the pH very
much towards the alkaline range (only several tenths of a
pH unit, measured on the product formulated "as is~') the
resulting boost in detergency performance, especially
enzymatic cleaning performance, is substantial.
Parenthetically, it is to be understood that with
regard to pH adjustments in the compositions up to about
pH 6.5-6.6, any of the well-known base materials can be
used, for example, triethanolamine, alkali metal hydroxide
and the like. Potassium hydroxide is preferred over
sodium hydroxide, inasmuch as the ease of formulation of
stable systems is increased substantially by the potassium
cation.
Dioctyl dimethyl ammonium chloride is a highly
preferred quaternary used herein as a pH-regulant, but
there can also be mentioned the following quaternaries in
increasing order of preference of use: coconut trimethyl
ammonium chloride (6.66); di-coconut dimethyl ammonium
chloride (6.84); coconut benzyl dimethyl ammonium chloride
(6.84); and dihexyl dimethyl ammonium chloride (6.89).
3~ The numbers in parentheses denote the pH achievable by
adding the respective quaternaries to a liquid
oil-in-water microemulsion containing fatty acid and
formulated at an "as is" pH of 6.5. For the preferred
dioctyl dimethyl ammonium chloride, the pH figure is 6.9q.
-- 24 -- ~2~0~3
Suitable alkyl and cyclo-alkyl amines useful herein
(with attendant pH's) include: coconutalkyl diethanol
amine (6.65): coconutalkyl dimethyl amine (6.75); trioctyl
amine (7.0): and cyclohexyl amine (7.5).
Suitable amine oxides herein include coconutalkyl
dimethylamine oxide (6.7) and dioctyl methylamine oxide
(est. 7).
It is to be understood that the foregoing ni~rogen
compounds can be added to the compositions until the
desired pH is obtained. To achieve the pH listed, from
0.5% to 5% of the compounds are typically used in the
compositions. Cyclohexyl amine (l-5%) is most preferred
for use herein.
In general terms, the most highly preferred
oil-in-water microemulsion form of the compositions herein
comprise:
a) 10% to 70% water (carrier):
b) 5% to 20% grease removal solvent or solvent mixture:
c) 5% to 35% fatty acid or fatty acid~soap mixture:
d) 1% to 40% detersive surfactant
e) 0.001% to 2% detersive enzyme:
f) at least 0.2% alkoxylated polyamine; and
g) said composition being adjusted to a pH (undiluted)
of 6.6-7.5 using a nitrogenous material (as described)
especially cyclohexylamine.
Microemulsion stability of such composition can be
estimated visually by watching for phase separation; or
can be monitored quantitatively by standard turbidometric
techniques. Product "as is" pH is measured at ambient (23C)
temperature using a commercial pH meter. The electrode
is immersed in the product and the meter is allowed to stabi-
lize before reading.
- 25 123~33
EXAMPLE XX
A highly preferred liquid laundry detergent by virtue
of the low odor properties o~ its grease removal solvent
system, its stability in microemulsion ~orm, and its
enzymatic cleaning activity (by virtue of its pH) is as
~ollows.
Inqredient Parts bY Weiqht
Alkyl(Cll 8)benzene sulfonic acid 11.0
Alkyl(C14/15)ethoxylate (~07) 12.0
Topped whole cut coconut fatty acid (l) 20~5
C10~ soparaffins 4
Diethyl phthalate 6.0
Cyclohexylamine 2.0
Monomethyl ethanolamine (2) 4.3
Potassium citrate monohydrate
(63.5% in water) 2.4
Dequest 2060 S 1.7
Ethoxylated polyamine (x=5, y=15) 1.5
Ethanol 3.0
Potassium hydroxide (50% in water) (2) 3.0
Formic acid O.Z
CaC12 2H20 0,05
Optical brightener (anionic) 0.18
Maxatase enzyme (3) 0.71
Termamyl 300L enzyme (9) 0.10
Dye 20 ppm
Perfume 0-5
Water up to 110 parts
Product pH 6.9
3~ (1) Chain length mixture: Clo(5%) C12(55%) C14(22%)
C18(2%) oleic(10%)
(2) To adjust pH to 6.6
(3) From KNGS
(4) From NOVO
- 26 ~230533
The composition of Example XX is used in an aqueous
laundry bath at a concentration of lOOml/10 liters and
provides an in-use pH of about 7,2 tvaries with water
hardness).
