Technical Field
[0001] 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 comprise a mixture of clay-based material and an oily or greasy
binder material. Compositions 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 designed to remove a broad
spectrum of stains and soils from fabrics, with particularly noteworthy benefits on
stains caused by cosmetics.
Background
[0002] Detergent formulators are faced with the task of devising products to remove abroad
spectrum of 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 enzymes are commonly used in detergents for blood and gravy stains;
amylase enzymes are used for carbohydrate stains; nonionic surfactants are used for
hydrocarbon oils; and anionic surfactants and builders ,are used for particulate soil.
Bleach is used to chemically degrade stains that are not amenable to removal by less
rigorous treatment.
[0003] One of the most difficult stains to remove from fabrics is the cosmetic stain, and
from time immemorial the persistent, telltale smudge of lipstick on a shirtcollar
or handkerchief has been the downfall of many a miscreant. Moreover, 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 unintentionally applied.
[0004] 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 hydrocarbon 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 detergent formulator, since cosmetics constitute
a mix of widely divergent soil types(oily, particulate, clay)all in intimate admixture
and often brightly colored. No single detergent ingredient can reasonably be expected
to handle such a complex milieu.
[0005] 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 the polyamine materials which disperse and remove it from fabrics.
[0006] The use of solvents of the type employed in this invention as grease and oil removal
ingredients in cleaners 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 48E and
81200540.3; British Patent 1.603.047.
[0007] However, the use of such solvents in combination with polyamine materials in the
manner disclosed herein is not believed to have been contemplated, heretofore.
Summary of the Invention
[0008] 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 thereof) and an alkoxylated
polyamine (as described more fully hereinafter) at a weight ratio of solvent:polyamine
of 100:1 to 1:20, preferably 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 detergent compositions
contain at least 5% of the solvent and at least 0.2% of the polyamine.
Detailed Description of the Invention
[0009] 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 ratios mentioned in
this specification are by weight, unless otherwise stated.
[0010] Solvent - The solvents employed herein can be any of the well-known "degreasing"
solvents commonly known for use in, for example, the commercial laundry and drycleaning
industry, in the hard-surface cleaner industry and the metalworking industry. Typically,
such solvents comprise hydrocarbon or halogenated hydrocarbon moieties of the alkyl
or cycloalkyl type, and have a boiling point well above room temperature.
[0011] 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 aesthetic considerations. For example, kerosene hydrocarbons function quite well
in the present compositions, but 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 reasonably modified by perfuming. Such solvents include, for example,
the terpenes and terpenoid solvents obtainable from citrus fruits, especially orange
terpenes and d-limonene. Benzyl alcohol is another relatively pleasant smelling solvent
for use herein.
[0012] 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-limohene 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 as dipentene, alpha-pinene, beta-pinene
and the mixture of terpene hydrocarbons expressed from lemons and grapefruit.
[0013] The examples disclosed hereinafter describe various other solvents which can be used
herein.
[0014] Polyamines - It is to be understood that the term "polyamines" as used herein represents
generically the alkoxylated polyamines, both in their amine form and in their quaternarized
form. Such materials can conveniently be represented as molecules of the empirical
structures with repeating units:

Amine form and

Quaternarized form wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms;
R may be a C
I-C
20 hydrocarbon; the alkoxy groups are polyethoxy, polypropoxy, and the 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.
[0015] The most highly preferred 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:

wherein x is an integer of 3 to 5 and y is an integer of 10 to 20.
[0016] Surfactants - In addition to the solvent and polyamine, it is optional, but highly
preferred, that the compositions herein contain organic surface-active agents ("surfactants")
to provide the usual cleaning benefits associated with the use of such materials.
[0017] Water-soluble detersive surfactants useful herein include 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,o(-
sulfonates of 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 C
9-C
18 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. C
11-C
16 alkyl benzene sulfonates, C
12-C
18 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols
are especially preferred in the compositions of the present type.
[0018] The surfactant component can comprise as little as 1% of the compositions herein,
but preferably the compositions will contain 1% to 40%, preferably 5% to30%, of surfactant.
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.
[0019] Fatty
Acid/Soap Ingredient - Fatty acids (generally C
10-C
18 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 detergency builder function
by virtue of their ability to interact with water hardness cations. As will be described
more fully hereinafter, fatty acids and soaps are particularly 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.
[0020] Other Optional Ingredients - The compositions herein can contain other ingredients
which aid in their cleaning performance. For example, it is highly preferred that
through-the-wash detergent compositions contain 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
thereof. Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate,
the amino-polyphos- phonates and phosphates (DEQUEST) 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 compositions.
[0021] 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 mixture
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 and calcium
can be added to help stabilize the enzymes in well-known fashion, according to the
desires of the formulator.
[0022] Moreover, the compositions herein can contain, in addition to ingredients already
mentioned, various other optional ingredients typically used in commercial products
to provide aesthetic or additional product performance benefits. Typical ingredients
include pH regulants, perfumes, dyes, optical brighteners, soil suspending agents,
hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives,
suds control agents and the like.
[0023] 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.
[0024] The compositions herein are preferably formulated in the neutral to alkaline pH range,
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.
[0025] The preferred compositions herein are in liquid form, 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.
[0026] 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 of the composition
directly onto and into the soiled area, followed by laundering, in standard fashion.
In a through-the-wash mode, the compositions are typically used at a concentration
of at least 50C ppm, preferably 0.1% tc 1.5% in an aqueous laundry bath at pH 6.5
- 10 to launder fabrics. The laundering can be carried out over the range from 5°C
to the boil, with excellent results.
Industrial Application
[0027] The following examples describe a variety of formulations 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 "x" and "y" are
stated in parentheses to designate the degree of polymerization and degree of alkoxylation
of the polyamine. For some "polyamines", the designation R is also included, thereby
denoting a quaternarized polyamine. For such quaternarized materials, the resulting
anion #is of no consequence to cleaning performance, and is not designated. In all
examples, R is -CH
2-CH
2- and alkoxyl is ethoxyl, unless otherwise specified.
Example I
[0028] Following the teachings of U.S. Patent 3,664,962, a spot remover in stick form is
prepared by blending the following ingredients, extruding the resulting mass through
a 1.25 cm die, and packaging the resulting stick in an aluminum foil wrapper.

[0029] In use, the foil wrapper is peeled 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
[0030] A liquid fabric pre-treatment and through-the-wash detergency booster is prepared
by blending the following ingredients.

[0031] In a preferred method of use, a few (1-10) milliliters of the composition of Example
II are applied directly to an area of 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 label instructions.
[0032] 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 detergent, to enhance
cleaning performance.
[0033] 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
[0034] A granular detergent composition comprising the solvent/ polyamine compositions of
the present invention can be prepared by blending the solvent/polyamine with a spray-dried
commercial laundry detergent. However, 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 in situ in the product. This method of formulating solvent-containing
granular detergents is described by A.Davidsohn in the report of the original lectures,
3rd International Congress of Surface Activity Cologne, pages 165 to 172 at 171 (1960).
[0035] Following the operating procedures suggested by David- sohn, there is prepared a
granular detergent of the formulation:
[0036]

[0037] The composition of Example III is used in standard fa
- shion to launder fabrics. In a preferred mode, ca. 2g. of the composition is admixed
with ca. 5ml.water to form a paste which is then rubbed into heavily soiled areas
of fabrics, prior to laundering with the composition.
Examples IV - IX
[0038] 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 plants, and the like. It will be appreciated by the formulator that some
of the solvents employed in such compositions may be unsuitable for general home use,
due to malodors, potential for skin irritation, low flash points, and the like. However,
such compositions are entirely suitable for use under properly controlled conditions
by professional operators who take such matters into consideration. In Examples IV-IX,
all ingredients are listed as parts by weight.

Heavy-Duty Liquid Detergents
[0039] Having thus described a variety of compositions in accordance with the invention,
special attention is now directed ro highly preferred formulations which are particularly
useful as heavy duty liquid detergents that are suitable for laundering all manner
of fabrics in a typical home laundering operation. The heavy duty liquid detergents
disclosed hereinafter are formulated with a variety of detersive ingredients to provide
excellent cleaning of a wide variety soils and stains, and wherein the solvent/polyamine
contributes significantly to the removal of clay/grease and dirty motor oil stains
from fabrics.
[0040] 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 importantly 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 in grease-cutting performance to water-in-oil
emulsions, which have much higher concentrations of solvent.
[0041] The compositions herein with high concentrations of surfactant and fatty acid/soap
may be
packaqed in high density polyethylene bottles without solvent loss.
Example X
[0042] A heavy-duty liquid detergent in the form of 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 :

[0043] 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.
[0044] 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.
EXAMPLE XI
[0045] 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 7.0. The resulting product is a homogeneous microemulsion.
EXAMPLE XII
[0046] The composition of Examples X and XI are modified by replacing the orange terpene
by a mixture of deodorized paraffin oil (iso-C
10-
12) (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
[0047] 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 solubilizing
a broad range of problem greasy soils. In this latter respect thermodynamic solubility
parameters (Hansen Parameters) are useful in making the solvent selection.
[0048] Any solvent can be described by the Hansen Parameters δ
d, δ
p, δ
h : δ
d being the dispersion component; δ
p the polarity component; and δ
h the hydrogen bonding component. Likerwise, 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 in turn for a fixed time (say, 5 minutes)
under fixed agitation. On removal, excess solvent is drained-off and the stained 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.
[0049] Although not intended to be limiting of the present invention, the above technique
indicates that mixed solvent/solvent compositions with Hansen Parameters in the range
δ
d (7 to 9), δ
p (0 to 4) , δ
h (0 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 δ
d (7 to 9), δ
h (0 to 4) δ
p (0 to 3) or marker ink, where the optimum range is δ
d (769), δ
h (2 to 11), δ
p (2 to 7), or targeted more broadly against mixed stains by selecting an intermediate
point in the range of Hansen Parameters.
[0050] Some preferred solvents and solvent mixtures herein, especially: orange terpenes
(d-limonene), paraffins (esnecially iso-C
10-C
12);cyclohexane; kerosene; orange terpene/benzyl alcohol; (60/40), n-paraffins (C
12-15) / hexanol (50/50), fall within the Hansen Parameters, as stated.
[0051] 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 at levels of 0 - 10%. Various other solvent mixtures are disclosed
in Example XIX, hereinafter.
[0052] As can be seen from the foregoing, the present invention encompasses a variety 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
[0053]

In Example XIII, the dibutyl phthalate can be replaced by an equivalent amount of
diethyl phthalate.
[0054] It will be appreciated that·many of the foregoing compositions comprising the terpene
hydrocarbons will necessarily 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 C
6-C
9 alkyl aromatic solvents, especially the C
6-C
9 Alkyl benzenes, preferably octyl benzene, exhibit excellent grease-removal properties
and have a low, pleasant odor. Likewise, the olefin solvents having a boiling point
of at least about 100°C, especially alpha-olefins, preferably 1-decene or 1-dodecene,
are excellent grease-removal solvents.
[0055] The combination 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 constitute additional examples of preferred non-polar/polar
solvents that are preferred for use in the practice of this invention.
[0056] The following additional examples further illustrate oil-in-water microemulsions.
in Example XVII, 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 microemulsion stability.
EXAMPLE XIV
[0057]

[0058] The composition of Example XIV is a stable, oil-in-water microemulsion suitable for
use as a laundry detergent.
EXAMPLE XV
[0059] The composition of Example XIV is modified by replacing the 1-Decene by the same
amount (9.1% total formulation) of n-octyl benzene. Product pH "as is" : 6.6.
EXAMPLE XVI
[0060] The composition of Example XIV is modified by replacing the 1-Decene by any of the
following solvent mixtures (percentages of total formulation being specified in parentheses):
1-Decene (6.1%)/Diethylphthalate (3.0%); 1- Dodecene (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%)/liquidC
10 iso-paraffin(2%)/ orange terpene(2%). Product pH's as is : 6.6.
EXAMPLE XVII
[0061] The compositions of Examples XIV, XV, and XVI are modified by adding sufficient cyclohexyl
amine or dioctyl- dimethyl ammonium chloride to adjust the "as is" pH of the compositions
from 6.6 to 6.94. The resulting compositions exhibit exceptionally good fabric cleaning
and whiteness maintenance.
EXAMPLE XVIII
[0062] An extra-heavy duty laundry additive composition is as follows.
[0063]

Another preferred olefin solvent herein by 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 alkyl benzene. P-4 is an isomer
mix of the condensation product of 4-moles of propylene, i.e., C
12 branched olefins. P-4 is nonpolar, and is preferably used in combination with a polar
solvent such as benzyl alcohol,diethylphthate, Butyl Carbitol, or the like.
[0064] Other useful polar solvents herein include the "cellosolves" e.g. alkoxyl alkanols
such as 2-butoxyethanol; C
6-C
12 alkanols (including benzyl alcohol) such as dodecanol, phenethyl alcohol, diglycolether
acetates,hexyl cellosolve and hexyl carbitol, and the like.
EXAMPLE XIX
[0065] The following are additional examples of grease-removal solvent mixtures which can
be used with the alkoxylated polyamines in the manner of this invention.

[0066] 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.
[0067] Nitrogen-functional Stabilizers/pH Re
QUlants - 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.
[0068] 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.
[0069] 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). 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 6.94.
[0070] 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).
[0071] Suitable amine oxides herein include coconutalkyl dimethylamine oxide (6.7) and dioctyl
methylamine oxide (est. 7).
[0072] It is to be understood that the foregoing nitrogen 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 (1-5%)
is most preferred for use herein.
[0073] 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.
[0074] 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 (23°C) temperature using a commercial
pH meter. The electrode. is immersed in the product and the meter is allowed to stabilize
before reading.
EXAMPLE XX
[0075] A highly preferred liquid laundry detergent by virtue of the low odor properties
of its grease removal solvent system, its stability in microemulsion form, and its
enzymatic cleaning activity (by virtue of its pH) is as follows.

[0076] The composition of Example XX is used in an aqueous laundry bath at a concentration
of 100ml/10 liters and provides an in-use pH of about 7,2 (varies with water hardness).