[0001] Modern home laundry cleaning compositions are very reliable and efficient in removing
soil from household clothing articles, linens, and the like. Household laundry detergent
compositions are formulated to remove soil and stains from various kinds of dirt depositions
in the fabric. Generally such formulations effectively remove dirt induced soil and
are even effective in removing low level stains or soil from oil or grease sources.
However, common laundry detergents are deficient in handling soil resulting from protein
sources, e.g., blood, grass; or soil where the proteins are combined with oils or
greases from animal or vegetable origin; or soils of heavy grease, fats, or starch
origin.
[0002] In order to effectively remove these difficult soils, various compositions are being
marketed as "pre-washes" or "pre-spotters." Such compositions are applied directly
to the difficult stains before the washing process. The "pre-wash" compositions are
formulated primarily to remove oily or greasy stains. For this purpose, such compositions
rely principally upon organic based solvents such as hydrocarbons, halogenated hydrocarbons
etc. in combination with hydrocarbon compatible surfactants. Such compositions effectively
dissolve and/or emulsify oily or greasy stains. These compositions, however, are not
nearly as effective in removing stains caused by protein sources such as blood, and
grass; or from combined protein and fat sources such as sebum; or from fats and starches.
These sources produce stains which are difficult to remove with solvent/surfactant
combinations alone.
[0003] In an effort to treat protein, fat and starch based stains, some producers have resorted
to the use of enzyme compositions that are available from various sources. These compositions
employ protease, amylase, or lipase enzymes to attack protein, fat and starch based
stains and chemically degrade these compounds so that they can more readily be removed
by subsequent or concurrent treatment with conventional surfactants. While enzyme
containing compositions are quite proficient in treating such stains, the enzymes
themselves are quite susceptible to deactivation if mixed with other components, especially
hydrocarbon solvents.
[0004] Thus the "pre-wash" manufacturer faces a dilemma if it is desired to effectively
treat both oil and grease based stains as well as protein, fat and/or starch based
stains on the same garments. Since enzymes are incompatible with hydrocarbon solvents,
it has heretofore been impractical to devise a single enzyme-hydrocarbon solvent product
that will effectively treat both grease stains and protein, fat and/or starch stains.
It is not practical to provide two separate formulations, one enzyme and one solvent,
since separate compositions would be more costly; and cause twice the work for the
user. Therefore such separate treatment procedures are unacceptable to the consumer.
[0005] The ideal solution to the problem would be a "pre-wash" composition which would simply
and easily treat both grease and protein, fat, and/or starch stains in a single treatment.
Such a composition should have a reasonable storage life during which the enzymes
would not excessively degrade or deteriorate; it should be quite liquid so that it
could be easily applied to the stains, as by spraying; it should be a single phase
composition, so that one component would not settle out thereby requiring agitation
or shaking to mix the components before use; and it should be dispersible in, or miscible
with laundry wash water so that it is easily removed when the fabrics are subsequently
washed in a conventional washing machine.
[0006] The present invention solves the problems enumerated above.
[0007] The present invention relates to laundry "pre-wash" compositions; and more particularly
to pre-wash compositions that are single phase liquids effective against both oil
and grease stains as well as protein, fat and/or starch stains. The invention compositions
effectively combine the advantages of both hydrocarbon oil and grease solvents and
enzymes in a single liquid composition. The normally incompatible hydrocarbon solvents
and enzymes are combined without expressively limiting the products' "shelf-life",
i.e., the enzyme component retains an effective activity against stains for extended
periods; and the hydrocarbon solvents retain their effectiveness against oil and grease
stains.
[0008] The enzymes are water soluble and they must remain in aqueous solution to retain
their activity against proteins, fats, and/or starches. The hydrocarbon solvents,
on the other hand are quite hydrophobic and immiscible in aqueous solutions. The hydrocarbon
solvents are effective against oil and grease in the absence of water. Any water present
in the "pre-wash" composition tends to interfere with the solvents' ability to remove
oil and grease.
[0009] The present compositions reconcile these adverse properties by dispensing aqueous
solutions of the enzymes as "reversed micelles" within the hydrocarbon solvent/surfactant
medium. The "reversed micelles" are formed by providing suitable surfactants which
facilitate encapsulation of an aqueous solution of the enzymes and subsequently dispersing
the enzyme/surfactant mixture in the hydrocarbon solvent medium. The enzymes are dissolved
in the aqueous solution; surfactants are added. The surfactants encapsulate the enzymes,
and then permit the dispersion of the enzyme-aqueous portion in the hydrocarbon medium.
[0010] In other words, the surfactants effectively facilitate the formation of reversed
micelles. In such reversed micelles the hydrophobic tail of the surfactant dissolves
in the hydrocarbon medium, while the hydrophilic head of the surfactant dissolves
in the aqueous enzyme solution. Under appropriate conditions minute micelles are formed
within the hydrocarbon medium. The enzymes are dissolved within the aqueous micelle
interior where they are effectively protected from attack and degradation by the hydrocarbon
solvent.
[0011] When the "pre-wash" composition is applied to a fabric, the hydrocarbon component
attacks and removes the oil and grease stains without interference from the aqueous
portion of the composition since the aqueous portion is but a minor amount, 5% or
less, of the composition. At the same time, the enzymes are released upon the fabric
surface where they can effectively attack the protein, fat, and/or starch stains.
[0012] The aqueous enzyme-surfactant "reversed- micelles" are extremely small and are dissolved
within the hydrocarbon medium to form a suspension or dispersion. Thus there is no
problem with phase separation. Further, due to the unique fine structure, i.e., reversed
micelles, the enzymes in the aqueous portion are protected from premature degradation
by the surrounding hydrocarbon medium.
[0013] From a component standpoint the invention compositions comprise a small percentage
(by weight) of the enzymes; somewhat larger percentages of enzyme stabilizers, e.g.,
sodium chloride, calcium chloride, or triethanolamine, all of which are dissolved
in aqueous solution with the total water content being less then 5% of the composition;
substantial percentages of one or more surfactants, preferably nonionic; and a large
percentage of hydrocarbon solvent. In addition, small percentages of hydrotropes,
such as glycols may also be present. Small amounts of perfumes or dyes may be included
for aesthetic purposes.
[0014] The pre-wash compositions are prepared in a prescribed procedure so as to produce
a solution of reversed micelles having the aqueous enzyme solution held within the
interior thereof; and with the micelles dispersed throughout the hydrocarbon solvent-surfactant
medium.
[0015] In general, the compositions may comprise several tenths of a percent of solution
(as a glycol/water solution) enzyme; about a tenth of a percent of NaCL (as enzyme
stabilizer); less than five percent water; about twenty-five to thirty-five percent
surfactant; about sixty to seventy percent hydrocarbon solvent; about two to three
percent of a glycol as a hydrotrope; and if desired, several tenths of percent perfume
and coloring material (dye).
[0016] In a preferred composition the water dissolved enzyme may comprise about 0.2 weight%;
about 1.5 weight% of 1M NaCl aqueous solution; about 2.5 weight% of ethylene glycol;
about 14.5 weight% of an ethoxy-propyloxy linear alcohol nonionic surfactant; about
14.5 weight% of an ethoxylated linear alcohol nonionic surfactant; with the remainder
being hydrocarbon solvent, e.g., a nominal C-12 to C-16 mixture of isoparaffins. Very
small percentages of perfumes or coloring agents may be added.
[0017] It will be understood that the enzyme component is present to effectively remove
protein based stains, fat based stains, and/or starch based stains. Of these types
of stains the most important are the protein based stains resulting from blood, grass,
body fluids, and the like. Therefore, proteases are most desirable in the invention
compositions. It should also be apparent that related enzymes having particular effectiveness
against other organic molecules, e.g., starches, fats, etc., may also be included
along with the proteases. If desired, amylases, lipases etc. may be combined with
the protease enzymes to produce a pre-wash composition that is effective against a
full spectrum of fabric stains. The only precaution to be taken if additional enzymes
are introduced, is that such added enzymes be compatible with the protease.
[0018] It is most important that the total amount of water in the compositions be maintained
at levels no greater than 5 weight%. Quantities of water greater than 5 weight% may
interfere'with the ability of the hydrocarbon solvent to effectively remove oil and
grease stains.
[0019] It is an object of the invention to provide improved pre-wash compositions.
[0020] It is another object of the invention to provide compositions that are useful for
removing both oil and/or grease based stains and protein, fat, and/or starch based
stains from fabrics.
[0021] It is another object of the invention to provide compositions wherein enzymes in
aqueous solution are encapsulated in surfactants dispersed within a surfactant-hydrocarbon
solvent medium to form reversed micelles therein.
[0022] It is still another object of the invention to provide compositions including hydrocarbon
solvents, surfactants, and enzymes as active ingredients and wherein the enzymes are
protected from the hydrocarbon solvent by encapsulating the enzymes within surfactants
and then dispersed in the solvent to form reversed micelles.
[0023] It is yet another object of the invention to provide a method for encapsulating enzymes
in aqueous solution within reversed micelles dispersed in a surfactant-hydrocarbon
solvent medium.
[0024] Other objects and advantages of the invention will become apparent from the-following
specification and claims.
[0025] Pre-wash compositions that exhibit the ability to simultaneously remove oil/grease
stains and protein, fat, and/or starch stains from fabrics are formulated from surfactants,
enzymes, and hydrocarbon solvents. While enzymes and hydrocarbon solvents are normally
incompatible, the invention compositions overcome this difficulty by enclosing the
enzymes in nonionic surfactants, and then dispersing the mixture in hydrocarbon solvents.
Reversed micelles are thus formed in the surfactant-hydrocarbon medium. The water
content of the compositions is kept very low, i.e., no more than 5 weight%, so that
the oil and grease stain removing ability of the hydrocarbon solvent substrate remains
unimpaired. At the same time the encapsulated enzymes are released to attack protein
stains when the pre-wash composition is applied to soiled fabrics.
[0026] More specifically, the pre-wash compositions comprise a hydrocarbon solvent medium
in which surfactants are dispersed, as well as an aqueous enzyme solution in the form
of reversed micelles. The dispersed surfactants form the "micelle" interface between
the aqueous enzyme solution and the surrounding hydrocarbon solvent medium. The hydrocarbon
solvent comprises the major component, ideally being present in amounts greater than
60% by weight. The surfactants comprise the next most abundant component, ideally
being present in an aggregate amount in the neighborhood of 30%. It is desirable that
the solvent-surfactant ratio be maintained at about 2:1, e.g., if the solvent is about
60%, then the surfactants should be present at about 30%. The total amount of solvent
and surfactant is not critical; however, together they should comprise well over 90%
of the composition.
[0027] The component that is critical to the effectiveness of the pre-wash compositions
is water. Water comprises the solvent for the enzymes and its presence is necessary
for that purpose. However, it has been determined that if water is present in quantities
greater than about 5% by weight, the oil and grease removal efficiency of the hydrocarbon
solvent is adversely affected. When the water content rises appreciably above 5%,
there is a noticeable decrease in the solvents' ability to thoroughly remove oil and
grease stains. Therefore, the water content is always kept at 5% or less, preferably
less.
[0028] The water acts as a solvent for the enzyme component, which is necessary to remove
protein, fat and/or starch based stains. The enzymes are dissolved in the water. The
enzymes are stabilized in the aqueous solution by the addition of salt (NaCl). Only
a small percentage, e.g., several (i.e. 1, 2,
3, 4, 5 or 6) tenths of a percent of the enzyme solution is needed to be effective.
Higher amounts of enzymes may also be utilized, but will add to the cost of materials.
In commercially available enzyme solutions having an enzyme activity equivalent to
8 K.N.P.U. (K.N.P.U. means Kilo Novo Protease Units. There is no industry-wide standard
for measuring activity.), about 0.2% by weight is an effective amount. Such enzyme
solutions may be further stabilized by the addition of 1-2% of a 1M NaCl solution.
[0029] A hydrotrope, such as ethylene glycol can be added in low percentages, e.g., 2-3%,
to aid the solubility of the surfactants in the solvent.
[0030] It will be understood that, except for the limit on water in the compositions, the
percentages of all components may be varied over relatively wide ranges, i.e., there
is nothing critical about the hydrocarbon solvent, surfactants, enzyme, salt or glycol
percentages. On the other hand, experimentation has developed a preferred composition
having the following percentages of components:

Perfume and dye remainder.
[0031] When produced in accordance with the procedure set forth below, the compositions
are a clear solution with the enzymes encapsulated in reversed micelles within the
surfactant-hydrocarbon solvent medium. The compositions exhibit excellent activity
against both oil and grease stains as well as protein, and/or starch and/or fat-based
stains. The compositions also retain an appreciable portion of the enzyme activity
when stored for extended periods.
[0032] The selection of the enzymes for use in the compositions may be made from any number
of commercially available liquid enzyme solutions that are useful against proteins,
lipids, and starchy substances. Such enzyme solutions are available from several commercial
sources.
[0033] For instance, the commercially available alkaline proteases (preferred in the invention)
are derived from various strains of the bacterial Bacillus subtilis. These proteases
are also known as subtilisins, and are available under the trademarks Esperase e,
Savinase o, and Alcalase ø, from Novo Industri A/S, of Bagsvaerd, Denmark; and also
under the trademarks Maxatase e and Maxacal from Gist-Brocades N.V of Delft, Netherlands.
[0034] These commercially available proteases are supplied as aqueous stabilized solutions
of the enzyme. The enzymes are generally stabilized by the addition of glycols such
as propylene glycol. These solutions are also supplied in various strengths wherein
the strengths are defined by the activity exhibited by the enzyme. Thus as noted above,
in the preferred composition the enzyme solution has an activity of 8 K.N.P.U. Of
course, enzyme solutions of lesser or greater activity can be utilized in the invention
compositions.
[0035] It should be noted that other enzymes may be used in the compositions in addition
to, or in place of, the proteases. Thus lipases effective against fats; or amylases,
effective against starches, can also be used in the formulations. Both types of enzymes
are commercially available, e.g. lipases - (see U.S. Patent 3,950,277 column 3, lines
15-55 for a description of lipase enzymes, their origins, and sources - incorporated
herein by reference) amylases; - Rapidase from Societa Rapidase, France; and Milezyme
e from Miles Labs., Elkhurst, Ind.
[0036] It has been determined that the addition of salt, NaCl, to the enzyme solutions will
further stabilize the enzymes against degradation in the presence of the hydrocarbon
solvents of the pre-wash compositions. To this end, the compositions also include
aqueous salt solution as stabilizing agent. While the exact amounts of the stabilizer
is not critical, the inclusion of roughly 1.5 weight% of 1M NaCl to the aqueous enzyme
solution has been found to aid in maintaining enzyme activity when the product is
stored.
[0037] Surfactants comprise a major component of the pre-wash compositions. Surfactants
that are compatible with the hydrocarbon solvent medium are most necessary; and in
addition such surfactants must not degrade, or interfere with the enzymes in the reversed
micelles. The surfactants are also responsible for the micelle formation within the
hydrocarbon medium. Nonionic surfactants are ideal for the above stated purposes.
The long chain alcohols such as linear ethoxylated and linear propoxylated alcohols
and mixtures thereof are particularly useful in the invention compositions. Such surfactants
are completely compatible with the hydrocarbon solvents; they efficiently form reversed
micelles to encapsulate the aqueous enzyme solutions; they do not degrade the enzymes;
and they contribute significantly to the removal of soil from fabrics to which the
compositions are applied.
[0038] Alkyl ethoxylated and propoxylated alcohols in the nominal C-12 to C-16 range are
most preferred. Such surfactants are available as standard articles of commerce under
the name "Biosoft" from the Stepan Chemical Co.; or under the name "Neodol" from the
Shell Chemical Co. The "Biosoft" series of nonionic surfactants are ethoxylated and
propoxylated fatty alcohols sold in liquid form. The "Neodol" series of surfactants
comprise a large group of nonionic surfactants including ethoxylated long chain alcohols
with ethoxy groups ranging from 3 to 12 and the carbon chains from 12 to 15.
[0039] All such nonionic surfactants are useful in the invention compositions, although
Neodol 25-3 is preferred. Neodol 25-3 is composed of carbon chains nominally in the
C-12 to C-15 range with an average of three ethoxy moieties per mole of alcohol. Biosoft
EA-10 is a mixture of ethoxylated and propoxylated long chain fatty alcohols wherein
the carbon chains are nominally in the C-10 to C-12 range with an average of 7.1 ethoxy
and 2 propoxy moieties per mole of alcohol.
[0040] Other similar nonionic surfactants can be substituted for the aforementioned surfactants
in the compositions so long as they met the criteria set forth above.
[0041] The surfactants are included in the compositions in substantial quantities making
up somewhat less than one-third of the weight. While the total surfactant percentage
is not critical, they should be present in roughly one-half the amount of hydrocarbon
solvent. It has been found that this ratio of surfactant to solvent is necessary to
achieve good removal of oil and grease based soil wherein both the hydrocarbon solvent
and surfactants play key roles.
[0042] The hydrocarbon solvent is the major component in the compositions and, in conjunction
with the surfactants, is the primary agent for treating oil and grease based stains.
The hydrocarbon solvent comprises well over half the compositions by weight; generally
the percentages are in the 60-70% range.
[0043] The solvent component can be selected from any number of hydrocarbon based oil and
grease solvents. Such materials are staple industrial products and may be procured
from a number of oil industry sources.
[0044] It is necessary however that the solvent component be compatible with the formation
of micelles, in this instance reversed micelles, i.e., micelles having an encapsulated
aqueous component dispersed within an organic solvent medium. Because of this requirement
it is desirable to employ solvents that are low in sulfur, acids, and oxygenated compounds.
Pure hydrocarbon solvents, especially paraffinic hydrocarbons having fairly long carbon
chains, e.g., C-10 to C-14 are highly preferred for use in the compositions. Such
solvents are available from the Exxon Corporation of Houston, Texas under the trademark
"Isopar" and "Norpar". Both of these groups of hydrocarbon solvents have a very high
( 98%) normal or isoparaffin content and very low concentrations of sulfur, acids,
carbonyls, chlorides, etc. These solvents, or their equivalents from other manufacturers,
are the preferred organic solvents for use in the compositions.
[0045] In order to produce the compositions wherein the aqueous enzyme component is protected
from degradation by the organic solvents, i.e., encapsulation within reversed micelles,
it is necessary to proceed according to the following method:
The desired amount of aqueous salt solution is prepared. The aqueous/glycol enzyme
solution as procured from the manufacturer is then mixed into the salt solution. (Gentle
agitation is used throughout the production process to thoroughly mix all components.
Violent agitation is to be avoided as it may actually degrade the enzymes by a physical
shearing of the enzyme molecules.)
[0046] A portion, perhaps one half, of the surfactant is then gently mixed into the aqueous
enzyme/salt solution. After thorough mixing is obtained, the remainder of the surfactant
is then added and thoroughly mixed in. At this stage, the aqueous enzyme/salt/surfactant
mixture is a rather viscous clear liquid. The glycol component is then added with
continuous mixing; after which, the hydrocarbon solvent is gradually added to form
the finished product.
[0047] The final product is a clear transparent liquid, principally solvent and surfactant
with small amounts ( 5%) of water, and smaller amounts of enzyme and enzyme stabilizer.
[0048] Although the preparation procedure seems very straightforward and uncomplicated,
it is emphasized that the sequence of addition of components should be closely adhered
to. It is particularly important to first mix the components that dissolve in the
aqueous phase; secondly mix in the surfactants; and finally add the hydrophobic organic
solvent component. Any variation in the procedure, may fail to produce the desired
reversed micelles and the enzymes will be unprotected from the solvent components.
Failure to produce the protective micelles will be apparent if a cloudy solution is
produced; or if a precipitate forms upon standing.
[0049] The clear liquid product may be packaged in any suitable container and stored for
periods of several months and yet retain a good percentage of the enzyme activity.
When used it is preferred to spray the product on the soiled fabrics a few minutes
before placing them into a washing machine. Normal laundering procedures may be utilized.
Of course, an effort should be made to spray the product directly on the visibly soiled
portions of the fabric as direct contact will ensure full opportunity for attacking
the oil/grease, and/or protein, fat or starch stains prior to the laundering process.
I
[0050] When prepared according to the above directions, the enzyme stability of the compositions
as noted above is quite good. In one test over 50% of the enzymes' initial activity
remained after six month's storage at 70°F.
[0051] In another group of tests loss in enzyme activity with time was studied for the following
composition made in accordance with the preferred method of the invention:

[0052] Samples of the above composition were then stored at various temperature for a period
of six months. Table I below sets/forth the results of tests on enzyme activity at
the end of the six month period.

[0053] A series of studies were carried out to evaluate the efficacy of the enzyme containing
pre-wash compositions of the invention.
[0054] In a first series, a number of compositions were prepared wherein the enzyme content
was varied from 0 up to 1.0%. These compositions were then tested for effectiveness
against various types of stains, i.e., grass, ballpoint pen ink, dirty motor oil,
and azocasein. Laundry detergent and a commercial pre-wash formulation, i.e., Clorox
pre-wash, were, in each instance, used for comparison purposes. Table II below sets
forth the compositions. Tables III, IV and VII set forth the results of % stain removal
as measured by instrument. Tables V, VI, and VIII set forth the results measured by
visual grading (on a scale of 1-5, with 5 highest, 1 lowest).

[0055] A review of the data in Tables III, IV, V, VI, VII, and VIII above will make it apparent
that as little as 0.1% added enzyme produces a significant increase in the ability
of the compositions to remove azocasein and grass stains.
[0057] The compositions set forth in Table IX above were stored for periods of time up to
2 months at storage temperatures varying between 35° and 100°F. The samples of the
compositions were tested against both grass and azocasein stains at intervals up to
the 2 months stated above. Table XIII below sets forth the results, thus indicating
the enzyme stability in the compositions as a function of time and storage temperature.

[0058] Further studies were undertaken to evaluate physical stability in varying compositions
prepared according to the invention. Table XIV below sets forth these formulations
along with statements concerning their physical stability after storage at various
storage temperatures.

[0059] TABLE XV below presents some prewash formulations wherein several different enzymes
were utilized. These formulations were also tested for performance on various stains.

These samples were evaluated for performance on grass, blood and gravy. All three
formulas provided a benefit on grass and gravy. The blood stain was totally removed
by detergent alone. No enzyme stability test was conducted.
[0060] Still another group of compositions were prepared having further variations in formulation.
Table XVI below sets forth some compositions wherein additional enzyme stabilizer
(triethanolamine - Formula F) was included; or wherein the solvent system (methylester
- Formula G) was varied. Table XVI also indicates the residual enzyme activity after
storage for the stated period.
1. A soil- or stain-removal composition comprising at least one enzyme dissolved in
aqueous solution encapsulated within reversed micelles, said micelles being a dispersion
of the aqueous enzyme solution within a medium comprising a surfactant and organic
solvent.
2. A composition according to claim 1 of which the water content is not more than
5% by weight.
3. A composition according to claim 1 or claim 2, wherein the enzyme is or are a protease,
lipase, or amylase, or mixtures of the same.
4. A composition according to claim 1, claim 2 or claim 3, wherein the surfactant
is a nonionic surfactant.
5. A composition according to any one of the preceding claims, wherein the organic
solvent is a hydrocarbon, for example a paraffinic hydrocarbon.
6. A composition according to any one of the preceding claims, wherein the aqueous
enzyme solution further includes an enzyme stabilizer.
7. A composition according to claim 6, wherein the enzyme stabilizer is sodium chloride.
8. A composition according to any one of the preceding claims, which includes organic
solvents and surfactants for removing oil and grease based stains, and enzymes for
removing protein, starch, and fat based stains.
9. A composition according to any one of the preceding claims, wherein the surfactant
forms the micelle interface between said aqueous enzyme solution and the surfactant/
organic solvent mixture.
10. A soil removal composition comprising about 60 to 70 weight % of a paraffinic
hydrocarbon solvent in admixture with about 25 to 35 weight % of a nonionic surfactant,
less than 5 weight % of an aqueous solution of one or more proteolytic, lipolytic
or amylolytic enzymes, said aqueous solution consisting essentially of water, sodium
chloride and the enzyme(s), said aqueous solution further dispersed in the solvent-surfactant
mixture in the form of reversed micelles.
11. A composition according to any one of the preceding claims, wherein the enzyme(s)
comprise(s) several tenths of one percent by weight of the composition.
12. A method for making a soil remover composition consisting essentially of organic
solvent, surfactant and at least one enzyme, comprising encapsulating an aqueous solution
of said enzyme(s) in reversed micelles within a mixture of said solvent and surfactants.
13. A method of claim 12, wherein said aqueous enzyme solution is combined with the
surfactants, and the solvent is then added.