Note: Descriptions are shown in the official language in which they were submitted.
l~ (
Pre-wash Compositions Containing ~nzvmes
Back~round of the Invention
-
Modern home laundry cleaning compositions are
very reliable and efficient in removing soil frvm
household clothing articles, linens, and the like.
Household laundry detergen~ compositions are formulatea
to remove soil and stains from various kinds of dirt
depositions in-the fabric. -GeneralIy 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.
In order to effectl~vely remove these diffi-
cult soils, various compositions are being mar~eted 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 hydrocarbonsj
halogenated hydrocarbons etc. in combination with
~,.
ci3~34~ ~
-- 2 --
hydrocarbon compatihle 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 comhinations alone.
In an effort to treat protein, fat and starch
based stainsj some producers have resorted to the use
of enzyme compositions that are available from various
sources. These ccmpositions 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.
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, lt
34~ t
-- 3 --
has heretofore been impractical to devise a single
enzyme-hydrocarbon solvent product that will
effectively treat both grease stains ancl 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.
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
applie~ 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.
The present invention solves the problems
5 enumerated above.
~6394~
- 4 -
Brief_Description of the Invention
The present invention relates to laundry
"pre-wash" compositions; and more particularly t~
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 xetains an effective activity
against stains for extended periods; and the
hydrocarbon solvents retain their effectiveness against
oil and grea5e stains.
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.
The present compositions reconcile thesé
adverse properties by dispensing aqueous solutions of
i3~3f~
-- 5
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.
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 en~yme solution. Under appropriate conditions
minute micelles are formed within the hydrocarbon
medium. The enzvmes are dissolved within the aqueous
micelle interior where they are effectively protected
from attack and degradation by the hydrocarbon solvent.
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
(
1~ ~3
-- 6
composition. At the same time, the enzymes are re-
leased upon the fabric surface where they can effec-
tively attack the protein, fat, and/or starch stains.
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.
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.
The pre-wash compositions are prepared in a
prescribed procedure so as to produce a solution of
(:
4~
-- 7 --
reversed micelles having the aqueous enzyme solution
held within the interior thereof; and with the micelles
dispersed th~oughout the hydrocarbon solvent-surfactant
medium.
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).
In a preferred composition the water
dissolved enzyme may comprise about 0.2 weight%; about
1.5 weight~ of lM NaCl aqueous solution; about 2.5
weight~ of ethylene glycol; about 14.5-weight% of an
ethoxy-propyloxy linear alcoh~l 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.
It will be understood that the enzyme compo-
nent is present to effectively remove protein based
stains, fat based stains, and/or starch based stains.
~ ` ~
3?~4
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 includ~d 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 en~ymes be compatible with the protease.
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.
It is an object of the invention to provide
improved pre-wash compositions.
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.
394(~
g
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.
It is still another object of the invention
to provide compositions including hydrocarbon solvents,
surfactants, and enz~nes 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.
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.
Other objects and advantages of the invention
will become apparent from the~following specification
and claims.
1~3~
-- 10 --
Detailed Descr~e~ion of the Invention
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 soilëd ~abrics.
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 soIvent medium. The hydrocarbon solvent
comprises the major component, ideally being present in
amounts greater than 60% by weight. The surfactants
~ ~39'~4
-- 11 --
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.
The component that is critical to the effec-
tiveness 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 ef~iciency of the hydrocarbon solvent is
adversely affected. When the water content rises ~
appreciably above 5~, there i~s a noticeable decrease in
the solventsl ability to thoroughly remove oil and
grease stains. Therefore r the water content is always
kept at 5~ or less, preferably less.
The water acts as a solvent for the enzyme
component, which is necessary to remove protein, fat
- and/or starch based stains. The enzy~es are dissolved
in the water. The enzymes are stabilized in the
aqueous solution by the addition of salt ~NaCl~. Only
34~L
- 12 -
a small percentage, e.g., several 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 l-~ of a lM NaCl
solution.
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.
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:
.
~;;3g4~
- 13 -
Component Wt%
Enzyme ~Savinase 8.0L) 0.2
(Enzyme dissolved in a solution
of 80% propylene glycol/20% H2O)
5 NaCl (lM in water) 1.5
Ethylene glycol 2.5
Nonionic surfactants 29.5
(50-50 mixture of ethoxylated
linear alcohols and ethoxylated-
10 propoxylated linear alcohols~
Hydrocarbon solvent 66.0
~isoparaffins~
having nominal 12 to 16 carbons~
Perfume and dye remainder.
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.
The selection of the enzymes for use in the
compositions may be made from any number of commercial-
ly available liquid enzyme solutions that are useful
against proteins, lipids, and starchy substances. Such
enzyme solutions are available from several commercial
sources.
~3~344 (-
- 14 -
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 o, Savinase ~, and Alcalase o, from Novo
Industri A/S, of Bagsvaerd, Denmark; and also under the
trademarks Maxatase ~ and Maxacal ~ from Gist-srocades
N.V of Delft, Netherlands.
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 composi-
tion the enzyme solution has an activity of 8-X~N.P.U. - -
Of course, enzyme solutions o~ lesser or greater
activity can be utilized in the invention compositions.
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
- 15 -
lipase enzymes, their origins, and sources);
amylases - Rapidase
~ from Societa Rapidase, France; and Milezyme o from
Miles Labs., Elkhurst, Ind.
It has been determined that -the aadition 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.
~hile the exact amounts of the stabilizer is not
critical, the inclusion of roughly 1.5 weight% of lM
NaCl to the aqueous enzyme solution has been ound to
aid in maintaining enzyme activity when the product is
stored.
Surfactan~s comprise a ma~or component of the
pre-wash compositions. Surfactants that are compatible
with the hydrocarbon solvent ~edium 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 hydrocar~on 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.
.
~: j
f~ 3'~
- 16 -
Such surfactan~s are completely compatible with the
hydrocarbon solvents; they efficiently form rev~rsed
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.
Alkyl ethoxylated and propoxylated alcohols
in the nominal C-12 to C-16 range are most preferred.
Such surfactants are available as stan~ard 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 atty
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.
All such nonionic sur~actants are useful in
the inventlon compositions, although Neodol 2S-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 o alcohol. Biosoft
EA-lO*is a mixture of ethoxylated and propoxylated long
chain fatty alcohols wherein the carbon chains are
,
* Trade Mark
. .
~394~
nominally in the C-10 to C-12 range with an average of
7.1 ethoxy and ~ propoxy moieties per mole of alcohol.
Other similar nonionic surfactants can be
substituted for the aforementioned surfactants in the
compositions so long as they met the criteria set forth - 1;
above.
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 rolesu
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.
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 oE oil
industry sources.
!
It is necessary however that the solvent
component be compatible with the formation of micelles,
in this instance reversed micelles, i.e., micellcs
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 paraf f inic
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 HoustoII, Texas under the trademark
"Isopar" and "Norpar". Both of these groups of
hydrocarbon solvents have a very high ( 98%) normal or
- 15 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.
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. Th~ aqueous/glycol enzyme solution as
39~4
-- 19 -- ,
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.)
A portion, perhaps one half, of the
surfactant is then gently mixed into the aqueous
enzy~e/salt solution. After thorough mixing is
obtained r the remainder of the surfactant is then added
and thoroughly mixed in. At this stage, the aqueous
enzyme/salt/surfactant mixture is a rather ViSGous
clear liquid. The glycol component is then added with
continuous mixing; after which, the hydrocarbon solvent
- 15 is gradually added to form the finished product.
The final product is a clear transparent
liquid, principally solvent and surfactant with small
amounts ( 5%) of water, and ~maller amounts of enzyme
and enzyme stabilizer.
2~ 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
-
i394~
- 20 -
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.
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 washiny 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.
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 70aF.
In another group of tests loss in enzyme
activity with time was studied for the following
- 21 -
composltion made in accordance with the preferred
method of the invention:
~E~ Wt.
Savinase 8.OL 0.2
lM NaCl (aq.) 1.5
Ethylene glycol 2.5
Biosoft EA-lO 14.65
Neodol 25-3 14.65
Isopar L 66.3
Perfume 0.2
Samples of the above composition were then
stored at various temperature for a period of six
month6. Table I belou sets/forth the results of tests
on enzyme activity at the end of the six month period.
-
l TABLE I
Enzyme Activity After Six Months Storage
Storage Wt.% ~ activity*
temperature active enzyme remaining
35F 0.17 85
70F 0.11 55
100F 0.02 10
*assumes 0.2 wt.% active enzyme in original sample
-
i3~4d~
- 22 -
A series o studies were carried out to
evaluate the efficacy of the enzyme containing pre-wash
compositions of the invention.
In a first series, a number of compositions
were prepared wherein the enzyme content was varied
from O 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. Laundr~ detergent and a commercial pre-wash
1~ 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).
39~
-- 23 -
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-- 24 --
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- 25
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- 26 -
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-- 27 --
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r ) O N
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-- 28 --
.....
In U~ O ~ O ~
E~ ~ ~ 1- oo OD r~ co
~10~7~1n ~r~
O~
o m ~ ~
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co ~ ~r ~ ~ ~
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E~ P; . o m G) a~
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r~
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U l4 ¢1 ooooo^\ X~
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,~
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39~(
-- 29 --
o ~ ~ In ~D ~
~ C~
u~ c~ ~ o In ~r ~ ~ o ~r
~ . . ~
o ~ ~C~J~ ~ o
I¢ t~ ~ t~ N ~ ~
~;
W'~ ~ ~
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~ ~¢ ~: æ o
m :~ ~1 E~r~ cn
o U~ ~; o ...... ..
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Pl a~
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00000~ X
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P~ H ~1
m v~ . o~
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- 30 -
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.
In a second series of tests, another group of
invention compositions were prepared and tested along
with Clorox pre-wash and laundry detergent against a
broad range of stains. In this second series, the
enzyme content was kept constant at 0.2%. Table IX
sets forth the various compositions. Tables X, XI, and
XII set forth the results when the formulations were
tested against the indicated stains on 100% cotton
fabric, 65/3S polyester/cotton fabric, and 100%
polyester fabric.
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- 32 -
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- 33 -
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m~ ~ ~ ~c,~ ~c~
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E~ æ ~ o o ~
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P~ E~
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:~ o~r :n~
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a~
a~ ~ ~ ~ ~ co a~
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t) ~l ~
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E-' Z O .¢ ~z; O
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- 35 -
The compositions set forth in Table IX above
were stored for periods of time up to 2 months at -
storage temperatures varying bet~een 35 and 100F~
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.
~39~4
-- 36 --
o ~ r~ ~ r~ D r~ ~) N
O O ~ t~ O It`l
a~ ~ ~ ~ ~ ~
~D N ~1 i--~D ~r ~ ~Cl~ Ct~ i_ tr) In
O ............
O ~ ~ ~ OD~ ~ ~ ~-~ ~ ~ ~ I
r~ I_ a~ N ~
I~o o~ ~ ~r
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W Irl N O O ~ ~
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oo ~ 1
O ~ ~1 O~~ ~ ~ ' ~ ~1 ~ X
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X ~ ~ O ~ ~ ~ ~ ~ ~) ~ ~ ~ 7 0 ~
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r~
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o - ........................................ - - -
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u~ ... ... . - - p ~ p
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4~
Further studies were undertaken to evaluate
physical stability in varying composi.tions prepared
according to the invention. Table XIV below sets forth
these formulaticns along with statements concerning
their physical stability after storage at various
storage temperatures.
~.26~
-- 38 --
o'P O O O U~ D O O ~
.........
3 r I o o ~ ~ O O :~
~o
d, ~ m ~ ~ ~ o o ~ ~ o
......... -~O
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3 o o ~ ~r ~ ~ u~ o o Q o
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3 o ~ o ~ o o
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dP ~ O O t~ , o o ~ ~n
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o o o ~r ~r ~ ~ o o
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dP ~ O O ~ ~ O~ O O ~ U~
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U) U~ Q
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X ~: d. ~ O U~ ~ ~ ~ O O
P ~ ...... ~
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O Ir) ~) ~) N O O N
.........
3 o o N ~ ~ r~) O Ll') O
1 ~00~9~p~00~
3 o ~l o ~r ~r ~r o In o
~1 ~1
d~~ ~ O O 1--r--cn o o ~ dPI O O U~ ~ ~ ~ O O
......... ~ .........
3 o o o ~ ~ ~r o u~ o 3 ~ ~ N ~ ~ ~ Lt-) O O
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a ~ ~z a) ~ ,~ ~æ Q~ ~J
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-- 39 --
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r-l
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.---.----- dP
o ~ ~ o ~ o ~r ~ ~ o ,~
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- 40 -
TABLE XV below presents some prewash
formulations wherein several different enzymes were --
utilized. These formulations were also tested for
performance on various stains.
/~ ~
-- 41 --
TABLE XV
RAW MATERIALS A B C
~wt% ) (wt% ) ~wt% )
lM NaCL 1,5 1.5 1.5
Ethylene Glycol 2.5 2.5 2.5
Neodol 25-3 14.63 14.51 14.65
Biosoft EA-10 14.65 14 . 51 14.65
`Isopar K 66.3 66.14 66.3
Perfume 0.2 0.2 0.2
10 Esperase 8.OL 0.2 0.0 0.0
Alkalase 2.5L 0.0 0.64 0.0
Savinase 8.01 0.0 0.0 0.2
These samples were evaluated for performance on grassl
blood and gravy. All three formulas provided a benefit
on grass and gravy. The bloo stain was totally
removed by detergent alone. No enzyme stability test
was conducted.
i39~
- ~2 -
Still another ~roup 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 - Pormula G) was varied. Table XVI also
indicates the residual enzyme activity after storage
for the stated period.
Tables XVII, XVIII, and XIX below, present
performance data on various fabrics for the
compositions of Table XVI.
~39~ (
-- 43 --
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-- 46 --
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