U.S. patent number 3,860,536 [Application Number 05/107,423] was granted by the patent office on 1975-01-14 for enzyme-detergent combination.
This patent grant is currently assigned to CPC International Inc.. Invention is credited to Theodore H. Kritchevsky, Richard G. Landwerlen.
United States Patent |
3,860,536 |
Landwerlen , et al. |
January 14, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
ENZYME-DETERGENT COMBINATION
Abstract
A stable aqueous formulation of an enzyme-detergent combination.
The stability of this aqueous formulation permits a wider
applicability in laundering textile fabrics.
Inventors: |
Landwerlen; Richard G.
(Indianapolis, IN), Kritchevsky; Theodore H. (Chicago,
IL) |
Assignee: |
CPC International Inc.
(Inglewood Cliffs, NJ)
|
Family
ID: |
26804764 |
Appl.
No.: |
05/107,423 |
Filed: |
January 18, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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200382 |
Jan 2, 1970 |
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Current U.S.
Class: |
510/284; 510/321;
510/505; 435/188 |
Current CPC
Class: |
C11D
3/38663 (20130101); C11D 3/2044 (20130101) |
Current International
Class: |
C11D
3/38 (20060101); C11D 3/386 (20060101); C11D
3/20 (20060101); C11d 001/14 (); C11d 001/72 ();
C11d 007/42 () |
Field of
Search: |
;252/89,132,551,558,559
;195/63,68 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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962,321 |
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Jul 1964 |
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GB |
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6,715,387 |
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May 1968 |
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NL |
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6,216,696 |
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Oct 1962 |
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JA |
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Other References
Yasumatsu et al. "Stabilities of Enzymes in polyhydrie Alcohols,"
J. Agr. Biol. Chem., Vol. 29, No. 7, pp. 665-671, 1954..
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Primary Examiner: Willis; P. E.
Parent Case Text
This is a continuation-in-part of application Ser. No. 382, filed
Jan. 2, 1970, now abandoned.
Claims
We claim:
1. A stable enzyme-detergent combination comprising an aqueous
solution of (a) the equivalent of from about 0.001 percent to about
3.0 percent of a protease having an average activity of 165,000 PCA
units per gram (b) from about 0.05 percent to about 40 percent of a
detergent and (c) from about 5 to about 60 percent propylene glycol
as a stabilizing agent, said aqueous solution having a pH within
the range of from about 6.0 to about 9.5.
2. The enzyme-detergent combination of claim 1 wherein the protease
is active either in neutral or alkaline media.
3. The enzyme-detergent combination of claim 1 wherein the protease
is of bacterial origin.
4. The enzyme-detergent combination of claim 1 wherein the protease
is derived from Bacillus subtilus,
5. The enzyme-detergent combination of claim 1 wherein the
detergent is a non-ionic detergent.
6. The enzyme-detergent combination of claim 1 wherein the
detergent is a polyoxyethylene alkyl phenyl ether.
7. The enzyme-detergent combination of claim 1 wherein the
detergent is a polyoxyethylene alkyl phenyl ether having at least 5
oxyethylene units.
8. The enzyme-detergent combination of claim 1 wherein the
detergent is an anionic detergent.
9. The enzyme-detergent combination of claim 1 wherein the
detergent is a polyoxyalkylene alcohol sulfate.
10. The enzyme-detergent combination of claim 1 wherein the
detergent is a metal alkyl benzene sulfonate.
11. The enzyme-detergent combination of claim 1 wherein the
detergent is a sodium alkyl benzene sulfonate.
12. The enzyme-detergent combination of claim 1 wherein the
detergent is an amphoteric detergent.
13. The enzyme-detergent combination of claim 1 containing
additionally an amylase.
14. An aerosol formulation comprising the enzyme-detergent
combination of claim 1.
15. A method of cleaning stained textile materials comprising
applying to a stained textile material the enzymedetergent
combination of claim 1.
16. A stable enzyme-detergent combination consisting essentially of
an aqueous solution of (a) the equivalent of from about 0.001
percent to about 3.0 percent of a protease derived from Bacillus
subtilus having an average activity of 165,000 PCA units per gram
(b) from about 0.05percent to about 40 percent of a non-ionic
detergent and (c) from about 5 percent to about 60 percent of
propylene glycol, said aqueous solution having a pH within the
range of from about 6.0 to about 9.5.
17. An aerosol formulation comprising the enzyme-detergent
combination of claim 10.
18. A method of cleaning stained textile materials comprising
applying to a stained textile material the enzyme-detergent
combination of claim 16.
19. A stable enzyme-detergent combination consisting essentially of
an aqueous solution (a) having the equivalent of from about 0.001
percent to about 3.0 percent of a protease derived from Bacillus
subtilus and having an average activity of 165,000 PCA units per
gram, (b) from about 0.05 percent to about 40 percent of an anionic
detergent and (c) from about 5 percent to about 60 percent of
propylene glycol, said aqueous solution having a pH of from about
6.0 to about 9.5.
20. An aerosol formulation comprising the enzyme-detergent
combination of claim 19.
21. A method of cleaning stained textile materials comprising
applying to a stained textile material the enzyme-detergent
combination of claim 19.
22. An enzyme-detergent concentrate comprising (a) from about 0.001
percent to about 3.0 percent of a protease, based on an average
activity of 165,000 PCA units per gram, (b) from about 0.05 percent
to about 40 percent of a detergent and (c) from about 5 percent to
about 60 percent of propylene glycol as a stabilizing agent.
23. A stable enzyme-detergent combination comprising water, the
equivalent of from about 0.001 percent to about 3.0 percent of a
protease having an average activity of 165,000 PCA units per gram,
from about 0.05 percent to about 40 percent of a detergent, from
about 5 percent to about 60 percent of propylene glycol as a
stabilizing agent, and from about 10 percent to about 40 percent of
naphtha or a chlorinated aliphatic hydrocarbon having fewer than 6
carbon atoms.
Description
This invention relates to the laundering of clothing and, in
particular, to a novel enzyme-detergent combination which is
notably stable in aqueous formulations.
The laundering of clothing generally is accomplished by means of
solid detergent compositions dissolved in a large volume of water.
The dirty clothing is immersed in this solution, usually maintained
at an elevated temperature, and agitated therein for 10-30 minutes.
The so-called "wash water" then is removed and the clothing is
rinsed with clean water. Many different types of detergents have
been developed for this use and a wide variety are available which
produce quite satisfactory results. One exception to these
satisfactory results, however, consists of proteinaceous stains.
These are removed only with great difficulty and the above
laundering process usually is not effective to remove them. Typical
proteinaceous stains of this type are those derived from blood,
perspiration, albumen, fecal material and the like.
In the prior art, the housewife had to pre-spot any stain on a
textile before laundering. Each type of stain had to be treated
individually and required a variety of chemicals for different
stains, definite operator skill, and much patience to perform a
variety of steps. Stain removal or even stain reduction was not
always accomplished by these methods.
Combinations of such enzymes and detergents have been used in an
effort to solve this problem and these efforts likewise have been
successful. It has been necessary to select the detergent and the
enzyme very carefully so as to assure compatibility. A wide variety
of non-ionic and anionic detergents can be used effectively in
combination with these enzymes.
One disadvantage involved in the use of these enzyme-detergent
combinations is the fact that a pre-soak period is necessary for
stain removal. That is, the stained clothing must be soaked in a
solution containing the enzyme-detergent combination for at least
30 minutes prior to subjecting the clothing to the usual laundering
cycle. This not only lengthens the overall time required to launder
the clothing, but poses a particular problem in view of the fact
that most automatic home clothes washers are not adapted to
accommodate this extra 30 minutes soaking period. Thus, the
housewife must make certain manual adjustments in the operation of
the ordinary home washing machine, so that in effect it is not an
automatic operation. This is no problem in Europe where the
European housewife, through familial habits, has been predisposed
to soak her laundry prior to the washing cycle for more active
cleaning. In fact, many Europeans routinely soak their family wash
overnight to soften and remove stubborn soil and stains prior to
washing with a detergent. Required pre-soak periods are built into
European washing machine cycles so that the overall washing time is
increased up to 30 minutes, which gives the enzyme portion of the
formula sufficient contact time to be effective. In the United
States, however, it is a problem and it is highly desirable to
devise some means by which the housewife can benefit from the
effectiveness of enzyme-detergent combinations without, at the same
time, rendering her automatic washing machine less convenient to
operate and without the extended soaking period.
As noted above, these enzyme-detergent combinations are marketed as
solids. The reason for this is that liquid solutions of the
enzyme-detergent combinations are not stable. They deteriorate on
standing, i.e., the enzyme gradually loses its activity. An aqueous
solution of such an enzyme may retain sufficient activity to
effectively remove soil and stains for as long as 24 hours, but
beyond that, its activity will decrease so that the enzyme solution
will no longer effectively remove soil and stains. For this reason,
it has been quite impractical to market enzyme-detergent
combinations as aqueous solutions, however desirable they would
be.
Accordingly, it is an object of this invention to provide a stable
aqueous formulation of an enzyme, suitable for use in
enzyme-detergent combinations.
Another object of the present invention is to facilitate the use of
enzyme-detergent combinations.
Still another object of the present invention is to provide a more
convenient means and more complete removal of proteinaceous stains
from clothing.
Still another object of the present invention is to provide a
stable water solution of an enzyme-detergent combination.
These and other objects of the present invention are accomplished
by an aqueous formulation of a protease or a protease amylase
enzyme and a polyhydric alcohol, and by such formulations which
also contain a detergent.
A method has now been developed to stabilize a water solution of
enzyme and detergent that is stable over a long shelf life, is
usable as supplied and is very effective in removal of a large
number of common stains, such as ground-in dirt, body soil,
perspiration, blood, grass stains, milk, coffee, tea and fruit
juices. The stability that is achieved is particularly remarkable
since the enzyme is present in the formulation in extremely low
concentration; in other words, it is very dilute.
The proteases contemplated herein are those detergent compatible
enzymes which are active in alkaline to weakly acid media, i.e.,
those with a minimum pH of 6.0. Acid-active proteases are not used
because they are not effective soil and stain removers and in
general are not compatible with home laundry detergents. Most of
the more effective enzymes have been bacterial in origin although
more recently, effective enzymes have been derived from molds and
vegetable sources. Those derived from bacteria, however, are
preferred. Particularly preferred are those derived from Bacillus
subtilus. The concentration of enzyme is within the range of from
about 0.001 to about 3.0 weight percent, based on the total aqueous
formulation.
In order to determine the proteolytic activity of the alkaline
protease herein, the casein digestion test is employed. In this
method, 3 ml. of a substrate solution, which contains 1.3 percent
casein dissolved in 0.6 percent tris(hydroxymethoyl)aminomethane
with the pH adjusted to 7.5, 3 ml. of 0.02N sodium hydroxide and 3
ml. of distilled water are measured into a test tube. This solution
is held at 37.degree.C. for 10 minutes and then there is added 3
ml. of a mixture consisting of 8 g. of the enzyme detergent sample
and 400 ml. of tris buffer (an aqueous solution of 0.6 percent
tris(hydroxymethyl)aminomethane and 0.4 percent sodium chloride,
with the pH adjusted to 8.5). Incubate for 15 minutes at
37.degree.C., then add 10 ml. TCA Reagent, which contains 40
percent glacial acetic acid mixed with 1.8 percent trichloroacetic
acid and 1.9 percent sodium acetate. Place in 37.degree.C. bath for
15 minutes. The contents of the test tube are then filtered and the
optical density of the filtrate is measured at 277 mu. The activity
of the sample in PCA units (the initials stand for Proteolytic
Activity, Casein Substrate, Alkaline) per gram is calculated by the
following formula.
A.sub.277 of hydrolyzate .times. 136/ gram of enzyme prep. in test
= PCA units per gram
The protease enzymes referred to herein have an average activity of
165,000 PCA units per gram.
The detergent may be one or a combination of anionic, non-ionic or
amphoteric surfactants. Illustrative detergent examples include
nonionic surfactants such as polyoxyethylene nonylphenols,
polyoxyethylated fatty alcohols, polyoxyethylated fatty acids,
glyceryl mono fatty acid esters of 90 percent or higher monoester;
anionic surfactants such as the salts of alkyl aryl sulfonates, the
salts of the fatty alcohol sulfates, polyoxyalkylene fatty alcohol
sulfates and the salts of complex organic phosphate esters; and
amphoteric surfactants such as complex fatty compounds containing
amide and ester linkages as well as an amine group and an acid
group, fatty beta-amino-propionic acids and fatty
beta-iminodipropionic acids with the acid portion of the amphoteric
molecule as an uncombined acid or as an alkaline metal salt. The
detergent or the detergent combination is present in the
compositions of this invention within the range of from about 0.05
percent to about 40 percent by weight.
The polyhydric alcohols contemplated herein include those having up
to 6 carbon atoms and from 2 to 6 hydroxyl groups, e.g., ethylene
glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexylene glycol,
d-sorbital dextrose and pentaerythritol; and also the polyalkylene
glycols wherein the alkylene group contains up to 6 carbon atoms.
Illustrative species of such polyalkylene glycols include
polyethylene glycol, polypropylene glycol, polybutylene glycol,
polyamylene glycol. The molecular weight of the polyalkylene glycol
may range up to about 6,000. The polyhydric alcohol should be water
soluble, i.e., at least to the extent of 30 grams in 100 grams of
water. Propylene glycol and glycerine are preferred species,
although others within this group are similarly effective. The
concentration of alcohol is within the range of from about 5 to
about 60 percent. Mixtures of these polyhydric alcohols may be
used.
As noted above, the pH of the aqueous solution of this invention is
a critical feature thereof. The detergent-compatible enzymes
contemplated for use in these compositions are effective over a
specific pH range. Tests show that the aqueous detergentenzyme
solutions of this invention are effective and stable within the pH
range of from about 6 to about 9.5. Outside this pH range, these
solutions are less effective or ineffective in stain and soil
removal or the enzyme is unstable.
The aqueous solutions of this invention may contain other
ingredients that are used for their known function. Certain
ingredients may be used to adjust the pH of the solution to a value
within the specified pH range such as tetrapotassium pyrophosphate,
tribasic sodium phosphate, dibasic sodium phosphate, monobasic
sodium phosphate, sodium hydroxide or citric acid. Soil suspending
agents such as sodium carboxymethyl cellulose or
polyvinylpyrrolidone may be optionally incorporated for their known
function. Fluorescent whitening agents may be optionally
incorporated with those brighteners of the anionic or nonionic
types preferred. Perfumes may be employed for their known purpose.
Preservatives such as sodium chloride, sodium sulfate, methyl
paraben, propyl paraben or potassium sorbate may be used to prevent
bacterial inactivation of the enzyme during shelf storage and
before use.
An important optional ingredient in the compositions herein is an
amylase enzyme. In combination with the protease, it exerts a
complementary influence on the soil and stain-removing qualities of
the enzyme-detergent combination. Preferred amylases are those
derived from Bacillus subtilus.
Another important optional ingredient is an organic solvent such as
a naphtha or a chlorinated lower aliphatic hydrocarbon such as
perchloroethylene or 1,1,2-trichloroethylene. Chlorinated aliphatic
hydrocarbons having fewer than 6 carbon atoms can be incorporated
into solutions of this invention with those having 1 or 2 carbon
atoms being preferred and their incorporation into the compositions
of this invention in concentrations within the range of from about
10 to about 40 percent renders such compositions especially
effective in removing oil and grease stains from fabrics in
addition to the protein and carbohydrate stains removed by the
enzymes. Aqueous compositions containing a chlorinated lower
aliphatic hydrocarbon are not solutions, of course, but they
nevertheless are useful for the purposes of this invention.
The stability of the aqueous formulations of enzyme and detergent
of this invention permits this combination of materials to be
stored, transported and marketed as such. They can be used by the
housewife who need only apply the aqueous formulation directly to
the soiled fabric where it is available in concentrated form to
perform its intended function more efficiently than otherwise. An
especially significant advantage is the fact that these aqueous
formulations can be marketed in aerosol containers from which they
may be applied directly to the soiled fabric. This eliminates the
necessity for the housewife to get a bucket or pan, fill it with
water, add the solid enzyme-detergent combination and wait for it
to dissolve, then immerse the soiled fabric in the solution. In
addition to aerosol formulations, the enzyme-detergent combinations
of this invention may be marketed in liquid form, or in a stick
paste form. The holding time is also less than one-half that of the
solid enzyme-detergents. In aerosol formulations it is desirable in
specific cases to incorporate an anti-foam agent to break the foam
quickly after application to a stained surface and thus facilitate
penetration of the enzyme and detergent into the stain. Any of
various silicone emulsions presently available in the trade are
useful for this purpose.
The invention is illustrated by the following specific examples,
which are not to be construed as limiting. All parts and
percentages herein, unless otherwise expressed, are by weight.
EXAMPLE 1 ______________________________________ PER CENT
______________________________________ Alkaline protease 1.0
Tetrapotassium pyrophosphate 0.2 Propylene glycol 20.0 Water 78.8
EXAMPLE 2 Polyoxyethylene (9-10 units) nonylphenol 10.0
Tetrapotassium pyrophosphate 0.4 Propylene Glycol 10.0 Alkylene
Protease 1.0 Water 78.6 EXAMPLE 3 PER CENT Polyoxyethylene (9-10
units) nonylphenol 10.0 Tetrapotassium pyrophosphate 0.4 Glycerin
20.0 Alkaline Protease 1.0 Water 68.6 EXAMPLE 4 Sodium lauryl
sulfate 10.0 Propylene Glycol 20.0 Alkaline Protease 1.0 Water 69.0
EXAMPLE 5 Gafac LO-529, a product of GAF Corp., New York, N.Y.,
believed to be an 88% aqueous solution of the sodium salt of a
P.sub.2 O.sub.5 -ethoxylated alkyl phenol reaction product 11.4
Tetrapotassium pyrophosphate 4.0 Propylene Glycol 20.0 Alkaline
Protease 1.0 Water 63.6 EXAMPLE 6 Polyoxyethylene (9-10 units)
nonylphenyl 35.0 Propylene Glycol 30.0 Methyl paraben 0.1 Propyl
paraben 0.05 Tetrapotassium pyrophosphate 0.55 Alkaline
protease-amylase 2.0 Anti-foam 0.5 Water 31.8 EXAMPLE 7 PER CENT
Polyoxyethylene (10-11 units) nonylphenol 3.50 Polyoxyethylene (30
units) nonylphenol 2.25 Polyoxyethylene (4 units) nonylphenol 2.75
Antaron FC-34, a product of GAF Corp.., New York, N.Y., believed to
be a 37% aqueous solution of a sodium alkyl amide sulfonate 4.00
Glyceryl monostearate (90% mono ester) 2.0 Citric Acid 0.09
Propylene Glycol 20.0 Optical Whiteners 0.85 Alkaline Protease 1.0
Water 63.56 EXAMPLE 8 Polyoxyethylene (30 units) nonylphenol 3.83
Polyoxyethylene (4 units) nonylphenol 4.67 Anatron FC-34, a product
of GAF Corp., New York, N.Y., believed to be a 37% aqueous solution
of a sodium alkyl amide sulfonate 4.0 Glyceryl monostearate (90%
mono ester) 2.0 Propylene Glycol 20.0 Citric Acid 0.09 Alkaline
Protease 0.5 Water 64.91 EXAMPLE 9 Polyoxyethylene (9-10 units)
nonylphenol 10.0 Tetrapotassium pyrophosphate 0.25 Propylene Glycol
20.0 Alkaline Protease 1.0 Perchloroethylene 20.0 Water 48.75
EXAMPLE 10 Polyoxyethylene (30 units) nonylphenol 8.1
Polyoxyethylene (4 units) nonylphenol 9.7 Polyoxyethylene (10-11
units) nonylphenol 12.5 Antaron FC-34, a product of GAF Corp., New
York, N.Y., believed to be a 37% aqueous solution of a sodium alkyl
amide sulfonate 8.0 Alkaline protease-amylase 2.0 Propylene Glycol
30.0 Potassium Sorbate 1.0 Citric Acid 0.2 Anti-foam 0.5 Water 28.0
______________________________________
The composition shown in Example 7 was incorporated into an aerosol
formulation and applied as a foam to several different stains that
had been heavily applied to fabric swatches with the stains derived
from a variety of materials. After 30 minutes, the fabric was
washed for 15 minutes in one liter of water at 130.degree.F.,
containing 1.5 grams of Tide, a sodium alkyl sulfonate detergent.
The results are shown in the Table below where the cleanliness
rating is based on a scale of 1 to 10, with 1 indicating the
complete absence of stain and 10 indicating a fabric from which no
stain has been removed.
TABLE I
__________________________________________________________________________
Treatment with Composition of Ex. 7 Followed Washed With by
Detergent Wash Detergent Only
__________________________________________________________________________
Stain Cotton Dacron/Cotton Cotton Dacron/Cotton
__________________________________________________________________________
Liver 1 1 6 3 Tea 3 1 7 5 Coffee 1 1 5 4 Grape Juice 1 1 2 4 Grease
3 4 8 8 Chocolate 3 1 5 2 Mustard 4 1 8 2 French Dressing 2 1 6 7
Standard Soil Cloth 8 2 5 7
__________________________________________________________________________
From Table I, it is apparent that the enzyme-detergent combination
of this invention is effective to remove stains which are not
ordinarily removed by the use of detergents alone.
The instability of enzymes in aqueous solutions is well known.
Ordinarily, they must be stored in the dry state and then put into
solution immediately before use. For required shelf stability, care
must be taken so that the final formulation has a moisture content
less than 4-5 percent.
The stability of the aqueous solutions of this invention, however,
is shown by a comparison of an ordinary enzyme-detergent
combination with that same combination supplemented by the addition
of 20 percent of propylene glycol. The compared solutions had the
following compositions:
Composition A Composition B Alkylphenoxypolyoxyethylene Ethanol
10.0 10.0 Tetrapotassium Pyrophosphate 0.4 0.2 Alkaline Protease
(165,000 PCA units) 1.0 1.0 Propylene Glycol -- 20.0 Water 88.6
68.8
After two months' storage Composition A had retained only 24
percent of its enzyme activity, i.e., 396 PCA units per gram of the
composition with respect to its original activity of 1650 PCA units
per gram, whereas Composition B (illustrative of this invention)
after three months, retained 83 percent of its enzymic activity,
i.e., 1,369 PCA units per gram with respect to its original
activity of 1,650 PCA units per gram.
Cotton and dacron/cotton fabric samples are heavily stained with
various types of stains. In each case the stains (on the fabric)
are aged for 3 months. The stained cloth is treated with an aerosol
formulation of the composition of Example 9, allowed to stand for
15 minutes and then washed for 15 minutes in 1 liter of hot
(130.degree.F.) water containing 1.5 grams of a home laundry
detergent. The washed samples are rated visually on a scale of 1-10
where 1 indicates complete removal of stain and 10 indicates no
removal of stain. A second series of tests are run, for purposes of
comparison, with the initial step of treatment with the composition
of this invention (product of Example 9) being omitted. The results
of these tests are shown below, in Table II.
TABLE II
__________________________________________________________________________
Treatment with Composition of Example 9, Followed by Washing with
Detergent Washing with Detergent Cotton Dacron/Cotton Cotton
Dacron/Cotton
__________________________________________________________________________
Liver 2 1 9 9 Blood 1 1 9 9 Tea 3 2 4 4 Coffee 3 2 4 3 Lipstick 2 1
8 8 Chocolate 1 1 2 2 Cocoa 1 1 5 3 Blood-milk-ink (Empa 116) 2 --
5 -- Cocoa-milk-sugar (Empa 112) 2 -- 4 --
__________________________________________________________________________
While the invention has been described in connection with specific
embodiments thereof, it will be understood that it is capable of
further modification, and this application is intended to cover any
variations, uses, or adaptations of the invention following, in
general, the principles of the invention and including such
departures from the present disclosure as come within known or
customary practice in the art to which the invention pertains and
as may be applied to the essential features hereinbefore set forth,
and as fall within the scope of the invention.
* * * * *