U.S. patent number 3,723,327 [Application Number 05/259,638] was granted by the patent office on 1973-03-27 for granular proteolytic enzyme composition.
This patent grant is currently assigned to Lever Brothers Company. Invention is credited to Foscarina Pasztor NEE Rozzo, Daniel Marten van Kampen.
United States Patent |
3,723,327 |
van Kampen , et al. |
March 27, 1973 |
GRANULAR PROTEOLYTIC ENZYME COMPOSITION
Abstract
The invention is directed to an improvement in the storage
stability of granular proteolytic enzyme compositions. The
proteolytic enzymes are contained in granules to which an acidic
substance has been added. The granules will comprise a neutral or
alkaline carrier material, for example an alkali metal phosphate; a
gluing agent, for example a nonionic surface active agent; a
proteolytic enzyme and an acidic material, for example citric
acid.
Inventors: |
van Kampen; Daniel Marten
(Vlaardingen, NL), NEE Rozzo; Foscarina Pasztor
(Abcoude, NL) |
Assignee: |
Lever Brothers Company (New
York, NY)
|
Family
ID: |
22985741 |
Appl.
No.: |
05/259,638 |
Filed: |
June 5, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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20019 |
Mar 16, 1970 |
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Current U.S.
Class: |
510/374; 435/188;
510/306; 510/530; 510/392; 510/320; 435/187 |
Current CPC
Class: |
C11D
17/0039 (20130101); C11D 3/38672 (20130101) |
Current International
Class: |
C11D
3/38 (20060101); C11D 3/386 (20060101); C11D
17/00 (20060101); C11d 007/08 (); C11d 007/42 ();
C11d 017/06 () |
Field of
Search: |
;195/63,68
;252/89,132,135,DIG.12 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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747,740 |
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Sep 1970 |
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BE |
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1,107,824 |
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Mar 1968 |
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GB |
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1,558,495 |
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Feb 1969 |
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FR |
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Primary Examiner: Rosdol; Leon D.
Assistant Examiner: Albrecht; Dennis L.
Parent Case Text
Cross-Reference to Related Application
This application is a continuation-in-part of our earlier filed
application Ser. No. 20, 019, filed 16th Mar., 1970 now abandoned.
Claims
What is claimed is:
1. A granular proteolytic enzyme composition, adapted to be
formulated with a detergent composition, the proteolytic enzyme
composition consisting essentially of
i. a core of a non-acidic, non-hygroscopic, nonfriable carrier
material selected from the group consisting of
alkalimetaltripolyphosphates, -pyrophosphates, -orthophosphates,
alkalimetalsulphates, -borates, -silicates, -carbonates,
gelatinized starch and starch derivatives,
ii. a coating layer enrobing said core, consisting of a nonionic
detergent surfactant selected from the group of alkyl phenols with
eight to 18 carbon atoms in the alkyl chain, and condensed with 8
to 15 moles of ethylene oxide, C.sub.8 -C.sub.20 monohydric
aliphatic alcohols condensed with 6 to 25 moles of ethylene oxide,
secondary C.sub.11 -.sub.15 alcohols condensed with 9 moles of
ethylene oxide, fatty acid mono and dialkylol amides with 10 to 20
carbon atoms in the fatty acid residue, and ethoxylated derivatives
thereof,
iii. an acidic substance, dissolved or dispersed in said coating
layer, said acidic substance having a pH of 4 to 6 in a 1%-aqueous
solution, selected from the group consisting of citric acid, and
adipic acid, said acidic substance being present in an amount of
0.5 to 10 percent by weight of the granule, the weight ratio
between the nonionic detergent surfactant coating layer and the
acidic substance being from 10:1 to 1:1,
iiii. proteolytic enzymes, attached to the coating layer of the
core, in such an amount that the weight ratio between the
proteolytic activity, calculated to a standard activity of 1.5
Anson unit/g, and the acidic substance is from 10:1 to 1:10.
2. A composition according to claim 1, in which the granular
proteolytic enzyme composition comprises furthermore an outer
coating layer of the nonionic detergent surfactant, in which the
acidic substance has been dispersed or dissolved.
3. A composition according to claim 1, in which the acidic
substance is citric acid.
4. A composition according to claim 1, in which the amount of the
acidic substance is from 2 to 8 percent by weight of the
granule.
5. A detergent composition consisting essentially of
a. from 2 to 20 percent by weight of an anionic detergent
surfactant selected from the group consisting of
alkylbenzenesulphonates with 12 to 18 carbon atoms in the alkyl
group, alkylsulphonates with 10 to 24 carbon atoms in the alkyl
group, olefinesulphonates with 10 to 20 carbon atoms,
acylisethionates with 12 to 18 carbon atoms in the acyl group and
acyltaurates with 12 to 18 carbon atoms in the acyl group.
b. from 1 to 10 percent by weight of a nonionic detergent
surfactant selected from the group consisting of the condensation
products of ethylene oxide or propylene oxide with alcohols having
from 12 to 24 carbon atoms in the alkyl group, with alkylphenols
having from eight to 18 carbon atoms in the alkyl group, with fatty
acid amides with a C.sub.10 -C.sub.24 fatty acid residue, with
polyalkyleneglycols and with mixed alkylene oxide condensation
products,
c. from 1 to 10 percent by weight of an alkalimetal soap of
C.sub.12 -C.sub.22 fatty acids,
d. from 20 to 50 percent by weight of a water-soluble alkalimetal
builder salt,
e. from 0 to 45 percent by weight of a bleaching agent,
f. from 0.5 to 15 percent by weight of a granular proteolytic
enzyme composition consisting essentially of
i. a core of a non-acidic, non-hygroscopic, non-friable carrier
material selected from the group consisting of
alkalimetaltripolyphosphates, -pyrophosphates, -orthophosphates,
alkalimetalsulphates, -borates, -silicates, -carbonates,
gelatinized starch and starch derivatives,
ii. a coating layer enrobing said core, consisting of a nonionic
detergent surfactant selected from the group of alkyl phenols with
eight to 18 carbon atoms in the alkyl chain, and condensed with 8
to 15 moles of ethylene oxide, C.sub.8 -C.sub.20 monohydric
aliphatic alcohols condensed with 6 to 25 moles of ethylene oxide,
secondary C.sub.11 -C.sub.15 alcohols condensed with 9 moles of
ethylene oxide, fatty acid mono- and dialkylol amides in the fatty
acid residue, and ethoxylated derivatives thereof,
iii. an acidic substance, dissolved or dispersed in said coating
layer, said acidic substance having a pH of 4 to 6 in a 1%-aqueous
solution, selected from the group consisting of citric acid and
adipic acid, said acidic substance being present in an amount of
0.5 to 10 percent by weight of the granule, the weight ratio
between the nonionic detergent surfactant coating layer and the
acidic substance being from 10:1 to 1:1.
iiii. proteolytic enzymes, attached to the coating layer of the
core, in such an amount that the weight ratio between the
proteolytic activity, calculated to a standard activity of 1.5
Anson unit/g, and the acidic substance is from 10:1 to 1:10.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to granular proteolytic enzyme
compositions, adapted to be formulated with a detergent
composition, and to detergent compositions containing these
granular proteolytic enzyme compositions.
2. Description of the Prior Art
Enzymic cleaning compositions are old. See, for example, German
patent specifications 283,923 (Rohm, 1915) and 329,958 (Rohm,
1920). The enzymes aid in cleaning by attacking the soil and stains
of the soiled objects to be cleaned. Proteinaceous soil and stains
are attacked by proteolytic enzymes. Such proteolytic enzymes,
suitable for cleaning purposes, are normally found in the form of
fine powders. Such fine powders are difficult to handle and
difficult to formulate. When such fine powders are incorporated in
detergent compositions, their stability is often greatly impaired
by several ingredients of the detergent composition, and by
moisture, which may be taken up by the detergent composition during
storage. It is believed that this moisture brings the proteolytic
enzymes into contact with the other ingredients of the detergent
composition, which are harmful to the proteolytic enzymes.
It has already been proposed in U.S. Pat. No. 3,519,570 to enhance
the stability of proteolytic enzymes by bringing them in granular
form. This is done by rendering the surfaces of base carried
detergent granules glutinous with a low-melting, ordinarily solid,
water-soluble nonionic surface-active agent which liquefies between
100.degree.F and 200.degree.F, and subsequently conglutinating with
said glutinous surfaces the proteolytic enzymes in a powdered form.
The granules thus obtained may be additionally coated with the
nonionic surface-active agent to encapsulate the proteolytic
enzymes and to protect them from moisture and other harmful
ingredients.
Although such granular proteolytic enzyme compositions are much
more stable than the fine, powdered proteolytic enzymes, their
stability in detergent compositions is still often not satisfactory
for detergent formulation purposes.
Object of the Invention
It is therefore an object of the present invention to further
improve the storage stability of granular proteolytic enzyme
granules. Further objects will become apparent from the detailed
description of the invention given hereafter.
SUMMARY OF THE INVENTION
It has been found that incorporating an acidic substance in the
nonionic layer of the granular proteolytic enzyme compositions of
the type as heretofore described, greatly enhances the storage
stability of said granular proteolytic enzyme compositions. The
present invention therefore relates to a granular proteolytic
enzyme composition, adapted to be formulated with a detergent
composition, the granular proteolytic enzyme composition consisting
essentially of:
1. a core of a non-acidic carrier material
2. a coating layer enrobing said core, the coating layer being a
nonionic surface-active agent
3. proteolytic enzymes, attached to said coating layer
4. an acidic substance, dissolved or dispersed in said coating
layer.
In another aspect of the invention, the granular proteolytic enzyme
composition also contains an outer layer of a nonionic
surface-active agent, in which an acidic substance is dissolved or
dispersed.
DETAILED DESCRIPTION OF INVENTION
The granular proteolytic enzyme composition consists essentially
of
1. a core of non-acidic carrier material
2. a coating layer of a nonionic surface-active agent enrobing said
core, said coating layer containing an acidic substance dissolved
or dispersed therein
3. proteolytic enzymes.
Core of non-acidic carrier material
The core of the granules consists of a non-acidic carrier material,
i.e. a neutral or alkaline carrier material, from which granules
can be made. The particle size of the carrier material should lie
between 0.05 mm and 1.5 mm, preferably between 0.3 and 1.5 mm. The
carrier material should have a porosity of lying between 0.15 ml/g
and 1 ml/g preferably between 0.15 and 0.50 ml/g, determined by the
mercury method. This method consists of adding mercury to the
carrier material under vacuum and measuring the apparent mercury
density in an apparatus as described by J.M. Vleeskens in his
Thesis of Delft University, Holland 1959, using the equation
(.DELTA.Hg/.epsilon.Hg) = volume of pores + (M/.epsilon.s),
where
.DELTA.Hg = difference in weight of mercury before and after
addition to the sample
.epsilon.Hg = density of mercury
M = weight of sample of carrier material
.epsilon.s = density of sample of carrier material
The carrier material must be sufficiently strong, i.e. must be
non-friable, and may not be hygroscopic. Crystal water may be
present, provided the carrier material does not melt in its own
water of crystallization at temperatures below 40.degree.C (as e.g.
Na.sub.2 SO.sub.4.sup.. 10 aq). Suitable examples of neutral and
alkaline carrier materials are alkali metal phosphates, such as
penta sodium and penta potassium triphosphate, tetrasodium
pyrophosphate, sodium or potassium orthophosphate, sodium or
potassium sulphate or mixtures thereof, alkalimetal borates and
carbonates, alkalimetal silicates, gelatinized starch and starch
derivatives. In general, those granulatable carrier materials are
preferred that are desirable in a detergent composition, e.g. penta
sodium or penta potassium tripolyphosphate.
Coating Layer
The coating layer consists of a nonionic surface-active agent that
is liquid or semi-paste-like at room temperature. Higher melting
liquefiable nonionic surface-active agents may also be used.
Examples of suitable nonionic surface-active agents are alkyl
phenols with eight to 18 carbon atoms in the alkyl chain, and
condensed with 8 to 15 moles of ethylene oxide, such as nonylphenol
condensed with 10 moles of ethylene oxide, C.sub.8 -C.sub.20
monohydric aliphatic alcohols condensed with 8 to 25 moles of
ethylene oxide, such as tallow fatty alcohol condensed with 25
moles of ethylene oxide, isotridecyl alcohol condensed with 11
moles of ethylene oxide secondary C.sub.11 -C.sub.15 alcohols
condensed with 9 moles of ethylene oxide, fatty acid mono- and
dialkylol amides with 10 to 20 carbon atoms in the fatty acid
residue, and ethoxylated derivatives thereof. Other suitable
nonionics can be found in Schick, M.J. "Nonionic Surfactants" 1967,
which is hereby incorporated by way of Reference.
Acidic Substance
The acidic substances that are used in the present invention should
have an acid pH value, preferably between 4 and 6, in a 1%-aqueous
solution. Any suitable organic and/or inorganic acid substance may
be used, provided it does not affect the enzyme negatively.
suitable examples are acid salts, such as sodium or potassium acid
pyrophosphate, alkali metal acid orthophosphate, inorganic acids
such as phosphoric acid, and organic acids like citric acid and the
sodium salt thereof, adipic acid and the like.
Particularly preferred are acidic substances which are soluble or
dispersible in the nonionic surface-active agent, such as citric
acid.
Proteolytic enzymes
The proteolytic enzymes which can be used in the present invention
may be of animal and vegetable origin or may be obtained from micro
organisms, including bacteria and fungi. Examples of such
proteolytic enzymes are pepsin, trypsin, papain, aspergillus
peptidase. The preferred proteolytic enzymes are those produced by
micro organisms, such as the proteases produced by Bacillus
subtilis. The commercial proteolytic enzymes are normally in the
form of a fine powder containing the enzymes and an inert carrier
material, such as sodium or calcium sulphate or clay. The preferred
proteolytic enzymes are of the subtilisine type, commercially
available under the trade names Alcalase and Maxatase. Alcalase is
a serine protease, produced by Novo Industrie A/S Copenhagen, by
submerged fermentation of a special strain of Bacillus subtilis.
Maxatase is also a protease, produced from Bacillus subtilis,
manufactured by the Royal Dutch Fermentation Industries at Delft,
Holland.
The granular proteolytic enzyme composition of the present
invention can be prepared in various ways. It is preferred to
incorporate the acidic substance in the nonionic surface-active
agent first, admixing this coating material with the granular
carrier material and subsequently affixing the proteolytic enzyme
powders thereon.
The granular proteolytic enzyme compositions are usually further
coated with a suitable coating material. Suitable coating materials
are those, which are also suitable as coating agents for the core
of the granular proteolytic enzyme compositions as described above,
but other film-forming agents such as polyvinylalcohol,
polyvinylpyrrolidone, shellac, fatty acids, esters, waxes, etc. can
be used.
The outer coating layer thus formed may also comprise the acidic
substance, and it constitutes a preferred embodiment of the present
invention when the inner and outer layers contain the acidic
substance. The layer that contains the acidic substance forms, as
it were, an acidic barrier against the harmful influences of e.g.
particular ingredients of the detergent composition as well as a
barrier to moisture present therein.
The amount of acidic substance required in the present invention is
dependent upon the activity of the proteolytic enzymes as well as
upon the amount of proteolytic enzyme present. In general, the
granular proteolytic enzyme composition should contain an amount of
acidic substance such that the weight ratio between the proteolytic
enzyme, calculated to a standard activity of 1.5 Anson unit/g, and
the acidic substance is from 10:1 to 1:10. Preferably the weight
ratio is 2:1 to 1:2. The ratio between the nonionic surface-active
agent and acidic substance is from 10:1 to 1:1. The acidic
substance is from 0.5 to 10 percent, preferably from 2 to 8 percent
by weight of the granule. The granular proteolytic enzyme
composition is adapted to be particularly formulated with a
detergent composition. Such a detergent composition may comprise
one or more detergent surfactants, such as anionic and nonionic
detergent surfactants, soap and mixtures thereof.
In general, the detergent composition may contain from 2 to 20
percent by weight of an anionid detergent surfactant. Examples
thereof are alkylbenzenesulphonates with 12 to 18 carbon atoms in
the alkyl group, alkylsulphates with 10 to 24 carbon atoms in the
alkyl group, olefinsulphonates prepared by sulphonating
straight-chain .alpha.-olefins with 10 to 20 carbon atoms and
subsequently neutralizing and hydrolyzing the sulphonation reaction
product, acylisethionates with 12 to 18 carbon atoms in the
acyl-group and acyltaurates with 12 to 18 carbon atoms in the acyl
group. The composition may furthermore contain 1 to 10 percent by
weight of a nonionic detergent surfactant. Examples thereof are the
condensation products of alkylene oxide, such as ethylene oxide and
propylene oxide with alcohols having from 12 to 24 carbon atoms in
the alkyl group, with alkylphenols having from eight to 18 carbon
atoms in the alkyl group, with fatty acid amides with a C.sub.10
-C.sub.24 fatty acid residue, with polyalkyleneglycols and mixed
alkylene oxide condensation products.
The compositions may also contain as alkali metal soap in an amount
of 1 to 10 percent by weight. Examples thereof are the alkali metal
soaps of C.sub.12 -C.sub.22 fatty acids, such as palm oil-,
hardened fish oil, coconut oil, and tallow fatty acids.
For medium sudsing compositions the amount of the different
detergent surfactants are
8 to 15 percent by weight of the anionic detergent surfactant
1 to 6 percent by weight of the nonionic detergent surfactant
1 to 5 percent by weight of the alkali metal soap whereas for low
sudsing compositions the amounts are:
2 to 9 percent by weight of the anionic detergent surfactant
2 to 10 percent by weight of the nonionic detergent surfactant
5 to 10 percent by weight of the alkali metal soap.
The remaining part of the composition may consist of the normal
constituents of a detergent composition. They may contain from 20
to 50 percent of a condensed phosphate, such as pentasodium
triphosphate. If desirable, part of the condensed phosphate may be
replaced by an organic builder, such as trisodium
nitrilotriacetate.
Furthermore, from 2 to 10 percent of sodium silicate may be
present, 0.5 to 3 percent of sodium carboxymethylcellulose or other
suitable soil-suspending agent may be present. If desired, up to 45
percent by weight of a bleaching agent, such as sodium perborate
may be added for heavy-duty purposes.
The compositions may furthermore contain alkali metal salts, such
as sodium sulphate, sodium carbonate, sodium borates, and
furthermore other adjuvants, such as tarnish inhibitors, perfumes,
germicides, coloring agents, lather modifiers, fluorescers,
solvents, bleach precursors.
The granular proteolytic enzyme compositions of the invention may
be present in an amount of 0.5-15 percent, preferably 5-10 percent,
by weight of the detergent composition.
Examples of detergent compositions according to the invention will
now be given by way of illustration only and in a non-limitative
manner.
EXAMPLE I
Granules of the composition as given in Table I were prepared by
dry-mixing the granular anhydrous carrier materials having a
particle size of 50-250 .mu. with a commercially available powdered
proteolytic enzyme, manufactured by submerged fermentation with a
strain of Bacillus subtilis known under the trade name Alcalase
(with an activity of 1.5 Anson unit/g), in a mixing apparatus.
Subsequently this dry mixture was granulated by quickly dropwise
adding liquid nonylphenol condensed with 10 moles of ethylene
oxide, to which citric acid had been added first. The granules
obtained were then sieved with a sieve having apertures of 0.5-1 mm
and added in an amount of 5 percent to detergent composition of the
following formula:
sodium salt of straight chain dodecylbenzenesulphonate 5.5 sodium
soap of commercial stearic acid 8.0 nonylphenol condensed with 14
moles of ethylene oxide 3.0 sodium silicate 5.0 sodium sulphate 9.9
sodium carboxymethylcellulose 1.0 pentasodium triphosphate 36.0
sodium perborate 30.0 water, perfume, etc. rest
The residual activity of the proteolytic enzyme was determined
after 7 days' storage of the detergent composition with the enzyme
granules at 30.degree.C and 80 percent R.H. The results are given
in Table I. ##SPC1##
EXAMPLE II
Granules were prepared of the composition as given in Table II.
TABLE II
Pentasodium triphosphate 58 66 70 66 70 74 Nonyl phenol condensed
with 10 moles of ethylene oxide 10 10 10 10 10 10 Citric Acid 8 4
Boric Acid 8 4 KH.sub.2 PO.sub.4 16 Alcalase 16 16 16 16 16 16
Number 1 2 3 4 5 6 (blank)
The granules were prepared from granular anhydrous pentasodium
triphosphate having a particle size of 50-250 .mu..
The powdered proteolytic enzyme Alcalase was mixed with the acidic
substance and subsequently attached to the carrier material by
means of dropwise addition of liquid nonylphenol condensed with 10
moles of ethylene oxide. The granules thus formed were coated by
means of a second layer of the nonionic. These granules were sieved
with a sieve with apertures of 0.5-1 mm and added in an amount of 5
percent to the detergent composition of Example I. Storage tests
were carried out for several weeks at 30.degree.C -- 80 percent
R.H. in laminated and unlaminated carton containers. The residual
enzymatic activity was determined, the results of which are shown
in Table III.
TABLE III
N.degree. of residual activity (in %) granule 1 week 3 weeks 4
weeks 6 weeks 8 weeks not not not not not lam. lam. lam. lam. lam.
lam. lam. lam. lam. lam. 1 37 88 14 59 6 47 0 27 0 15 2 57 109 12
74 6 79 0 66 0 47 3 50 96 10 77 5 72 0 36 0 50 4 37 10 54 5 44 0 25
0 14 5 35 97 12 72 4 51 4 40 0 22 6 26 78 9 56 1 44 0 24 0 9
EXAMPLE III
Several enzyme-containing granules were prepared from granular
pentasodium triphosphate which had a particle size of 50-250 .mu.
and a powdered proteolytic enzyme from Bacillus subtilis, sold
under the trade name Maxatase. The composition of the granules is
given in Table IV.
Granules nos. 1 and 4 were prepared in the following way. Citric
acid was dispersed in tallow fatty alcohol condensed with 25 moles
of ethylene oxide, under heating to 60.degree.C in a homogenisator
for half an hour. The dispersion was a clear liquid, which became
viscous at lower temperatures. This dispersion was heated up and
sprayed on the granular pentasodium triphosphate by means of a
two-fluid nozzle. Subsequently the powdered enzymes were added, and
on the so-obtained granules again the dispersion of citric acid in
the nonionic was sprayed.
Granules nos. 2 and 6 were prepared in an identical way, with the
exception that first solely the tallow fatty alcohol condensed with
25 moles of ethylene oxide was sprayed onto the granular
pentasodium triphosphate, and after addition of the proteolytic
enzyme powders the citric acid nonionic dispersion was sprayed on
the granules so obtained.
Granules nos. 3 and 5 were prepared as follows. On the granular
pentasodium triphosphate first the tallow fatty alcohol condensed
with 25 moles of ethylene oxide was sprayed, followed by the
addition of the dry mixture of the proteolytic enzyme powder and
citric acid, and subsequently again the nonionic was sprayed upon
the granules.
Granule no. 7 was prepared by spraying the nonionic on the granular
pentasodium triphosphate, adding the enzyme powder and again
spraying the nonionic thereupon. Granule no. 7 was made for
comparison purposes. All the granules contained 5 percent nonionic
in the inner and 5 percent nonionic in the outer layer. From each
of these granules, 7.5 percent by weight was added to the detergent
composition as given in Example I, and the residual proteolytic
activity was determined after 7 days' storage of the composition at
30.degree.C and 80 percent relative humidity. The results are also
given in Table IV. ##SPC2##
* * * * *