Note: Descriptions are shown in the official language in which they were submitted.
11~0064
l,ackgrourld Or the invention
Field Or the invention
______________________
The present invention relates to particulate enzyme
preparations, which consist of solid spheronized particles,
also called "marumes".
Descri~tion of the ~rior art
______ ____________ ________
Enzyme-containing marumes are well-known. These marumes are
solid granules containing enzymes homogeneously distributed
therethrough, and are usually prepared by extruding a mix-
ture of enzymes and organic or inorganic extrudable material,
to form an extrudate, and subsequently spheronizing said
extrudate by tangential forces in an apparatus which com-
prises a cylinder with a smooth wall having positioned
therein a roughened, horizontal rotatable table.
The extrudate, for example noodles, is fed into this
apparatus, and by the centrifugal forces exerted upon the
noodles by the rotation of the table, the noodles are
; transformed into spheronized granules, called marumes.
The apparatus is known in the art under the registered
~arK
B 20 trade n~me "Marumerizer", manufactured by Fuji Paudal KK,
Japan. The apparatus is more fully described in German Patent
Specification 1,294,351 and US Patent Specification
3,277,520.
Enzyme rnarumes and their method Or preparation have
been described in UK Patent Specification 1,362,365 (Novo)
and US Patent Specification 3,775,331 (Borrello). According to UK
Patent Specification 1,362,365, the extrudate is prepared
from enzyme powder which may contain lubricating agents,
2 ~
~ IJIJ~
11~006g
I`illers, ~)irlding agcnts or enzyme-stabili2ing agents. The
fillers are inorganic salts, such as sodium sulphate, sodium
chloride, sodiumtripolyphosphate, or organic materials such
as cellulose powder, starch, gelatin, casein,etc. However,
according to the examples, the extrudates are made from
mixtures of enzyme powder and a predominantly inorganic ex-
trudable material, such as the inorganic salts.
Although such marumes have satisfactory properties as
regards enzyme stability, and storage stability in detergent
powders, they may give rise to a dusting problem on handling
these marumes. Their core is relatively hard, and when they
are spiit during handling they crush under pressure (e.g.
when they are walked on or driven over on the factory floor),
which results in an undesirable formation of dust particles.
According to US Patent Specification 3,775,331 (Borrello)
enzyme marumes are prepared from an extrudate which has
been made from a mixture of enzymes and a synthetic deter-
gent-active material. The extrudate further contains inor-
ganic salts, which form the cores for the enzymes and the
synthetic detergents in the preparation of these marumes.
These marumes may also suffer from the above-mentioned
drawback as regards dust formation when crushed under
pressure.
Summary of the invention
It is therefore an object Or the present invention
to provide enzyme marumes which do not yield said unde-
sirable dust formation when they are crushed under pressure.
It has now been round that these drawbacks are sig-
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nificantly reduced, when the marumes are prepared from an
extrudate which has been made from a mixture of enzymes and
a potassium fatty acid soap.
The invention therefore relates to enzyme marumes
essentially comprising enzymes and a potassium fatty acid
soap, as well as to a method for preparing these.
Description of the preferred embodiments
The potassium fatty acid soaps to be used in the present
invention are potassium salts of saturated or unsaturated
C10-Cl8 fatty acids, i.e. aliphatic monocarboxylic acids
containing from 9-17 carbon atoms in their alkyl chain.
They may be natural or synthetic fatty acids, and may have
7-' some degree of branching. Typical examples of suitable fatty
acids are capric, undecylic, lauric, tridecylic, myristic,
pentadecylic, palmitic, margaric and stearic acid, as well
as decenoic, dodecenoic, tetradecenoic, hexadecenoic and
oleic acid.The potassium soaps should have a sufficient
rate of solution, and it has been found that the potassium
soaps of coconut fatty acids, i.e. fatty acids obtained from
coconut oil by hydrolysis thereof, predominantly consisting
of lauric and myristic acid, with a small amount of oleic
acid, are particularly suitable in the present invention.
It has furthermore been found that the marumes, in
order to contain a sufficiently plastic core~ should pref-
erably further contain a plasticizing agent. Suitable
plasticizing agents are polyethylene glycols with an average
molecular weight of 200-1200, glycol, fatty acid glycerides,
C10-Cl8 fatty acids, waxes, lanolin and the like. It has
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been found, however, that a superfatted potassium C10-Cl8
fatty acid soap is particularly suitable for the purposes
of the present invention. Such a superfatted soap can be
obtained by adding a free C10-Cl8 fatty acid to the potassium
soap, or by not fully neutralizing the C10-cl8 fatty acids
with a suitable potassium-containing neutralizing agent, or
by forming some free fatty acid in the potassium fatty acid
soap by adding some acid thereto, such as phosphoric or
citric acid. A preferred superfatting agent is coconut
fatty acids. In general the superfatted soap contains from
0.5-10% by weight of the free fatty acids as superfatting
agents.
In the preparation of the mar~es of the present
invention, it is essential that the mixture from which the
extrudate is formed, or the extrudate itself, contains
water, which functions as a lubricating agent. This water,
if not already sufficiently present in the raw materials
from which the mixture is made, is either added to the
mixture to be extruded or to the extrudate before or
during the marumerizing operation, and is subsequently
driven off by suitable means, such as drying or aeration.
The marumes of the present invention may further contain
other usual ingredients, such as colouring agents, whitening
agents, enzyme stabilising agents, binding agents, hydro-
tropes and the like. They may further be coated with a
coating layer of a suitable material, such as nonionic sur-
face-active agents, polyethylene glycols of an average
molecular weight of 1200-3600, cellulose derivatives, fatty
4 C 3 ~ L ~ ~ )
acid esters, mineral oils, waxes, resins, film-forming
copolyrners etc.
The enzymes which may be incorporated in t~e marumes
o~ the present invention may be proteases, amylases, lipases,
5 and cellulases and mixtures thereof. Although such enzymes
may be of vegetable or animal origin, they are preferably
of bacterial or fungal origin.
Suitable examples of proteases are the subtilisin
(~-4-~
protease~, obtained by submerged fermentation with strains
of B. subtilis, such as Alcalase ~ and Esperase ~ ex Novo
Industri, Denmark, Maxatase ~ ex Gist-Brocades, Holland.
Suitable examples of amylases are bacterial ~-amylases~3
obtained from B. subtilis strains such as Thermamyl ~
ex Novo Industri, Maxamyl ~ ex Gist-Brocades. Suitable
(3-ll3~
lipases~ are obtained from Candida lipolytica or Candida
cylindracea, from strains of Pseudomonas such as Ps.
stutzeri. Commercial lipases are e.g. Lipase My 10,000
(3~4~4)
(from Cand. cyl.) ex Meito Sangyo Co. Suitable cellulase~
are those obta;ned from strains ofTrichoderma, from Asper-
gillus oryzae, Aspergillus niger, from Streptomycetes and
Hymenomycetes. A commercially available cellulase is
Meicelase~ (from Trichoderma) ex Meiji Seika Kaisha, Japan
and Enzyme 19 AF ex Rohm and Haas (from Asp. niger).
If necessary, the enzyme maru~emay contain pH-ad-
justing agents to provide the pH-value suitable for activity/
stability of the enzyme present in the marume.
The marumes of the present invention may furthermore
be coated with a suitable dusting agent, such as finely
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divided organic or inorganic materials, such as anhydrous
sodiumsulphate, silica, calciumsulphate, magnesia, magnesium
carbonate and magnesium silicate, aluminiumsilicate or mix-
tures of these materials.
In general, the enzyme marume of the present invention
comprises from 60-90% by weight of the potassium fatty
acid soap, from 0.5-10% by weight of a plasticizing agent
as described above and from 5 to 20% by weight of enzymes
as described above. Preferably they further contain from
0.5-5% of a whitening agent such as titanium dioxide, from
0.5-10~ of a coating material as described above, and from
0.5-5% of a dusting agent as described above. In preparing
the marumes of the present invention, water should be
present at some stage before the marumes are ultimately
obtained. The amount of water present or added is from 1.0
to 8.o% by weight.
The marumes are prepared by homogeneously mixing the
enzymes (either as powder or as a liquid concentrate) with
the potassium fatty acid soap, extruding said mixture through
an extrusion plate to fGrm noodles, and subsequently charging
the noodles in a marumerizing apparatus. Water is added
either before or after extrusion, and is subseouently driven
off during or after the marumerizing step.
The plasticizing agent is added before extrusion, as
are the various ingredients desirably present in the
rnarumes, such as titanium dioxide, enzyme-stabilizing
agents, pH-adjusting agents and so on. The marumes may
be coated with a coating material and~or a dusting powder,
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either during the marumerizing operation or thereafter.
The Marumes of the invention are particularly suitable
for incorporation in powdered detergent compositions. They
have a satisfactory storage stability therein, and their
tendency to form dust on crushing under pressure is sig-
nificantly reduced. The detergent compositions, in which
the enzyme marumes may be incorporated, generally in an
amount of 0.5 to 7.5% by weight, comprise an active deter-
gent material which is an anionic, nonionic, cationic or
zwitterionic detergent surfactant or soap or mixture there-
of, and builder salts, bleaching agents, soil-suspending
agents, lather boosters, hydrotropes, alkaline materials,
; perfumes, colouring agents, bactericides and so on. Such
detergent compositions are well-known in the art.
The invention will now further be illustrated by
' way of example.
! Example I
The fcllowing ingredients:
2.785 kg potassium coconut soap (containing 3-5% water),
¦ 20 0.635 kg proteolytic enzyme, obtained by submerged J
B fermentation of a strain of B. subtilis~, known
! under the registered Trade Mark Or Alcalase ~,
~ sold by Novo Industri A/S, Copenhagen, Denmark,
j having an activity of abt 10 Anson units/g,
0.420 kg coconut fatty acids,
0.170 kg citric acid,
were mixed in a small Erweka mixer for 5 minutes, and
~, this mixture was subsequently extruded through an extrusion
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plate into noodles. 1.5 kg of these noodles were then
spheronized in a batch marumerizer at a temperature of about
40C. After 2 minutes marumes were formed, and the
marumerizer was discharged.
These marumes were tested for storage stability, and
were also subjected to a crushing test. This crushing test
was carried out as follows:
In a small drum, diameter 21.5 cm, length 16.5 cm,
open at one side, 5 grammes of the marumes were added. In
the drum a massive cylinder, diameter 11.3 cm, weight
10.7 kg, is placed, and the drum is rotated at a speed
of 16 rpm. for 5 minutes. This whole apparatus is placed
in front of a continuous dust monitor just before the
air-inlet opening, which is funnel-shaped. In this way all
the air around the rotating drum is sucked through the
monitor at a speed of 0.2-0.3 m/sec., and the enzymatic
activity of the dust collected is measured in glycine
j units per cubic meter.
The results of these tests are given in Table I
below.
j Example II
! The fo]lowing ingredients:
40.0 kg potassium coconut soap,
7.0 kg Alcalase ~ (activity 8 Anson units/g ),
1.5 kg coconut fatty acids,
1.5 kg titanium oxide,
2.0 kg water,
were mixed in a Lodige mixer for 2 minutes, and the mixture
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was then formed into noodles on a pelletizer. These noodles
were then continuously fed through two marumerizers in
cascade at a speed of abt.20 kg/hr into a sieving machine.
About 45 kg of marumes were obtained of the required size.
These marumes were also tested for storage stability
~- and crushing effects.
; The marumes of Examples I and II were also compared with
other enzyme encapsulates, such as common marumes, prills
and speckles.
Table I
Residual enzymatic Crushing
activity after 4 test in
weeks accelerated GU/m3
stora~e (in %)
Commerical marumes (1.0 AU/g) 90 > 200
Commercial marumes (1.5 AU/g) 91 > 200
Enzyme speckles 70 < 5
Enzyme prills 95 > 250
Marumes of Example I 95 < 5
Marumes of Example II 95 ' 5
These results show that the marumes of the invention
have an excellent storage stability and do not yield any
significant dusting on crushing.
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