Note: Descriptions are shown in the official language in which they were submitted.
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C 585 (R)
"Liquid enzymatic detergent composition"
The present invention relates to a stable, aqueous built liquid
enzymatic detergent composition. Aqueous liquid enzymatic detergent
compositions are well-known in the art. The major problem which
is encountered with such compositions is that of ensuring a
sufficient storage-stability of the enzymes in these compositions.
There have already been various proposals for the inclusion of
special stabilizing agents in such liquid enzymatic detergent
compositions, especially unbuilt liquid enzymatic detergents.
In the case of built 1i4uid enzymatic detergent compositions, how-
ever, there is not only the additional problem of the possible
effect of the builder material on the enzymes, but also the effect
of the builder material on the overall physical (storage) stability
of the liquid composition.
It has already been proposed to use a mixture of a polyol and boric
acid or an equivalent thereof in enzymatic liquid detergent compo-
sitions, whereby the ratio of the polyol to the boric acid is smaller
than 1. These mixtures are preferably used in unbuilt liquids.
It has been found that, for built liquids, this ratio should be
greater than 1 if no special measures are taken to keep the pH
of the composition constant, but that the presence of builder
materials do cause a physical stability problem, in that the com-
positions tend to separate into different phases.
According to the invention it has now been found that stable, aqueous,built liquid enzymatic detergent compositions can be obtained by
the inclusion in an aqueous, built liquid enzymatic detergent com-
position of a mixture of a polyol and boric acid or an equivalentthereof in a weight ratio of more than 1, and a particular cross-
linked polymer to be defined more fully hereafter. By using these
three ingredients, a stable, aqueous built enzymatic liquid deter-
gent composition can be obtained, which has a satisfactory enzyme
stability, especially at a higher pH, as well as a satisfactory
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physi CAl storage s-tability.
The invention will now be explained in more detail.
The polyols for use in the present invention contain only C-, H-
and 0-atoms. They are free from other (functional) substituting
atoms such as N-, S- and the like. The polyols should contain at
least 2 hydroxy groups and may contain even up to 6 hydroxy groups.
Typical examples of polyols particularly suitable for use in the
present invention are diols such as 1,2-propanediol, ethylene-
glycol, erythritan, polyols such as glycerol, sorbitol,:nannitol,
~lucose, fructose, lactose, etc.
In general, the polyol is present in an amount of at least 1,
preferably at least 4% by weight of the final composition, up
to 25~ by weight. Preferably the amount ranges from 5-15% by
weight of the final composition.
The boric acid or the boron-equivalent thereof, such as boric oxide,
borax and other alkali metal borates capable of reacting with a
polyol, such as sodium, ortho-, meta- and pyroborates, is used in
an amount such that the weight ratio of the polyol to the boron
compound is more than 1 (calculated on the basis of borax). This
means that the bnron compound is used in an amount that is smaller
than the amount of the polyol. Generally the amount of the polyol
varies from ~ 100-200%, and preferably from > 100-160% by weight
of the boric acid or equivalent thereof (calculated on the basis
of borax).
The cross-linked polymer to be used in the present invention is a
water-soluble polymer of acrylic acid cross-linked with not more
than 10% of a vinyl group-containing cross-linking agent. These
cross-linked polymers are more fully described in French Patent
Specification No. 1,153,560.
Especially suitable are the water-soluble polymers of acrylic
acid, cross-linked with about 1% of a polyallyl ether of sucrose
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having an average of about 5.~ allyl groups for each sucrose mol-
ecule, the polymer having a molecular weight in excess of
1,000,000. Examples of such polymers are Carbopol 934, 940 and
941. Carbopol is the Registered Trademark of B.F.Goodrich Co. Ltd,
the manufacturers of these polymers. The preferred polymer is
Carbopol 941. The cross-linked polymer is used in the present
invention in an amount of 0.1-2.0, preferably 0.25-1.0 and espe-
cially preferably 0.4-0.8% by weight of the total composition.
These cross-linked polymers are normally acidic, and it is essen-
tial that they are present in the final composition in a neutral-
ized form. In this respectit has been found that this neutral-
ization should preferably be carried outin situ; separately neu-
tralized polymer (i.e. by first dispersing the acidic polymer
in water and subsequently adding a suitable base) did not provide
a fully satisfactory stable liquid composition. The neutraliza-
tion in situ is carried out by adding the polymer to an aqueous
medium which contains a suitable alkaline material in a suffi-
cient amount to at least partially, and preferably fully neutral-
ize the polymer. In this respect it has been found that borax is
a particularly suitable alkaline material.
The aqueous liquid compositions in which the stabilizing systems
of the invention are incorporated are aqueous, built, liquid en-
zymatic detergent compositions further comprising as essential
ingredients enzymes, builders and active detergents.
The enzymes to be incorporated can be proteolytic, amylolytic
and cellulolytic enzymes as well as mixtures thereof. They may
be of any suitable origin, such as vegetable, animal, bacterial,
fungal and yeast origin. However, their choice is governed by
several factors such as pH activity and/or stability optima,
thermostability, stability versus active detergents, builders
and so on. In this respect bacterial or fungal enzymes are
preferred, such as bacterial amylases and proteases~ and fungal
cellulases. Although the liquid compositions of the present in-
vention may have a near-neutral pH value, the present invention
is of particular benefit for enzymatic liquid detergents with
a pH of 7.5 or above, especially those incorporating
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bacterial proteases of which the pH-optima lie in the range between
8.0 and 11.0, but it is to be understood that enzymes with a some-
what lower or higher pH-optimum can still be used in the compo-
sitions of the invention, benefiting from it.
Sui-table examples of proteases are the subtilisins which are ob-
tained from particular strains of B. subtilis and B. licheniformis,
such as the commercially available subtilisins Maxatase ~ (ex
Gist-Brocades N.V., Delft, Holland) and Alcalase C?(ex Novo
Industri A/S, Copenhagen, Denmark).
As stated above, the present invention is of particular benefit
for enzymatic liquid detergents incorporating enzymes with pH-
activity and/or stability optima of above 8.0, such as enzymes
also commonly called high-alkaline enzymes.
Particularly suitable is a protease, obtained from a strain of
Bacillus, having maximum activity throughout the pH-range of
8-12, developed and sold by Novo Industri A/S under the registered
trade name Esperase'R~ The preparation of this enzyme and
analogous enzymes is described in British Patent Specification
No. 1,243,784 of Novo.
High-alkaline am~ylases and cellulase can also be used, e.g.
~ -amylases obtained from a special strain of B. licheniformis,
described in more detail in British Patent Specification No.
1,296,839 (Novo).
The enzymes can be incorporated in any suitable form, e.g. as a
granulate (marumes, prills etc.), or as a liquid concentrate.
The granulate form has often advantages.
The amount of enzymes present in the liquid composition may
vary from 0.001 to 10% by weight, and preferably from O.Ol to
5% by weight.
The liquid detergent compositions of the invention furtherrnore
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comprise as essential ingredient an active detergent material, which
may be an alkali metal or alkanol amine soap of a C1o-C24 fatty
acid, including polymerized fatty acids or an anionic, nonionic.
cationic, zwitterionic or amphoteric synthetic detergent material,
or mixtures of any of these.
Examples of anionic synthetic detergents are salts (including
sodium, potassium, ammonium, and substituted ammonium salts such
as mono-, di- and triethanolamine salts) of Cg-C20 alkylbenzene-
sulphonates, C8-C22 primary or secondary alkanesulphonates, C8-C24
olefinsulphonates, sulphonated polycarboxylic acids, prepared by
sulphonation of the pyrolyzed product of alkaline earth metal
citrates, e.g. as described in British Patent Specification No.
1,082,179, C8-C22 alkyl sul phates, C8-C24 alkylpolyglycolether-
sulphates (containing up to 10 moles of ethylene oxides); further
examples are described in "Surface Active Agents and Detergents"
(Vol. I and II) by Schwartz, Perry and Berch.
Examples of nonionic synthetic detergents are the condensation
products of ethylene oxide, propylene oxide and/or butyleneoxide
with C~-C18 alkylphenols, C8-C18 primary or secondary aliphatic
alcohols, C8-C18 fatty acid amides; further examples of nonionics
include tertiary amine oxides with one C8-C18 alkyl chain and two
C1 3 alkyl chains. The above reference also describes further
examples of nonionics.
The average numb~r of moles of ethylene oxide and/or propylene
oxide present in the above nonionics varies from 1-30; mixtures
of various nonionics, including mixtures of nonionics with a lower
and a higher degree of alkoxylation, may also be used.
Examples of cationic detergents are the quaternary ammonium com-
pounds such as alkyldimethylammonium halogenides, but such
cationics are less preferred for inclusion in enzymatic detergent
compositions.
Examples of amphoteric or zwitterionic detergents are N-alkylamino
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acids, sulphobetaines, condensation products of fatty acids with
protein hydrolysates, but owing to their relatively hight costs
they are usually used in combination with an anionic or a nonion-
ic detergent. Mixtures of the various types of active detergents
may also be used, and preference is given to mixtures of an an-
ionic and a nonionic detergent active. Soaps (in the form of
their sodium, potassium, and substituted ammonium salts such as
of polymeri~ed fatty acids, may also be used, preferably in con-
junction with an anionic and/or a nonionic synthetic detergent.
The amount of the active detergent material varies from 1 to 60%,
preferably from 2-40 and especially preferably from 5-25%; when
mixtures of e.g. anionics and nonionics are used, the relative
weight ratio varies from 10:1 to 1:10, preferably from 6:1 to
1:6. When a soap is also incorporated, the amount thereof is from
1-40% by weight.
The liquid compositions of the invention further contain up to
60% of a suitable builder, such as sodium, potassium and ammonium
or substîtuted ammonium pyro- and tripolyphosphates, -ethylene-
diamine tetraacetates, -nitrilotriacetates, -etherpolycarboxyl-
ates, -citrates, -carbonates, -orthophosphates, zeolites, car-
boxymethyloxysuccinate, etc. Particularly preferred are the
polyphosphate builder salts, nitrilotriacetates, zeolites, and
mixtures thereof. In general the builders are present in an
amount of 1-60, preferably 5~50% by weight of the final compo-
sition.
The amount of water present in the detergent compositions of the
invention varies from 5 to 70% by weight.
Other conventional materials may also be present in the liquid
detergent compositions of the invention, for example soil-sus-
pending agents, hydrotropes, corrosion inhibitors, dyes, per-
fumes, silica-tes, optical brighteners, suds boosters, suds de-
pressants such as silicones, germicides, anti-tarnishing agents,
opacifiers, fabric softening ayents, oxygen-liberating bleaches
such as hydrogen peroxide, sodium perborate or percarbonate,
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diperisophthalic anhydride, with or without bleach precursors,
reducing bleaches such as sodium sulphite, buffers and the like.
The pH of the final composition is near neutral, preferably high-
er than 7.5 and should preferably lie within the range of 8.0 to
10.0, and is, if necessary, buffered to a value within that range
by addition of a suitable buffer system. The pH of the wash li-
quor, when using the composition, is about 1 pH unit higher than
the above values at an in-use concentration of about 1%.
The invention will now be further illustrated by way of Example.
In the Examples the percentages are by weight. In all the Examples
the polyrner was added in an acidic form to the aqueous medium
from which the liquid detergent composition was obtained, said
medium already contalning a sufficient amount of a suitable alka-
line material for neutralization of the polymer.
Exam~
lhe following composition was prepared:
%
potassiurn dodecylbenzene sulphonate 10
C -C linear primary alcohol, condensed
13 15 with 7 moles of ethyleneoxide 5
sodium tripolyphosphate 20
borax 10
glycerol 15
Carbopol 941 0,65
enzyme (Maxatase ~ in the form of a slurry) 0.3
fluorescer and perfume 0.25
water to 100.0
The pH of this product was 8.0-8.5; the pH rose to 9.0 - 9.5 at
an in-use concentration of about 1,o. The physical storage stabil-
ity after storing for more than 1 month at room temperature and
at 37C was quite acceptable for practical purposes. The enzyme
stability after storing for 1 month at room temperature and at
37C was abt. 80% (residual activity), respectively 90% (resid-
ual activity), and the breakdown of the sodium tripolyphosphate
was 15%, respectively 0- 5% under these conditions.
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Example 2
The following compositions were prepared:
a b c d e f g
sodium dodecylbenzene sulphonate - - - - 7.5 5 5
C -C 5 linear prim. alcohol, con-
de3nse~ with 7 moles of alkylene
oxide (a mixture of ethylene- and
propylene oxide in a weight ratio
of 92:8) 10 10 10 10 2.5 5 5
anhydrous sodium tripolyphosphate 20 20 20 20 20 20 20
sorbitol - - - - - - 6
glycerol - 10 20 10 10 10
borax 7 7 7 7 7 7 7
Na20.3.3SiO2 - - - 2.7
Carbopol 941 0.8 0.8 0.8 0.8 0.65 0.7 0.7
enzyme (Alcalase or Esperase)~
water balance
pH 8.5 7.4 6.7 7.7 7.5 7.5 7.5
half-life time of enzymes (in days)
at 37 C
Alcalase 2 55 80 50 100 90 12
Esperase 3 55 140 60 10 40 4
The enzyme was added in such an amount that the final product
had a proteolytic activity of 8.5 GU,~mg (733 GU/mg = 1 Anson
Unit/g)
The compositions were stable for several months at room tempera-
ture.
Example 3
The following composition was prepared:
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_t.%
sodium dodecylbenzene sulphonate 6
C12-C1 linear prim. alcohol condensed with
59 moles of ethylene oxide 3
sodium oleate
sodium citrate 2.aq 7
zeolite (type 4A) 28
sodium carboxymethylrellulose 0.5
borax 7-5
Carbopol 941 0.2
fluorescer 0.1
glycerol 7.5 or 10
water balance
enzyme (Alcalase) (as in Example 2)
These liquids were physically stable; the half-life time at 37C
of the enzymes was 10 days with 7.5% glycerol and 11 days with
10% glycerol.
Example 4
The following composition was prepared:
wt. o/o
sodium dodecylbenzene sulphonate 5
C1 -C linear prim. alcohol condensed with
3 15 7 moles of alkylene oxide (a mixture
of ethylene- and propylene oxide in
a weight ratio of 92:8) 2
anhydrous sodium tripolyphosphate 20
glycerol 10
borax 7
sodium sulphite 5
sodiunn carboxymethylcellulose 0.4
fluorescer 0.1
Carbopol 941 0.5
Alcalase (1163 glycine units/mg) 0.7
silicon oil 0.25
water balance
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The enzyme had a half-life time of 4 months at 37C, and the
product was physically stable still after Z months at 3, 23,
37 and 52C.
