Note: Descriptions are shown in the official language in which they were submitted.
-- 2~39~0
C 3370 (R)
PRo~T~ FR pR~l~RTNG T TOUID EN~YMATIC DETERGENT COMPOSITIONS
5 TEo~NTçAI FT~T n
This invention relates to a process for preparing liquid
enzymatic detergent compositions and to their use, especially
for example as laundry detergents.
10 I~P.ÇKGROUND AND PRIOR ART
It is well known to prepare detergent compositions in the
form of a liquid concentrate to be diluted to give an aqueous
wash liquor. Such liquid concentrates can themselves be
prepared in the form either of an aqueous or a non-aqueous
15 liquid, and both f orms are known .
It is also known to add enzymes to a variety of detergent
compositions, especially laundry detergents. The most common
enzyme for this purpose is protease, e.g. subtilisin, and
20 others, e.g. amylase, c~ qe~ lipase, have also been used.
Such enzymes are presented in a variety of forms: as solid
compositions, such as marumes or granulates, e.g. multilayer
composite granulates, or as powder concentrates; or as liquid
25 compositions such as slurries or stabilized aqueous
preparations. The manufacture of stabilized aqueous and some
non-aqueous enzyme concentrates is described for example in
US-A-4 497 897 (Novo) and DE-A-29 37 012 (Henkel). Enzyme
slurries are mentioned for example, along with preparations
30 made up as aqueous (propanediol-water) concentrates, in a
bLuull~lLe 'Novo Enzymes for Household Non-Built Liquid
Detergents ', which gives some formulations of aqueous enzyme
concentrates incorporated into a non-built aqueous detergent
composition .
Existing aqueous enzymatic liquid laundry detergents are
commonly formulated using as additive a stabilized aqueous
liquid enzyme concentrate. Considerable efforts have been A
203~3~
2 C 3370 (R)
devoted to the stabilization of enzymes in aqueous liquid
detergent compositions, which represent a medium that is
problematical for the preservation of enzyme activity during
storage and distribution.
In his article in Tenside 27(1), p.30 (1990), G. Jensen
describes the difficulty of formulating built liquid
detergent compositions comprising proteolytic enzymes. Such
products are said to require a special type of enzyme in
10 order to obtain a satisfactory storage stability. The normal
liquid enzymes ( i . e . aqueous concentrates and nonaqueous
slurries) are loosing their activity too fast due to
dellal ul~lt.ion of enzyme protein structure by the ~lkAl ;n~
ingredients and sequestering agent present in the
15 composition. To solve this problem, the author believes it is
nP~ c;lry to use a protected enzyme system comprising a
dispersion of the enzyme in a silicone matrix, so-called
silicone slurries. An example is given of a liquid detergent
product comprising a phosphate-builder and a proteolytic
20 enzyme in the form of a slurry, which indeed shows a poor
enzyme stabi l ity .
US-A-4 090 973 (Procter & Gamble) describes aqueous liquid
detergents containing normally-unstable components
25 .on~ArS711 Ated in water-soluble normally-solid alkoxylated
nonionic surfactants and/or polyethylene glycol.
EP-A-238 216 and GB-A-2 186 884 (Albright & Wilson and Novo
Industri) describe protected enzyme systems for use (inter
30 alia) in liquid detergent compositions, based on dispersing
the enzymes in hydrophobic substances (e.g. petroleum jelly
or organosiloxane polymer) which do not dissolve on storage
and which are liquid under the conditions of use, thus
providing a discontinuous phase in the f inal liquid
3 5 detergent .
EP-A-351 162 (Albright & Wilson and Novo-Nordisk) describes
stAhi l i 7~d aqueous enzyme dispersions obtained by
. ~ 2~3~30
3 C 3370 (R)
(eo) preeipitating water-soluble polymer and enzyme from
water .
JP-A-47-35192 describes the use of glycerol or sorbitol with
5 borax under eertain eonditions and proportions, to stabilize
enzyme preparations including liquid washing materials.
DE-A-2 728 211 (Unilever) describes the use of polyols
eontaining 2 to 6 hydroxy groups together with borie acid or
10 borate in ratios less than 1, particularly in unbuilt
detergents .
GB-A-2 079 305 (Unilever) describes the use of polyols
together with boric acid and/or borate and polyacrylate
15 polymers as etabilizing agents, while EP-A-080 223 (Unilever)
describes the eombined use of boric acid or borate and polyol
or polyamino eompounds with reducing salts, and EP-A-126 505
(Unilever) describes the use of boric acid or borate and
redueing salts, together with succinic or other dicarboxylic
20 acids.
other prior art, e.g EP-A-028 $65 and EP-A-028 866 (Procter &
Gamble), and US-A-4 111 855 (Procter & Gamble), discloses use
of further stabilizers, such as calcium with short-chain
25 ~liphatie aeids such as formate or acetate, and ethanol.
Nevertheless, problems remain. Several of the published
techniques give a guantitative i ~ v ~t of enzyme
stability in aqueous liquid detergents. Some of them call for
30 stabilizing ingredients and additives which are expensive, or
which represent possibly undesirable additions from the point
of view of their effects on other components of the
compositions, or which are less desirable from an
environmental point of view. Therefore it remains desirable
35 to find further terhn;5[u~q for stabilizing enzymes in li~uid
detergent compositions, whieh might for example be usefully
eombinable with existing techniques so as to give increased
effect, as well as able to be used alone without also using
2~3~6~
4 C 3370 (R)
previously-known technique. It is also desirable to find such
techniques which present the advantage of not requiring such
costly additives as the existing techniques. The present
invention seeks to provide such advantages.
It has now surpri~ingly been found that improved stability of
en2yme can be achieved in ~queous liquid detergent
concentr~tes when the enzyme is added to the formulation as a
slurry of the enzyme in a nonionic detergent which is
10 normally liquid.
DEli INITION OF TTr~ INVENTION
According to a first aspect, the invention provides a process
for preparing an aqueous liquid enzymatic detergent
15 composition comprising a detergent active compound, a non-
phosphate builder and an enzyme, wherein the enzyme is added
in the form of a slurry of the enzyme in liquid nonionic
surfactant .
20 The invention also provides an aqueous liquid enzymatic
detergent composition prepared by the process of the
invention .
25 DES~2TPTION OF THE TNVFNTION
' Detergent concentrate ' and ' surf actant concentrate ' as used
herein, do not refer to normally-encountered aqueous wash
liquors themselves, but rather refer to surfactant
preparations sufficiently concentrated that they can be
30 diluted in a large ratio (water to detergent concentrate),
e.g. 15:1 or more, preferably 100:1 or more, to provide a
useful aqueous wash liquor.
The enzyme slurry contains the enzyme in the dispersed form
35 of e.g. powder or particles ~ p~n~ cl in a non-aqueous
(nonionic) liquid surfactant, especially one which is
substantially anhydrous. The enzyme particles may for example
be spray-dried or lyophilized, and can for example be milled
2039~30
C 3370 (F~)
after spray-drying and before dispersion in (e.g. anhydrous)
nonionic liquid detergent. Alternatively, they may be milled
a3~ter dispersing the enzyme in the nonionic detergent.
5 The enzyme level in the slurry can be from about 0. 5 to about
50~6 by weight, e.g. from about 1 to about 2096 by weight.
Commonly the enzyme slurry which is used in the manufacture
oe the compositions Or the present invention is
substantially anhydrous, with water content less than about
10 10~6, preferably less than about 596 w/w, sometimes less than
about 196. Using this slurry technique it is possible to use
a practically anhydrous liquid nonionic surfactant as the
continuous phase of the slurry. The liquid state of the
slurry enables a thorough mixing of the enzyme in the f inal
15 liquid detergent, and allows easy liberation of the enzyme
~fter dilution of the liquid detergent in the wash liquor.
The enzymes to be incorporated into a slurry for use in
making the compositions of the present invention may be
20 either crude preparations, or partly purified, decolourised,
or extensively purif ied preparations. They may be (and
preferably are) dried in any of the usual manners known per
se, before slurrying the enzyme in the liquid nonionic
surfactant. Examples of suitable purification methods for
25 this purpose include: micro-f iltration, high-salt
precipitation of the enzyme, e.g. from sodium or ammonium
sulphate solutions, or solvent precipitation by adding
water-miscible organic solvents (e.g. acetone or ethanol) to
aqueous enzyme preparations at any of various stages of their
30 isolation or purification. The compositions may contain
either crude or purified enzyme, e.g. enzyme free of cell
wall material as described in for example EP-A-322 082
(Gist-Brocades) .
35 Before slurrying, the enzyme preparation can be decolourised,
e.g. by the methods described in JP-A-63 11967~ (Lion Corp).
The enzyme may be crystallized before slurrying by adding
halide salts to a concentrated enzyme solution, thus
6 2039630 c 3370 (R)
resulting in the formation of microcrystalline enzyme
particles, e.g. as described in W0 89/08703 (Genencor). The
enzyme composition may be dried by lyophilization or
spray-drying, or by using a fluidised bed as detailed in DE-
5 A-2 134 555 (Novo) .
In practice it can happen that certain preparations of enzyme
have relatively high concentrations of salt, especially
calcium salt, e.g. calcium sulphate or chloride, associated
10 with them. It is preferred for certain purposes to avoid high
salt concentrations, especially of calcium. If calcium is
present, it is preferably at levels less than 4% w/w of the
slurry, more preferably less than 1% or 0.5%, most preferab~y
at trace levels.
In certain embodiments, neqatively-charged polymers, such as
hetero-polysaccharides including glucuronide and/or
galacturonide residues, can help storage stability of the
enzymes slurried in the manner described herein. Such
20 polysaccharides may for example include material produced by
tlle organisms from which the enzymes themselVeS have been
produced, and may remain as contaminants in the partially
purified enzyme preparations, or they may be added
separately, before spray-drying, e.g. in amounts up to about
25 1 to 5% by weight of the slurry, e.g. in amounts comparable
with those of the enzymes themselves.
It is not known why the results of adding enzyme in the form
of a slurry should contrast with the results obtainable when
30 the enzyme is added either as a powder concentrate or granule
or as a stabilized agueous liquid. The technique surprisingly
leads to improved stability in the final aqueous composition.
Thus, the invention opens the way to stabilization without
such expensive additives as normally used, and to improving
35 the stability obtainable by the use of other additives.
7 2039630 C 3370 (R)
A suitable example of an enzymatic slurry preparation for use
in the present invention is a preparation of Savinase (Trade
Mar3c - subtilisin protease, ex Novo-Nordisk) suspended in
liquid Tergitol 15-S-9 (Trade Mark, ex Union Carbide)
5 nonionic detergent consisting sUbstantially of Cll-C15
secondary alcohol condensed with 9 moles of ethylene oxide.
The liquid nonionic detergent of the slurry can otherwise be
for example a liquid secondary or primary linear alcohol
10 having 9 to 20 carbon atoms and r onr~Pr~cPr~l with about 3 to 20
moles/mole ethylene oxide, or may be a mixture of nonionic
surfactants. Alternatively the liquid nonionic surfactant can
be chosen from among the liquid surfactants described in
"Surface Active Agents" Vol. 1, by Schwartz & Perry,
(Interscience 1949), Vol. 2 by Schwartz, Perry & Berch,
(Interscience 1958), or in the current edition of
"McCutcheon's Emulsifiers and Detergents" published by
Manufacturing Confectioners Company or in
"Tenside-Taschenbuch", H. Stache, 2nd Edn. (Carl Hanser
20 Verlag, 19~1~, and can comprise nonionic surfactant chosen
from among the groups and examples of nonionic surfactants
mentioned in EP-A-346 995.
~he aqueous liquid enzymatic detergent compositions prepared
25 according to the present invention can for example include
protease, lipase, amylase, and/or cellulase enzyme(s).
Protease is still the most common enzyme specificity present
in laundry detergents. Most often, protease and/or a lipase
are used optionally with a further enzyme, e.g. an enzyme
30 selected from lipase, amylase, cellulase and oxidase. It has
been found (surprisingly in view of the known adverse effect
of proteases on other enzymes in aqueous conditions) that
both the protease and optional other enzymes present can be
stabilized together in these compositions.
Where at least one enzyme is added in accordance with the
present invention as a slurry in liquid nonionic detergent,
X
~ 3~3~
8 C 3370 (R)
it is within the scope of the invention to add at least one
further enzyme in either a similar or a different form, e.g.
as a liquid or a granular composition of enzyme with carrier
material (e.g. as described for the case of lipase in EP-A-
5 258 068, but applicable to other enzymes also, and as suchcomposition6 are concretely represented e. g . by the Savinase
and Lipolase products of Novo).
Protease can for example be used in an amount ranging from
10 about the order of 0 . 0002 to about the order of O . 05 Anson
units per gram of the detergent composition. Expressed in
other units, the protease can also be included in the
compositions in amounts of the order of from about 1 to 100
GUfmg detergent formulation. Preferably, the amount ranges
15 from 2 to 50 and particularly preferably from 5 to 20 GU/mg.
A GU iG a Glycine Unit, defined as the proteolytic enzyme
activity which, under Gtandard conditionG, during a
15-minute-incubation at 4 0C, with N-acetyl caGein aG
20 Gubstrate, produces an amount of NH2-group equivalent to 1
micromole of glycine.
Preferred exampleG of protease enzyme to be uGed in the
present compositions are the subtilisin varieties sold as
25 SavinaGe (TM of Novo-Nordisk A/S) or Maxacal (TM of
Gist-Brocades/IBIS) or as Opticlean (ex Solvay Enzymes) or
Biosam (ex Showa Denko), which have an isoelectric point (pI)
of approximately 10. Other useful examples of proteaGe
include Maxatase, Esperase, Alcalase (Trade 3!qarks),
30 proteinase K and subtilisin BPN'.
Where the compositions comprise lipase enzyme, there can be
uGed for example an amount in the range 50 to 30, 000 (LU)
lipase unitG per gram of the Gurfactant syGtem or of the
35 detergent compoGition. In thiG specification lipase units are
defined as they are in EP-A-258 068 (Novo).
9~3~
9 C 3370 (R)
There is, as is known, a tendency for lipase to be less
stable in the presence of protease than in the absence of
protease, however, in the presence of protease that is
incorpor~ted into the aqueous liquid detergent as a slurry in
5 liquid nonionic surfactant we obserYe that there is a
relative stabilization effect on the lipase also present
(e. g. when such lipase is incorporated as a stabilized
aqueous liquid preparation). Alternatively, i u~, -nt in
stability Or lipase in the presence of protease is achievable
10 by adding the lipase as a slurry in liquid nonionic
detergent, and the protease here may be added e . g . as another
slurry in liquid nonionic detergent or even in this case as
~n aqueous liquid composition. Good results as to enzyme
stability during storage are also obtainable where both
15 enzymes (if more than one) are added as slurries in liquid
nonionic detergent, either as separate slurries or as an
enzyme mixture dispersed in one type of nonionic surfactant.
The added amount of lipolytic enzyme can be chosen within
20 wide limits, for example 50 to 30, 000 LU/g of detergent
composition, e.g. often at least 100 LU/g, very usefully at
least 500 LU/g, sometimes preferably above 1000, above 2000
LU/g or above 4000 LU/g or more, thus very often within the
range 50-4000 LU/g and possibly within the range 200-1000
25 LU/g.
The lipolytic enzyme can be chosen from among a wide range of
lipases: in particular the lipases described in for example
the following patent specifications, EP-A-214 761 (Novo), EP-
30 A-258 068 (Novo), and EP-A-305 216 (Novo), and especially
lipases showing immunological cross-reactivity with antisera
raised against lipase from lrh. y~es lanuginosus ATCC
22070, EP-A-205 208 (Unilever) and EP-A-206 390 (Unilever),
and especially lipases showing immunological cross-reactivity
35 with antisera raised against lipase from Chromobacter
viscosum var lipolyticum NRRL B-3673, or against lipase from
Alcaligenes PL-679, ATCC 31371 and FERM-P 3783, also the
lipases described in specifications W0 87/00859
" ~ 2~3~63~
C 3370 (R)
(Gist-Brocades), W0 89/09263 (Gist-8rocades), EP-A-331 376
(Amano), DE-A-3 908 131 (Toyo Jozo) and EP-A-204 284
(Sapporo Breweries). Suitable in particular are for example
the following commercially available lipase preparations:
5 Novo Lipolase, Amano lipases CE, P, B, AP, M-AP, AML, and
CES, and Meito lipases MY-30, 0~, and PL, also esterase MM,
Lipozym, SP225, SP285, Saiken lipase, Enzeco lipase, Toyo
Jozo lipase and Diosynth lipase (Trade Marks).
10 Similar considerations ~pply mutatis mutandis in the case of
the other enzymes. Without limitation: Amylase can for
example be used when present in an amount in the range about
1 to about 100 MU (maltose units) per gram of detergent
composition, (or 0.014-1.4, e.g. 0.07-0.7, KNU/G (Novo
15 unlts) ) . A preferred form of amylase is that sold as
Termamyl (TM of Novo), or as Maxamyl (TM of Gist-Brocades).
Cellulase can for example be used when present in an amount
in the range about 0 . 3 to about 35 CEW units per gram of the
20 detergent composition. Preferred forms of cellulase are
Celluzyme (TM of Novo) or KAC500 (TM of Kao).
Genetic engineering of any of the above-mentioned enzymes can
be achieved e.g. by extraction of an appropriate gene, and
25 introduction and expression of the gene or derivative thereof
in a suitable producer organism.
EP-A-130 756 (Genentech), EP-A-214 435 (Henkel), W0 87/04461
(Amgen), W0 87/05050 (Genex), EP-A-405 901 (Unilever) and EP-
30 A-303 761 (Genentech) describe useful modified subtilisin
proteases . Useful modif ied lipase enzymes are also described
in for example W0 89-09263 (Gist-Brocades), EP-A-218 272
(Gist-Brocades), EP-A-258 068 (Novo), EP-A-407 225 (Unilever)
and EP-A-305 216 (Novo).
Typically, the present a~laueous liquid detergent compositions
comprise from 1-70%, e.g. up to 60%, often in the range of 5%
up to 50%, commonly at least 10% and up to 45%, by weight of
2039630
11 C 3370 (R)
one or more detergent-active, ,~ ds, from 5-605c by weight
of one or more organic and/or inorganic non-phosphate
builders, and optionally other conventional ingredients such
as enzyme stabilizers, soil-suspending agents, I.ydL.,~L~.~es,
5 corrosion inhibitors, dyes, perfumes, silicates, optical
Ibrighteners, suds depressants, germicides, anti-tarnishing
agents, opacifiers, fabric softening agents,
oxygen-liberating bleaches such as hydrogen peroxide or
sodium perborate, diperisophthalic anhydride, with or without
lO bleach precursors, oxygen-activating bleaches, buffers and
the like.
The detergent-active compounds in the compositions can for
example be anionic and/or nonionic surfactants, and the pH of
15 the liquid detergent compositions can be chosen at will from
a wide range, e.g. from about pH 7 to about pH 12, e.g. a
milder alkaline range from about pH 7.5 to about pH 9.5 or a
stronger alkaline range from about pH 9 to about pH 11 or
more .
In general, the surfactant(s~ of the present compositions may
be chosen from the surfactants described "Surface Active
Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol.
2 by Schwartz, Perry & Berch, Interscience 1958, in the
25 current edition of "McCutcheon's Emulsifiers and Detergents"
published by Manufacturing Confectioners Company or in
"Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hanser
Verlag, 1981. In this respect anionic and nonionic
surfactants are especially suitable, in particular the groups
30 and examples of anionic and nonionic surfactants pointed out
in EP-A-346 995 (Unilever),
Also applicable are surfactants such as those described in
EP-A-328 177 (Unilever), which show resistance to
35 salting-out, the alkylpolyglycoside surfactants described in
EP-A-070 074, and the alkyl monoglucosides described in
Wo88/10147 (Novo).
X
12 ~o~963 C 3370 (R)
Preferred anionic surfactants include for example linear and
branched-chain alkylbenzene sulphonates and primary alcohol
sulphates, e.g. those based on fatty radicals deriYed from
5 tallow or coconut oil or mixtures thereof, or those defined
by carbon ranges as e . g . C6-C16 sodium alkyl sulphates and
Cll-C15 sodium alkylbenzene sulphonates.
Anionic surfactants can be present for example in amounts in
lo the range from about 5% to about 50% by weight of the liquid
detergent concentrate. Preferably nonionic detergent is
present in amounts greater than 1%, e.g. 2-20% by weight of
the composition.
15 Among the compositions of the present invention are aqueous
liquid detergents having incorporated therein nonionic-based
enzyme slurries, and having for example a h~ nPo~1c
physical character, e.g. they can consist of a micellar
solution of surfactants in a continuous aqueous phase, so-
20 called isotropic liquids.
Alternatively, they can have a heterogeneous physical phaseand they can be structured, for example they can consist of a
dispersion of lamellar droplets in a continuous aqueous
25 phase, for example comprising a deflocculating polymer having
a hydrophilic backbone and at least one hydrophobic side
chain, as described in EP-A-346 995 (Unilever).
These latter liquids are heterogeneous
and may contain suspended solid particles such as particles
30 of builder materials e.g. of the kinds mentioned below.
The compositions prepared according to the invention further
comprise a builder of the zero-P type. For example they can
be built with zeolite particles. Typical examples of non-
35 rhosrh~ rus-containing builders include water-soluble alkali
~etal carbonates, bicarbonates, silicates and crystalline and
amorphous alumino-silicates. More specific examples are
sodium carbonate (with or without calcite seeds), potassium
X
2039630
13 C 3370 (R)
carbonate, sodium and potassium bicarbonate, silicates, and
zeolites, e.g. zeolite A.
The compositions may contain in aggregate form for example
5 from 1-50~6, e.g. at least about 5% and often up to about
35-40~ by weight, of one or more organic and/or inorganic
builders, especially 5-40%, e.g. 5-25% of non-soap builders.
In the context of several such builders, e.g. inorganic
10 builders ~nd/or zeolites, we prefer to include electrolytes
which promote the solubility of other electrolytes, for
example the use of potassium salts to promote the solubility
of sodium salts. Thereby the amount of dissolved electrolyte
can be increased, as described in GB-A-l 302 543.
Organic detergency builders include for example alkali metal
and ammonium and substituted ammonium polyacetates,
carboxylates, polycarboxylates, polyacetal carboxylates, and
PO1YIIYdLU~Y sulphonates. Specific examples include sodium,
20 potassium and lithium ammonium and substituted ammonium salts
of EDTA, NTA, oxydisuccinic acid, mellitic acid,
benzenepolycArboxylic acids, CMOS, tartrate monosuccinate,
tartrate disuccinate, and citrate.
25 When organic builders are used, it is often desirable to
inc~Ly~,Lc~te polymers which are only partly dissolved in the
aqueous continuous phase, as described in EP-A-301 882. This
allows viscosity reduction (due to dissolved polymer) while
in~;uL~uLil1_ing high enough amounts to achieve secondary
30 benefits such as building, because the undissolved part does
not bring about instability that might occur if all were
dissolved. Typical amounts are from 0 . 5-4 . 5% w/w.
Further polymers may be incorpor~ted as well as or instead of
35 these partly-dissolYed polymers, i.e. substantially
totally-soluble polymers having an average molecular weight
of at least 1000, having an electrolyte resistance of more
than 5 grams Na-NTA in 100ml of a 596 aqueous solution of the
2û39630
14 C 3370 (R)
polymer, and also having vapour pressure in 209~ aqueous
solution equal to or less than the vapor pressure of a 296
aqueous solution of polyethylene glycol of average molecular
weight 6000. These are as described in EP-A-301 882
5 (Unilever).
We have also found that the storage stability of the enzyme
incorporated into an aqueous detergent in the form of a
slurry may be significantly improved by inclusion of
10 electrolytes that cause salting-out of proteins into the
final product. Typical examples of suitable salting-out
electrolytes are alkali~ metal or ammonium salts of -borate,
-sulphate, -citrate, -carbonate and -nitrilotriacetate. When
sodium salts are used, the lyotropic number must be less than
15 9.5 (see also US-A-4 530 780).
The total level of salting-out electrolytes may vary from
about 2 to about 45% by weight of the final product,
preferably from 5 to 30% by weight.
According to convenience, e.g. to ensure desired pH in the
wash liquor during use, it can be convenient to include a pH
buffer such as triethanolamine (/HCl), optionally with
monoethanolamine .
Silicates and carbonates included for other reasons e.g. as
builders may provide some (possibly adequate) buffering
capacity. Tris buffer can also have an auxiliary st~h; 1; 7; n~
effect on the enzymes of the composition.
The detergent compositions may also include usual further
detergent ingredients in usual amounts. Further optional
ingredients of the liquid detergent compositions include e.g.
lather boosters such as alkanolamides, especially
35 monoethanolamides from palm kernel and/or coconut fatty
acids, lather/foam depressants, anti-corrosion agents,
soil-suspending agents, sequestering agents, anti-soil
redeposition agents, perfumes, dyes, colourants and 80 on.
2039630
C 3370 (R)
Compositions of the invention can be prepared by any
conventional method for the preparation of liquid detergent
compositions . A pref erred method comprises dispersing the
electrolyte ingredient(s) and minors (except for any
5 temperature-sensitive items such as enzymes and perfumes) in
water, followed by builder, and the detergent active
ingredient(s), optionally as a premix, with stirring. After
cooling, if n(~ ee~ry, the rr--~in;nq ingredients are added.
Deflocculating polymer can be suitably added just after the
10 electrolyte ingredients, or just after the builder
ingredients or after adding the detergent-active ingredients.
If zeolite is present, it is preferably added as the last
ingredient .
15 The final liquid formulation is adjusted to the desired pH.
The preferred stage for adding the enzyme slurry as described
above, as well as minor constituents such as perfumes and
colourants, etc, is after the stage of pH-adjustment.
20 The use of the present invention enables easy mixing of the
enzyme in the f inal liquid detergent. The liguidity of the
practically anhydrous slurry can give a benef it during
h~n~l ing of the enzyme preparation as compared with the
handling of solid preparations.
The compositions can be used for the washing of textile
materials, especially but without limitation cotton-, nylon-
and polyesterbased textiles and mixtures thereof. Especially
suitable are for example washing processes carried out at
30 temperatures of about 60-65 C or lower, e.g. about 30-35 C
or lower. It can be very suitable to use the compositions in
an amount sufficient to provide about 0 . 4-0 . 8 g/l surfactant
in the wash liquor, although it is of course possible to use
greater concentrations if desired. Without limitation it can
35 for example be stated that a range up to about 6$ of
detergent liquid in the wash liguor, but often below 3% and
usually below 196, can be suitable for use in the case when
the liquids are formulated as in the Examples below.
16 2039630 c 3370 ~R)
It is within the scope of the present invention to
incorporate other stabilizing systems for the enzymes, and
for this purpose it is possible to use the measures set out
S in the specif ications acknowledged by number above in
connection with enzyme st~hili 7~tion
There can for example be further included a quantity of an
enzyme-stabilizing system e.g. selected from (a) an
10 enzyme-stabilizing system comprising calcium and short-chain
aliphatic acid salt, and (b) a polyol-and-borate-containing
enzyme-stabilizing system.
Polyol at 2-25% w/w, e.g. glycerol or propylene glycol or
15 other polyol, with sodium borate or borax at 2-15% w/w, may
be used e.g. in compositions formulated according to EP-A-080
223 (Unilever),
In addition or alternatively, low-molecular weight mono
20 carboxylates (in salt or acid form) such as formate or
acetate (0.1-10%), enzyme accessible calcium ions (0.1-1
mmole/kg) and lower alcohols e . g . ethanol or propylene glycol
(up to 2096), may be used e.g. in compositions formulated
according to EP-A-028 g65 (Procter & Gamble),
It can be quite acceptable to use lesser quantities of these
stabilizers than those pointed out by the above-cited
specif ications .
30 The invention is further illustrated, without intent to limit
its scope, by the following examples, in which amounts and
percentages are by weight unless otherwise indicated.
17 203963~ C 3370 (R)
E~AMPLES 1-5
The following aqueous liquid detergent compo5itions were
prepared by nixing the following ingredients:
Example 1 2 3 4 5
5Anionic detergent
(Dodecyl benzene sulphonic acid) 10 . 3 6 . 7 8 . 4 23 . 0 10 . 0
(Linear alkyl ethoxysulphate) 3 . 4 -- -- -- 6 . 0
Nonionic detergent (Cl3-C15-
primary linear alkyl . 7E0) l . 7 2 . 4 3 . 0 10 . 0 8 . 0
lONonionic detergent (Cl3-C15-
primary linear alkyl . 3E0) -- 2 . 4 3 . o -- --
Zeolite 4A 20 20 -- -- --
Citric Acid -- 3 . 9 4 . 9 -- 4 . 5
Sodium citrate. 2aq 7 . 5 -- -- 16 . 5 --
15Polymer Narlex LD31 0.7 -- -- -- --
Polymer Sokalan PA50 -- 0 . 2 0 . 3 -- --
Deflocculating Polymer -- -- -- 1. 0 --
Monoethanolamine -- -- -- -- 2 . 0
Triethanolamine -- -- -- -- 2 . 0
20Sodium xylenesulphonate -- -- -- -- 3 . o
Minors 0 . 2 l . 8 2 . 3 0 .1 0 . 5
Enzyme preparation 0 . 5 0 . 5 0. 6 0 . 5 0. 5
Water - Balance -
pH adjusted to: 8 . 5 8 . 5 8 . 5 8 . 5 lO . 0
The compositions of Examples l to 4 were structured liquids,
the composition of Example 5 was an isotropic liquid. The
composition of Example 4 was prepared according to the
technique disclosed in EP-A-346 995 and the Dl~flr~rr~ tin~ Polymer
30 corresponded to the polymer A11 of the Examples of that 5p~orifir~tion The
enzyme was a slurry of Savinase (Trade Mark, Novo-Nordisk) in
Tergitol 15-S-9 nonionic detergent (Trade Mark), having a
specific activity of 8 KNPU (s) (kilo Novo protease units) /g.
Subsequently, the storage stability of the enzyme of the
35 compositions of Examples l to 5 was det-or-ninPd at 37C. The
results are shown in Table A.
18 2039530 C 3370 (R)
~AMPLES 6--10
The Examples 1-5 were repeated, except that the enzyme was a
slurry of Savinase (Trade Mark, Novo-Nordisk~ in Tergitol
15-S-9 nonionic detergent (Trade Nark), having a higher
5 Gpecific activity of 16 XNPU (8) (kilo Novo protease
units) /g. Subsequently, the stora~e stability of the enzyme
was det~rm1 n~d at 37C. The results are sho~n in Table A.
C-~MPARATIVE EXAMPLES lA-5A
10 The Examples 1-5 were repeated, except that the Savinase
enzyme was applied as a stabilized aqueous enzyme solutions:
Savinase 16 . OLDX ex Novo-Nordisk. Subsequently, the storage
stability of the Savinase enzyme was det-~rm; nod at 37C. The
results are shown in Table A.
COMPA~ATIVE EXAMPLE P
The following (phosphate-built) aqueous liquid detergent
composition was prepared by mixing the following ingredients:
Anionic detergent
(Dodecyl benzene sulphonic acid) 9 . O
Nonionic detergent
(C12-C15 primary linear alcohol 2 . 25
c~ncl~nc~d with 7 moles of ethylene oxide)
Pentasodium triphosphate 27. 0
Sodium hydroxide 1.1
Enzyme preparation O . 5
Water Balance
The pH of the composition was adjusted to 9 . O
The composition was prepared in accordance with EP-A-266 199
30 (Unilever~. Savinase enzyme was added in the form of a slurry
in nonionic detergent (as described in Example 6).
Subsequently, the storage stability of the enzyme of the
composition was determined at 37C. The results are shown in
Table A.
COMPAR1~TIVE EXANPLE Q
Comparative Example P was repeated, except that the Savinase
enzyme was applied as a stabili2ed aqueous enzyme solution:
203~535
19 C 3370 tR)
Savinase 16 . OLDX ex Novo-Nordisk. Subsequently, the storage
stability of the Savinase enzyme was determined at 37C. The
results are shown in Table A.
S EXAMPLES 11-12
The following aqueous liguid detergent compositions were
prepared by mixing the following ingredients:
Example 11 12
Anionic detergent 12 . 0 25 . 6
10(Dodecyl benzene sulphonic acid)
Nonionic detergent 12 . o 12 . O
(Cl2-C15 primary linear alcohol
condensed with 7 moles of ethyleneoxide)
Fatty acid 6 . O --
15Sodium citrate .2ag 10.0 9.9
Glycerol 2 . 0 4 . 9
Borax. lOag 1. 5 3 . 5
Potassium hydroxide 3 . 2 --
Sodium hydroxide -- 2 . 8
20Zeolite 4A 15. o --
Deflocculating Polymer 1.0 1.0
Triethanolamine -- 2 . O
Monoethanolamine -- 2 . O
Enzyme preparation 1. 0 1. O
25Water and minors - Balance -
p~I adjusted to 8 . 7 9 . 2
The above liquid compositions were prepared according to the
technique disclosed in EP-A-346 99~, and
the polymer corresponded to the polymer All
30 of the exampies of that specification. The enzyme preparation
was a mixture of Savinase and Lipolase (Trade Marks, Novo-
Mordisk). Both enzymes were obtained from Novo-Nordisk.
Savinase was applied as a slurry in Tergitol 15-S-9 nonionic
detergent (TM), having a specific activity of 16 KNPU (s)
35 (kilo Novo protease units) /g, and Lipolase as a stabilized
agueous liguid preparation: Lipolase lOOL ex Novo-Nordisk.
Subseguently, the storage stability of the Lipolase enzyme
was determined at 37C. The results are shown in Table B.
X
2039~
.
C 3370 (R)
l;~XAMP~ .S 13--14
The Examples 11-12 were repeated, except that the Lipolase
enzyme was a slurry in Tergitol 15-S-9 nonionic detergent
5 (Trade Mark) obtained from Novo-Nordisk as Lipolase lOOSL.
Subsequently, the storage stability of the Lipolase enzyme of
the compositions was detPrm;nPd at 37C. The results are
shown in Table B.
10 E~AMPLES 15--16
The Examples 13-14 were repeated, except that the Savinase
enzyme was applied as a stabilized aqueous enzyme solution:
Savinase 16. OLDX ex Novo-Nordisk. Subsequently, the storage
stability of the Lipolase enzyme of the compositions was
15 detprm; ned at 37C. The results are shown in Table B.
cOMp~R~rrIvE Ex~MpL~s llA-12A
The Examples 11-12 were repeated, except that the Savinase
enzyme was applied as a stabilized aqueous enzyme solution:
20 Savinase 16 . OLDX ex Novo-Nordisk. Subsequently, the storage
stability of the Lipolase enzYme of the compositions was
detPrm;nP-l at 37C. The results are shown in Table B.
TABLE A
ExamPle EnzYme tY~e Half-life Qf rotease-
activitY at 37--C (days)
Savinase Slurryl) 3 . 5
2 ,, ,, 5
3 ,, ,, 8
4 ,, ,, 10
6 Savinase Slurry2) 7.8
7 ,, ,, 10
8 ,, ,, 20
9 ,, ,, 25
,, ,, 6.5
P ,, ,, 0.8
lA Savinase Liquid3 ) 1. 9
2A ,, ,, 3
2~3~6~
21 C 3370 (R)
3A ,, ,, 6.5
4A ,, ,, 2
5A ,, ,, 2.8
Q ~ - 0.2
1)S~vinase-slurry containing 8KNPU/g; 8.0SL ex Novo
2) Savinase-slurry containing 16KNPU/g; ex Novo
3)St~hili7ed liquid concentrate containing 16KNPU/g; 16.0LDX
ex Novo
Substantial i v~ -nts in stabilization 2re evident from
the compari60n, in favor of the composition6 prepared
according to the invention, by incorporating the proteolytic
enzyme in the form of the slurry.
TABLE B
Example En7Yme tv~es Half-life of li~ase-
activitv at 37C (daYs)
11 Savinase Slurry1) /Lipolase Liquid2) 16
12 ,, ,, / ,, ,, 3
13 ., ~ ~ /Lipolase Slurry3) 12
Savinase Liquid4) / ,, ,, 8
llA ,, ,, /Lipolase Liquid2) 4
12A ,, ,, / ,, ,, 0. 6
25 1) Savinase-slurry containing 16KNPU/g; ex Novo
2)Lipolase-liquid containing lOOLU/g; lOOL ex Novo
3)Lipolase-slurry containing lOOLU/g; lOOSL ex Novo
4)Stabilized liquid concentrate containing 16KNPU/g; 16.0LDX
ex Novo
Substantial ilU~U}VV. ~S in stabilization are evident from
the comparison, in favor of the compositions prepared
according to the invention, by incorporating the lipolytic
enzyme in the form of the slurry. nhen the lipolytic enzyme
35 i8 present in the form of a liquid c:u~c~ L~te~ its stability
is surprisingly i vv~d when ~ny additional proteolytic
enzyme is present in the form of a slurry.
*****
