Note: Descriptions are shown in the official language in which they were submitted.
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ENZYMATIC COMPOSITIONS
FIELD OF THE INVENTION
The present invention relates to aqueous detergent
compositions which contain enzymes.
BACKGROUND OF THE INVENTION
It is well known in the art that enzymes can lose their
activity with time when included in an aqueous liquid
detergent composition, and various proposals have already
been made to retard that loss of activity by including in
such compositions an enzyme-stabilising system. Various
enzyme stabilisers have been suggested in the art for
inclusion in liquid detergent compositions, e.g. polyols
(e. g. glycerol), borax (preferably in combination with
glycerol), calcium ions, alcohols, low molecular weight
carboxylates (formate, acetate, propionate, etc.) and
polymers (e. g. poly-vinyl-pyrollidone).
Borax, usually in the presence of glycerol, is a very
commonly used enzyme stabiliser and is very effective.
However, concerns about the negative environmental impact
of boron mean that there is a need to formulate
substantially without use of boron-containing compounds yet
to achieve comparable enzyme stability.
It has now been found that this objective can be achieved
in the case of structured aqueous liquid detergent
compositions by a combination of two or more formulation
steps. By structured aqueous liquid detergent composition
is meant those compositions which contain sufficient
detergent-active material and, optionally, sufficiently
GUNFIRMfiTION COPY
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dissolved electrolyte to result in a structure of lamellar
droplets dispersed in a continuous aqueous phase.
Lamellar droplets are a particular class of surfactant
structures which, inter alia, are already known from a
variety of references, e.g. H.A. Barnes, "Detergents", Ch.
2, in K. Waiters (Ed), "Rheometry: Industrial
Applications", J. Wiley & Sons, Letchworth 1980.
Such lamellar dispersions are used to endow properties such
as consumer-preferred flow behaviour and/or turbid
appearance. Many are also capable of suspending
particulate solids such as detergency builders or abrasive
particles. Examples of such structured liquids without
suspended solids are given in US patent 4 244 840, whilst
examples where solid particles are suspended are disclosed
in specifications EP-A-160 342; EP-A-38 101; EP-A-104 452
and also in the aforementioned US 4 244 840. Others are
disclosed in European Patent Specification EP-A-151 884,
where the lamellar droplet are called 'spherulites'.
The presence of lamellar droplets in a liquid detergent
product may be detected by means known to those skilled in
the art, for example optical techniques, various
rheometrical measurements, X-ray or neutron diffraction,
and electron microscopy.
The droplets consist of an onion-like configuration of
concentric bi-layers of surfactant molecules, between which
is trapped water or electrolyte solution (aqueous phase).
Systems in which such droplets are close-packed provide a
very desirable combination of physical stability and solid-
suspending properties with useful flow properties.
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UK patent specification GB-A-2 245 280 discloses examples
of structured aqueous liquid detergents in which the ratio
of water-soluble salt to water :is more than 0.25:1 and
containing an enzyme of undefined solubility. The
compositions contain 0.1~ by weight of calcium acetate.
SUMMARY OF THE INVENTION
The selection of formulation steps to achieve the desired
enzyme stability without substantial use of boron-
containing enzyme stabilisers is defined by the present
invention which provides a liquid detergent composition
comprising a dispersion of lame:Llar droplets in an aqueous
continuous phase, the composition further comprising an
enzyme and being characterised by at least two of the
following three features (i) - (iii):-
(i) the weight ratio of total water-soluble salt to water
in the total composition is at least 0.25:1;
(ii) the solubility of the enzyme in a 25o sodium
citrate.0aq solution in deionis~~d water is at most 50% by
weight of the total added enzyme; and
(iii) the composition further comprises at least one non-
Boron-containing enzyme stabiliser at a level of at least
O.Olo by weight;
wherein the enzyme has a residual activity of at least 100
after storage of the composition at 37C for 4 weeks from
the time of making; and wherein the composition contains no
more than 0.01 by weight of Boron; provided that if only
features (i) and (iii) are present and the non-Boron
containing enzyme stabiliser comprises a water-soluble
calcium salt, then the total amount of water-soluble
calcium salt is at least 0.3o by weight of the total
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composition; and if all of features (i), (ii) and (iii) are
present, then the non-Boron containing enzyme stabiliser
comprises at least one material other than a lignin
compound.
The solubility of the enzyme is defined as the percentage
of total enzyme activity present in the supernatant after
centrifuging for 15 minutes at 16,OOOg a solution of
deionised water comprising of sodium citrate (25o by
weight) and enzyme. A typical enzyme dosage for this
solubility test is 0.4o by weight of a (commercial) liquid
enzyme preparation containing typically 4o enzyme protein.
In case of proteases the activities before and after
centrifugation are determined at 40°C and pH 9.0 using
acetylated caseine as a substrate and reacting
quantitatively the formed amine-groups with 2,4,6-
trinitrobenzene sulphonic acid. The change in absorbance
at 405nm is used a measure for activity.
DETAILED DESCRIPTION OF THE INVENTION
The pH of compositions according to the present invention
is preferably greater than 6, more preferably greater than
7 and most preferably greater than 7.5. On the other hand,
the pH is preferably less than 11, more preferably less
than 10 and most preferably less than 9.5.
Especially preferred are those compositions which combine
all of features (i) - (iii) .
If feature (iii) is utilised, the amount of the non-Boron-
containing enzyme stabiliser in. the composition is at least
O.Olo by weight but more preferably, this minimum is 0.030,
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especially 0.050. In ascending order, still more preferred
minima for this amount (by weight) are O.lo, 0.2o and 0.5°.
The non-Boron-containing enzyme stabiliser may for example
5 be selected from lignin compounds, alkali metal mono- or
dicarboxylates, sources of calcium ions preferably in the
presence of sequestrants and enzyme stabilising polymers.
Suitable lignin compounds are those described in our co-
pending European Patent Applicai=ion No. 95304401.3, filed
22 June 1995 (unpublished at the priority date of the
present application but subsequently published in the form
of an International Patent Application No. WO 97/00932).
The latter document exemplifies compositions exemplifying
all of features (i), (ii} and (iii} of the present
invention wherein a lignin compc>und is used as a non-Boron
containing enzyme stabiliser. These compositions are thus
disclaimed from the scope of the present invention.
Generally speaking, the lignin compounds are mixtures of
components and are usually referred to as a polymer which
contains, amongst others, phenylpropane units. Lignin
compounds can be prepared from the chemical pulping of
hard- and softwoods. Lignin compounds have been found to
be very effective compounds according to the present
invention. There are various lignin compounds which are
preferred enzyme stabilisers according to the invention,
including lignosulphonates, Kraft lignins and oxylignins.
All these compounds are considered lignin compounds. These
compounds may be prepared from Lignin by various ways,
including:
1) treatment with hot (acid) solution of calcium
bisulphate which generates Lignosulphonates. The Lignin
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undergoes a sulphonation and a hydrolysation process under
the influence of sulphite.
2) treatment with hot alkaline (pH 13-14) solution of
sodium sulphate generates Kraft Lignins, which may
subsequently be modified in various ways, e.g. sulphonated,
methylated, carboxylated and/or fractionated.
3) reducing the sulphur content of lignosulphonate raw
material and optionally applying condensation, cleavage
and/or rearrangement, to reduce the number of sulphonic and
methoxyl groups and to increase the number of functional
phenolic, hydroxyl and carboxylic groups generates
oxylignins.
Further variations to Lignin or any of its derivatives may
be made by varying the kind of cation (Na+, K+, Caz+, Mg?+,
NHq+, the degree of sulphonation and/or the average
molecular size).
Examples of lignin derivatives that have been found useful
are Borresperse NA, Borresperse CA, Kelig FS, Maracarb N-l,
Marasperse N-22, Marasperse N-3, Norlig BD, Norlig 415,
Ufoxane 2, Ufoxane 3A, Maracell 3A, Vanisperse CB,
Ultrazine NA, Ultrazine CA (all ex Borregaard) and
lignosulphonates ex Aldrich and ex Sigma as well as ex a
number of pharmaceutical companies.
We have found that inclusion of lignin compounds
significantly retards the enzyme deactivation, and most
surprisingly, lignin compounds are effective as stabiliser
at low concentration. Consequently, lignin compounds are
included in effective amounts in the composition, in
particular in the range of 0.0001 to 100, preferably 0.001
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to 50, more preferably at least 0.01 and more preferably at
most 3o by weight of the composition.
Although the weight ratio between lignin compound and
enzyme (as defined as the weight of the active enzyme
protein material, which does not include any additives that
for example may be present in the enzyme preparations as
supplied by the enzyme manufacturers) may be varied widely,
as long as the enzyme is effectively stabilised, a weight
ratio between 1000:1 and 1:10 has been found to be
preferred, more preferably lower than 500:1, most
preferably lower than 100:1, in particular lower than 50:1,
whereas it is more preferred to have a weight ratio of
higher than 1:5, most preferabl:~r higher than 1:3, in
particular 1:2, more in particu:Lar 1:1.
Preferably, the molar ratio between the total lignin
compound and total enzyme is from 0.1 to 10,000, more
preferably at least 1 and at most 5,000, most preferably at
least 2.
Suitable enzyme stabilising alkali metal mono- or di-
carboxylate include alkali metal formates, e.g. sodium
formate and acetate and propionate, as well as sodium
succinate, sodium maleate, sodium glutamate and sodium
aspartate.
Suitable enzyme-stabilising sources of calcium ions include
any water-soluble calcium salt, such as calcium chloride,
as well as calcium formate and calcium acetate.
Preferably, sequestants are pre~;ent when calcium is
present, for example, phosphorous containing bequest (Trade
mark of Monsanto) and non-phosphorous containing
sequestrants, for example the amino(poly)carboxylates, e.g.
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salts of glutamic acid N,N-diacetic acid, beta-alanine
diacetic acid, ethylenediamine triaceticacid, methyl
glycine diacetic acid, diethylenetriamine penta-acetic
acid, ethylenediamine-N,N-disuccinic acid and
ethylenediamine di(sulfosuccinate)
Suitable enzyme-stabilising polymers include polyvinyl
pyrrolidone, polyvinyl alcohol, polyvinyl acetate,
polyvinyl immidazole, as well as copolymers thereof.
More than one non-boron containing enzyme stabiliser may be
utilised in the same formulation.
The composition must contain no more than O.Olo by weight
of Boron. Preferably the composition is substantially
Boron-free. It is more preferred that the maximum Boron
content by weight of the total composition is 0.0050, still
more preferably 0.003 and especially 0.001$.
If feature (ii) of the present invention is utilised, then
one suitable class of enzymes which meet the solubility
criterion defined by feature (ii) is that described in our
co-pending European Patent Application No. 95201161.7,
filed 5 May 1995 (unpublished at the priority date of the
present application). These enzymes are subtilase variants
wherein one or more amino acid residues situated in or in
the vicinity of a hydrophobic domain of the parent
subtilase have been substituted for an amino acid residue
more hydrophobic than the original residue, said
hydrophobic domain comprising the residues P129, P131,
I165, Y167, Y171 of BLS309 (in BASBPN numbering), and the
residues in the vicinity thereof comprises residues
corresponding to the residues E136, 6159, 5164, 8170, A194
and 6195 of BLS309 (in BASBPN numbering), with the
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exception of the R170M, 81701 and R170V variants of BABP92.
The substitutions) may be combined with substitutions,
insertions or deletions in any other position.
Preferably the original amino acid residue has been
substituted for a residue selected from the group
comprising Val (V) , Ile (I) , Lev,~ (L) , Met (M) , Phe (F) , and
Trp (W), preferably Val, Ile or Leu.
The parent subtilase is preferably chosen from the sub-
group I-SI or I-S2.
Another example of a suitable enzyme variant meeting the
solubility criterion of feature (ii) is Relase as marketed
by Novo Nordisk and described in Patent application
EP-A-405 901.
Apart from enzyme variants, also "wild-type" enzymes can
meet the solubility criterion o~_ feature (ii).
Enzymes can be available in various forms, such as:
- enzyme liquids, where the enzyme is present in an
aqueous solvent. Examples of this class are the L-type
liquids as marketed by Novo Norclisk
- enzyme slurries, where the enzyme is present in a
substantially non-aqueous solvent, such as a liquid
nonionic surfactant. Examples of this class are the SL-
type and SL LDP-type slurries as marketed by Novo Nordisk
- encapsulates of enzymes.
Liquids, slurries and encapsulates may contain a mixture of
enzymes selected from protease, lip(ol)ase, amylase,
cellulase, etc. All these enzyme forms can be used in the
present invention.
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The residual activity of the enzyme is at least loo as
determined as hereinbefore described. Preferably though,
this minimum is at least 250, more preferably 400, still
more preferably 50o and most preferably 750.
5
Moreover, the enzyme solubility when determined as
hereinbefore described in respect of feature (ii) is at
most 50o by weight of the total added enzyme. Preferably
though, this maximum is 250, more preferably 100, still
10 more preferably 5o and especially 20.
If feature (ii) is not utilised, then the enzyme may be
chosen from any of those known in the art of formulating
enzyme-containing detergent compositions and even if
feature (ii) is utilised the composition may additionally
contain one or more additional enzymes selected from such
known enzymes. In general, such enzymes may be selected
from proteases, amylases, lipases, cellulases and mixtures
of one or more of these enzymes. Proteases are preferred
enzymes for use in the present invention, as we have seen
the best results with protease stabilisation.
Depending on the type of composition and whether or not an
enzyme meeting the criterion of feature (ii) is actually
incorporated, the enzymes) preferably provide (as
appropriate) a proteolytic activity between 0.1 and 50
GU/mg, a lipolytic activity between 0.005-100 LU/mg and an
amy.lolytic activity between 103 and 10' MU/kg, wherein GU,
LU and MU units are well known in the art and have e.g.
been defined in lines 8-14 of column 3 and lines 8-12 and
21-24 of column 9 of US 5,112,518.
Depending on the composition type, the level of active
enzyme protein will be higher (up to 100, preferably up to
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5o by weight for concentrated enzyme preparations, e.g. as
supplied by enzyme manufacturers) or lower (up to 30,
preferably up to l.Oo, although levels up to 0.50 or up to
0.1° or even as low as up to 0.050 are also suitable for
more dilute systems, e.g. commercial liquid detergent
compositions in which the concentrated enzyme preparations
are used during production). T~ze active enzyme protein
level may be as low as 0.0001°, preferably at least O.Olo
by weight of the composition. Again in more concentrated
enzyme preparations, the lower :Level will be higher, e.g.
at least 0.5o by weight.
If feature (i) is utilised, the weight ratio of the total
water-soluble salt (electrolyte,' to water in the total
composition is at least 0.25:1 but preferably it is of at
least 0.35:1, more preferably ate least 0.40:1, still more
preferred minima for this weight. ratio are, in ascending
order: 0.45:1, 0.50:1, 0.55:1, 0.60:1 and 0.65:1.
Preferably also, the maximum value of this weight ratio is
1Ø
As used herein the term "water-~>oluble salt" includes both
the salts) from the formulation that totally dissolves and
the dissolved part of the salt(:.) that does not totally
dissolve, expressed as anhydrous; salts.
The compositions of the present invention are aqueous
dispersions of lamellar droplets,. Although it is possible
to form lamellar dispersions of surfactant in water alone,
in many cases it is preferred for the aqueous continuous
phase to contain dissolved electrolyte. As used herein,
the term electrolyte means any ionic water-soluble
material. However, in lamellar dispersions, not all the
electrolyte is necessarily dissolved but may be suspended
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as particles of solid because the total electrolyte
concentration of the liquid is higher than the solubility
limit of the electrolyte. Mixtures of electrolytes also
may be used, with one or more of the electrolytes being in
the dissolved aqueous phase and one or more being
substantially only in the suspended solid phase. Two or
more electrolytes may also be distributed approximately
proportionally, between these two phases. In part, this
may depend on processing, e.g. the order of addition of
components. On the other hand, the term 'salts' includes
all organic and inorganic materials which may be included,
other than surfactants and water, whether or not they are
ionic, and this term encompasses the sub-set of the
electrolytes (water-soluble materials).
The only restriction on the total amount of detergent-
active material and electrolyte (if any) is that in the
compositions of the invention, together they must result in
formation of an aqueous lamellar dispersion. Thus, within
the ambit of the present invention, a very wide variation
in surfactant types and levels is possible. The selection
of surfactant types and their proportions, in order to
obtain a stable liquid with the required structure will be
fully within the capability of those skilled in the art.
However, it can be mentioned that an important sub-class of
useful compositions is those where the detergent-active
material comprises blends of different surfactant types.
Typical blends useful for fabric washing compositions
include those where the primary surfactants) comprise
nonionic and/or a non-alkoxylated anionic and/or an
alkoxylated anionic surfactant.
In addition to the above described conventional structured
liquids, the stability of compositions of the present
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invention may be enhanced, or the rheology of such
compositions may be controlled by incorporation of a
deflocculating polymer such as any described in EP-A-346
995 or in any of W091/06622; W0~31/06623;
GB-A-2,237,813; W091/09109; US-A-5,494,602; EP-A-623,670;
US-A-5, 489, 397; and EP-A-691, 39~~.
In many (but not all) cases, the total detergent-active
material may be present at from 2o to 60o by weight of the
total composition, for example from 5% to 40~ and typically
from loo to 30Q by weight. However, one preferred class of
compositions comprises at least 20°, most preferably at
least 250, and especially at least 300 of detergent-active
material based on the weight of the total composition. In
the case of blends of surfactants, the precise proportions
of each component which will result in such stability and
viscosity will depend on the types) and amounts) of the
electrolytes, as in the case with conventional structured
liquids.
In the widest definition the detergent-active material in
general, may comprise one or more surfactants, and may be
selected from anionic, cationic, nonionic, zwitterionic and
amphoteric species, and (provided mutually compatible)
mixtures thereof. For example, they may be chosen from any
of the classes, sub-classes and specific materials
described in 'Surface Active Agents' Vol. 1. By Schwartz &
Perry, Interscience 1949 and 'Surface Active Agents' Vol.
II by Schwarz, Perry & Berch (Interscience 1958), in the
current edition of "McCutcheon's Emulsifiers & Detergents"
published by the McCutcheon division of Manufacturing
Confectioners Company or in 'Ten;sid-Taschenbuch', H.
Stache, 2nd Edn. , Carl Hanser Ve:rlag, Miinchen & Wien, 1981 .
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Suitable nonionic surfactants include, in particular, the
reaction products of compounds having a hydrophobic group
and a reactive hydrogen atom, for example aliphatic
alcohols, acids, amides or alkyl phenols with alkylene
oxides, especially ethylene oxide, either alone or with
propylene oxide. Specific nonionic detergent compounds are
alkyl (C6-C18) primary or secondary linear or branched
alcohols with ethylene oxide, and products made by
condensation of ethylene oxide with the reaction products
of propylene oxide and ethylenediamine. Other so-called
nonionic detergent compounds include long chain tertiary
amine oxides, long-chain tertiary phospine oxides and
dialkyl sulphoxides.
Suitable anionic surfactants are usually water-soluble
alkali metal salts of organic sulphates and sulphonates
having alkyl radicals containing from about 8 to about 22
carbon atoms, the term alkyl being used to include the
alkyl portion of higher acyl radicals. Examples of
suitable synthetic anionic detergent compounds are sodium
and potassium alkyl sulphates, especially those obtained by
sulphating higher (C8-C,fl) alcohols produced, for example,
from tallow or coconut oil, sodium and potassium alkyl (C9-
CZO) benzene sulphonates, particularly sodium linear
secondary alkyl (C,o-C15) benzene sulphonates; sodium alkyl
glyceryl ether sulphates, especially those ethers of the
higher alcohols derived from tallow or coconut oil and
synthetic alcohols derived from petroleum; sodium coconut
oil fatty monoglyceride sulphates and sulphonates; sodium
and potassium salts of sulphuric acid esters of higher (C8-
C,8) fatty alcohol-alkylene oxide, particularly ethylene
oxide, reaction products; the reaction products of fatty
acids such as coconut fatty acids esterified with
isethionic acid and neutralised with sodium hydroxide;
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sodium and potassium salts of fatty acid amides of methyl
taurine; alkane monosulphonates such as those derived by
reacting alpha-olefins (C8_ZO) with sodium bisulphate and
those derived from reacting paraffins with SOZ and C12 and
5 then hydrolysing with a base to produce a random
sulphonate; and olefin sulphonates, which term is used to
describe the material made by reacting olefins,
particularly Clo-Czo alpha-olefins, with S03 and then
neutralising and hydrolysing the reaction product. The
10 preferred anionic detergent compounds are sodium (Cm-Cls)
alkyl benzene sulphonates and sodium (C,F-C18) alkyl
sulphates.
Also possible is that part or all of the detergent active
15 material is a stabilising surfactant, which has an average
alkyl chain length greater than 6 C-atoms, and which has a
salting out resistance, greater than, or equal to 6.4.
These stabilising surfactants a:re disclosed in our European
patent application EP-A-328,177. Examples of these
materials are alkyl polyalkyloxated carboxylates, alkyl
polyalkoxylated phosphates, alkyl polyalkoxylated
sulphosuccinates; dialkyl diphenyloxide disulphonates;
alkyl polysacccharides and mixtures thereof.
It is also possible, and sometimes preferred, to include an
alkali metal soap of a long chain mono- or dicarboxylic
acid for example one having from 12 to 18 carbon atoms.
Typical acids of this kind are oleic acid, ricinoleic acid,
and fatty acids derived from castor oil, rapeseed oil,
groundnut oil, coconut oil, palm kernel oil or mixtures
thereof. The sodium or potassium soaps of these acids can
be used.
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Preferably the amount of water in the composition is from 5
to 950, more preferred from 25 to 750, most preferred from
30 to 500. Especially preferred less than 45o by weight.
The compositions optionally also contain electrolyte in an
amount sufficient to bring about structuring of the
detergent-active material. Preferably though, the
compositions contain from to to 600, especially from 10 to
950 of a salting-out electrolyte. Salting-out electrolyte
has the meaning ascribed to in specification EP-A-79 696.
Optionally, some salting-in electrolyte (as defined in the
latter specification) may also be included, provided if of
a kind and in an amount compatible with the other
components and the composition is still in accordance with
the definition of the invention claimed herein. Some or
all of the electrolyte (whether salting-in or salting-out),
or any substantially water-insoluble salt which may be
present, may have detergency builder properties. In any
event, it is preferred that compositions according to the
present invention include detergency builder material, some
or all of which may be electrolyte. The builder material
is any capable of reducing the level of free calcium ions
in the wash liquor and will preferably provide the
composition with other beneficial properties such as the
generation of an alkaline pH, the suspension of soil
removed from the fabric and the dispersion of the fabric
softening clay material.
Examples of phosphorous-containing inorganic detergency
builders, when present, include the water-soluble salts,
especially alkali metal pyrophosphates, orthophosphates,
polyphosphates and phosphonates. Specific examples of
inorganic phosphate builders include sodium and potassium
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tripolyphosphates, phosphates and hexametaphosphates.
Phosphonate sequestrant builders may also be used.
Examples of non-phosphorus-containing inorganic detergency
builders, when present, include water-soluble alkali metal
carbonates, bicarbonates, silicates and crystalline and
amorphous aluminosilicates. Specific examples include
sodium carbonate (with or without calcite seeds), potassium
carbonate, sodium and potassium bicarbonates, silicates and
zeolites.
In the context of inorganic builders, we prefer to include
electrolytes which promote the .solubility of other
electrolytes, for example use of potassium salts to promote
the solubility of sodium salts. Thereby, the amount of
dissolved electrolyte can be increased considerably
(crystal dissolution) as described in UK patent
specification GB 1 302 543.
Examples of organic detergency builders, when present,
include the alkaline metal, ammonium and substituted
ammonium polyacetates, carboxylates, polycarboxylates,
polyacetyl carboxylates, carboxymethyloxysuccinates,
carboxymethyloxymalonates, ethy7_ene diamine-N, N, disuccinic
acid salts, polyepoxysuccinates, oxydiacetates, triethylene
tetramine hexacetic acid salts, N-alkyl imino diacetates or
dipropionates, alpha sulpho- fatty acid salts, dipicolinic
acid salts, oxidised polysaccharides,
polyhydroxysulphonates and mixtures thereof.
Specific examples include sodium, potassium, lithium,
ammonium and substituted ammonium salts of
ethylenediaminetetraacetic acid, nitrilitriacetic acid,
oxydisuccinic acid, melitic acid, benzene polycarboxylic
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acids and citric acid, tartrate mono succinate and tartrate
di succinate.
In the context of organic builders, it is also desirable to
incorporate polymers which are only partly dissolved in the
aqueous continuous phase. This allows a viscosity
reduction (owing to the polymer which is dissolved) whilst
incorporating a sufficiently high amount to achieve a
secondary benefit, especially building, because the part
which is not dissolved does not bring about the instability
that would occur if substantially all were dissolved.
Examples of partly dissolved polymers include many of the
polymer and co-polymers salts already known as detergency
builders. For example, may be used (including building and
non-building polymers) polyethylene glycols, polyacrylates,
polymaleates, polysugars, polysugarsulphonates and co-
polymers of any of these. Preferably, the partly dissolved
polymer comprises a co-polymer which includes an alkali
metal salt of a polyacrylic, polymethacrylic or malefic acid
or anhydride. Preferably, compositions with these co-
polymers have a pH of above 8Ø In aeneral. the amn"nfi
viscosity-reducing polymer can vary widely according to the
formulation of the rest of the composition. However,
typical amounts are from 0.5 to 4.5~ by weight.
It is further possible to include in the compositions of
the present invention, alternatively, or in addition to the
partly dissolved polymer, yet another polymer which is
substantially totally soluble in the aqueous phase and has
an electrolyte resistance of more than 5 grams sodium
nitrilotriacetate in 100 ml of a 5o by weight aqueous
solution of the polymer, said second polymer also having a
vapour pressure in 20o aqueous solution, equal to or less
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than the vapour pressure of a reference 2o by weight or
greater aqueous solution of polyethylene glycol having an
average molecular weight of 6,000; said second polymer
having a molecular weight of at least 1,000.
The incorporation of the soluble polymer permits
formulation with improved stability at the same viscosity
(relative to the composition without the soluble polymer)
or lower viscosity with the same stability. The soluble
polymer can also reduce viscosity drift, even when it also
brings about a viscosity reduction. Here, improved
stability and lower viscosity mean over and above any such
effects brought about by the deflocculating polymer.
It is especially preferred to incorporate the soluble
polymer with a partly dissolved polymer which has a large
insoluble component. That is because although the building
capacity of the partly dissolved polymer will be good
(since relatively high quantities can be stably
incorporated), the viscosity reduction will not be optimum
(since little will be dissolved). Thus, the soluble
polymer can usefully function to reduce the viscosity
further, to an ideal level.
The soluble polymer can, for example, be incorporated at
from 0.05 to 20o by weight, although usually, from 0.1 to
loo by weight of the total composition is sufficient, and
especially from 0.2 to 3.5 - 4.5o by weight. It has been
found that the presence of deflo cculating polymer increase
the tolerance for higher levels of soluble polymer without
stability problems. A large number of different polymers
may be used as such a soluble polymer, provided the
electrolyte resistance and vapour pressure requirements are
met. The former is measured as the amount of sodium
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nitrilotriacetate (NaNTA) solution necessary to reach the
cloud point of 100 ml of a 5o solution of the polymer in
water at 25°C, with the system adjusted to neutral pH, i.e.
about 7. This is preferably effected using sodium
5 hydroxide. Most preferably, the electrolyte resistance is
10 g NaNTA, especially 15 g. The latter indicates a vapour
pressure low enough to have sufficient water binding
capability, as generally explained in the Applicants'
specification GB-A-2 053 249. Preferably, the measurement
10 is effected with a reference solution at loo by weight
aqueous concentration, especially 180.
Typical classes of polymers which may be used as the
soluble polymer, provided they meet the above requirements,
15 include polyethylene glycols, Dextran, Dextran sulphonates,
polyacrylates and polyacrylate/maleic acid co-polymers.
The soluble polymer must have an average molecular weight
of at least 1,000 but a minimum average molecular weight of
20 2,000 is preferred.
The use of partly soluble and the use of soluble polymers
as referred to above in detergent compositions is described
in our European patent applications EP-A- 301 882 and EP-A-
301 883.
Although it is possible to incorporate minor amounts of
hydrotropes such as lower alcohols (e.g. ethanol) or
alkanolamines (e. g. triethanolamine), in order to ensure
integrity of the lamellar dispersion we prefer that the
compositions of the present invention are substantially
free from hydrotropes. By hydrotrope is meant any water
soluble agent which tends to enhance the solubility of
surfactants in aqueous solution.
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21
Apart from the ingredients already mentioned, a number of
optional ingredients may also be present, for example
lather boosters such as alkanolamides, particularly the
monoethanolamides derived from palm kernel fatty acids and
coconut fatty acids, fabric softeners such as clays, amines
and amine oxides, lather depressants, oxygen-releasing
bleaching agents such as sodium perborate and sodium
percarbonate, peracid bleach precursors, chlorine-releasing
bleaching agents such as trichloroisocyanuric acid,
inorganic salts such as sodium sulphate, and, usually
present in minor amounts, oily-soil release polymers, e.g.
those described in our copending European patent
application EP 95300175.7 and EP 95308630.3 and EP
95308629.5 and those sold under Trademarks Permalose,
Aquaperle and Gerol, fluorescent agents, perfumes,
germicides and colorants.
The invention will now be illustrated~by way of the
following Examples. In all Examples, unless stated to the
contrary, all percentages are b:y weight.
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22
EXAMPLES
Example 1
Component ~w/w
LAS -acid 16.5
Nonionic (Dobanol 25-7) 9
Oleic acid (Priolene 6907) 4.5
Zeolite 15
KOH, neutralisation of acids
and pH to 8.5
Citric acid 8.2
deflocculating polymer* 1
Protease 0.38
Lipolase 0.2
Oily soil release polymer 0.5
Aquaperle
Minors 0.4
Water to
100$
* polymer All from EP 346,995
Enzyme Residual activity Features which are
4 weeks 37°C fulfilled
Savinase SL 660 (i) and (ii)
LDP
Relase 16 72% (i), (ii) and (iii)
EXI Note: enzyme contains
PVP
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23
Example 2
Component ~w/w
K-LAS 25.2
LES 6.0
STPP 15.0
K-citrate 15.4
deflocculating 1
polymer*
Protease var
Enzyme stabiliser of x
feature (iii)
Tinopal CBS-X 0.18
Perfume 0.5
Water to
100$
pH, adjusted with KOH
to 7.5 - 8
* polymer All from EP
346, 995
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24
Enzyme (x) Enzyme Residual Features
which
stabiliser activity 4 are fu lfilled
(iii) weeks 37C
0. 7 o none 30 ~ (i)
Alcalase
2.34L
ditto 0.5o CaCl2 + 450 (i) and (iii)
0.5o bequest
2066
ditto 0.050 PVP 55~ (i) and (iii)
ditto 0.5 PVP 62 0 (i) and (iii)
0.3o none 350 (i)
Savinase
16L EXI
ditto 0.5o CaCl2 + 500 (i) and (iii)
0.5o bequest
2066
ditto 0.050 PVP 550 (i) and (iii)
ditto 0.5o PVP 610 (i) and (iii)
0.2o none 350 (i) and (ii)
Relase
8.9L**
ditto 0.5o CaCl2 + 550 (i) , (ii)and
(iii)
0.5o bequest
2066
ditto 0.050 PVP 670 (i), (ii) and
(iii)
ditto 0.5o PVP 810 (i), (ii) and
(iii)
** A Relase preparation
without PVP
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Example 3
Component ~w/w
K-LAS 25.2
LES 6.0
STPP 22.0
K-citrate 3.1
deflocculating 1
polymer*
Protease 0.4%
Enzyme stabiliser of x
feature (iii)
Tinopal CBS-X 0.18
Ti02 0.5
Perfume 0.5
Water to
100$
pH, adjusted with KOH
to 7.5-8
* polymer All from EP
346, 995
Enzyme Enzyme, Residual Features
stabiliser activity 4 which are
(iii) weeks 37°C fulfilled
Relase 16L none 44o (i), (ii) and
EXI
(iii)
ditto 0.250 extra 650 (i), (ii) and
PVP
(iii)
Note: enzyme contains already F?VP.
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26
Example 4
Component ~w/w
K-LAS 23.6
Nonionic (Dobanol 25- 7.5
7)
STPP 21.0
KTPP 9.0
deflocculating 2
polymer*
Protease 0.40
Enzyme stabiliser of x
feature (iii)
Tinopal CBS-X 0.18
Ti02 0.5
Perfume 0.5
Water to
1000
pH, adjusted with KOH
to 7.5-8
* polymer A11 from EP
34 6, 995
Enzyme Enzyme Residual Features
stabiliser activity 4 which are
(iii) weeks 37°C fulfilled
Relase 16L none 52o (i), (ii) and
EXI
(iii)
ditto 0.5% extra 70o (i), (ii) and
PVP
(iii)
Note: enzyme contains already PVP
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27
Example 5
Component $w/w
LAS-acid 7_7
Nonionic (Dobanol 25-;~) 2.3
STPP/KTPP vac
Na?SOQ/KZSOq vac
Enzyme stabiliser of vac
feature (iii)
deflocculating polymer* 1
Relase 16L EXI 0.4
Tinopal CBS-X 0.1
Perfume 0.17
Proxel 0.02
Silicone oil, anti foam 0/0.25
Water to 1000
pH, adjusted with KOH to
7.5-8
* polymer All from EP
346, 995
Electroly Enzyme Residual Features
te(s) stabiliser activity 4 which are
(iii) weeks 37C fulfilled
21o STPP none Oo
(ii) and
(iii)
ditto 0.5~ PVP 0$
(ii) and
(iii)
30$ KTP 0.5o PVP about 40s (i), (ii) and
(iii)
21o STPP 0.5o PVP about 500 (i), (ii) and
(iii)
l0 o KzS04
Note: enzyme contains already PVP
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28
Example 6
Component ~w/w
LAS-acid 11.25
Nonionic (Dobanol 25- 3.75
7)
STPP var
Na2S0q var
deflocculating 3
polymer*
Relase 16L EXI 0.4
Tinopal CBS-X 0.1
Perfume 0.17
Proxel 0.02
Silicon oil, anti foam 0/0.25
Water to 100$
pH, adjusted with KOH
to 7.5-8
* polymer All from EP
346, 995
Electrolytes Enzyme Residual Features
stabiliser activity 4 which are
(iii) weeks 37°C fulfilled
5$ STPP none 89$ (i), (ii) an
(iii)
20 $ Na2S0q
7.5$ STPP none 74$ (i), (ii) and
(iii)
15 $ NazS04
Note: enzyme contains already PVP
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29
Example 7
Component ~w/w
LAS-acid 120
LES 3 0
STPP 100
KOH 2.44$
Protease 0.40
Enzyme stabilise .. of 150
feature (i)
Tinopal CBS-X 0.09
Deflocculating 0.250
polymer*
Water to
laoo
* polymer All from
EP 346 995
Enzyme Enzyme Residual Features
stabiliser (i) Activity 4 wh ich
are
weeks at fu lfilled
37C
Relase 16L 15% Na-sulphate 610 (i),(ii)
EXI Oaq and (ii)
Savinase 16L 15o Na-sulphate 380 (i),(ii)
EXI Oaq and (ii)
Savinase SL 15o Na-sulphate 45o (i),(ii)
LDP Oaq and (ii)
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Example 8
Component ~w/w
K-LAS 23.6
Nonionic (Doba nol 25- 7.5
7)
K-citrate 3.1
STPP 22
Protease 0.4
Enzyme stablis er of 0.3
feature (iii)
Tinopal CBS-X 0.18
Soil Release 0.5
Polymer**
Deflocculating 1
polymer*
Ti02 0.5
Perfume 0.5
Antifoam*** 0.6
Water to
100$
*polymer All from EP 346995
**Aquaperl SRL ex ICI
***DB100 ex Dow Corning
Enzyme Enzyme Residual Features
stabiliser Activity 4 which are
(iii) weeks at 37C fulfilled
Relase 16L 0.3o PVP 760 (i), (ii)
and
EXI
(iii)
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31
Raw Material Specification
Component Specification
LAS-acid Linear Alkyl Benzene Sulphonic-acid, Marlon
AS3, ex Huls
K-LAS LAS-acid neutralised with KOH
Dobanol 25-7 C12-15 ethoxylated alcohol, 7E0, ex Shell
LES Lauryl Ether Sulphate, Dobanol 25-S3, ex
Shell
Oleic acid Priolene 6907, ex Unichema
Zeolite Wessalith P, ex Degussa
STPP Sodium Tri Polyphosphate, Thermphos NW, ex
Hoechst
KTPP Potassium Tri Polyphosphate
Proxel Preservative, ex ICI
CaCl? ex Chemproha
bequest 2066 Metal chelating agent, ex Monsanto
Silicone oil Antifoam, DB 100, ex Dow Corning
PVP Poly Vinyl Pyrollidon, ex ISP Global
Technologies
Tinopal CBS-X Fluorescer, ex Ciha-Geigy
Aquaperle SRL Oily Soil Release polymer, ex ICI
Lipolase type 100L, ex Novo
Savinase SL Protease, ex Novo
LDP
Relase 16L Protease, ex Novo
EXI
Alcalase 2.34 Protease, ex Novo
L
Savinase 16L Protease, ex Novo
Savinase 16L Protease, ex Novo
EXI
Relase 8.9L Protease, ex Novo
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32
In the light of this disclosure, modifications of the
described examples, as well as other examples, all within
the scope of the present invention as determined by the
appended claims will now become apparent to persons skilled
in the art.
