Note: Descriptions are shown in the official language in which they were submitted.
LIOUID BLEACH COMPOSITION
The present invention relates to a liquid detergent
composition comprising an aqueous base, detergent active
materials and a bleach material.
It has been proposed in EP 293 040 (P&G) to formulate
liquid detergent compositions which comprise a perborate
bleach material and a water-soluble solvent system to
increase the stability of the bleach in the aqueous
phase. Similar solvents in combination with bleaches
are proposed in EP 294 904 (P&G), this document also
discloses the in-situ preparation of perborate by
reacting metaborate with hydrogen peroxide. Fr 2.140.822
describes the stabilisation of bleach by using from 5 to
15% of borax.
In formulating liquid aqueous detergent compositions
comprising a bleach material, we have noted that bleach
instability problems sometimes occur. Although not yet
fully understood this instability is believed to be
caused by the solubilisation of the bleach materials in
the aqueous phase, followed by the decomposition of the
dissolved bleach materials.
Surprisingly it has now been found that stable bleach
containing liquid aqueous detergent compositions can be
formulated, provided that said compositions also
comprise a specific boron electrolyte, obtainable by
using metaborate.
Accordingly, the present invention relates a liquid
detergent composition comprising an aqueous base, a
bleach material and from 2-60 % by weight of detergent
active materials, wherein the composition also comprises
a metaborate electrolyte or a boron electrolyte
obtainable by using a metaborate electrolyte.
UTE SHEEI-
WO9l/~M~2 PCT/EP90/01
h~ ~ ~ff ~ 2
~ bleach material
Compositions according to the present invention
comprise a bleach material, which is preferably à
peroxygen bleach. This bleach component may be present
in the system in dissolved form, but preferred is that
only part of the peroxygen bleach is solubilized, the
remaining part preferably being present as solid
peroxygen particles which are suspended in the system.
Examples of suitable bleach compounds include hydrogen
peroxide, the perborates, persulfates, peroxy
disulfates, perphosphates and the crystalline
peroxyhydrates formed by reacting hydrogen peroxide with
urea or alkali metal carbonate. Also encapsulated
bleaches may be used. Preferred bleaches are only
partially soluble in the system. Especially preferred is
the use of perborate or percarbonate bleaches.
The bleach component is preferably added in an amount
corresponding to 0.1 to 15% by weight of active oxygen,
more preferred from 0.5 to 10% active oxygen, typically
from 1.0 to 5.0% active oxygen. Typical amounts of
bleach will be between 1 and 40 % by weight of the
2S aqueous composition, more preferred from 7 to 30~,
especially preferred from 10 to 25 % by weight of the
composition.
metaborate electrolYte
Compositions of the invention also comprise a metaborate
electrolyte or a boron electrolyte obtainable by using
metaborate. Suitable metaboric compounds include for
example metaboric acid, alkali metal metaborates and
alkali earth metal metaborates.
Surprisingly it has been found that from the class of
boron com~oul,ds especially the use of metaborate and its
,
~g~ lT~TE SHEE~
WO 91/00902 ~ ~ S 2 ~ ~ ~
derivatives is preferred because of their excellent
ability to stabilize bleach systems. Although not yet
fully understood it is believed that the metaborate
electrolyte can have two functions, firstly it prevents
the solubilisation of the bleach material, therewith
minimizing the amount of instable dissolved bleach and
secondly it retards the decomposition of the dissolved
bleach materials.
The level of metaborate electrolyte is preferably more
than 0.1 % by weight of the compositions, especially
preferred more than 0.2 % by weight of the composition.
most preferred more than 0.4 %. Generally the level of
metaborate electrolyte is less than 10%, more preferred
less than 7 %, especially preferred less than 5 %.
Typical levels of metaborate electrolytes are from 0.5
to 5 %.
The percentages for the metaborate electrolyte are
calculated on the basis of the anhydrous metaborate
equivalent of the electrolyte. For the purpose of the
present invention the metaborate level is preferably
determined by measuring the boron content of the
formulation and subsequently calculating the
corresponding level of metaborate at a stAnAArd pH of
11. Preferably the calculated level of the metaborate
at the stAnAArd pH is then defined as the metaborate
level in the composition.
Preferably the molar ratio of metaborate or boron
equivalent thereof to hydrogen peroxide (if any) in the
ready to use composition is more than 1 : 1, preferably
more than 2 : 1, most preferred more than 5 : 1.
detergent active materials
Compositions of the present invention also comprise
detergent active materials. Surprisingly it has been
$~ r~
WO91/~2 PCT/E ~ /01
r~ i. 4
found that a combination of bleach materials and
metaborate electrolytes or boron derivatives thereof is
suitable for use in ready to use aqueous liquid
detergent compositions.
In the widest definition the detergent active materials
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. I, by Schwartz & Perry, Interscience 1949 and
"Surface Active Agents" Vol. II by Schwartz, Perry &
Berch (Interscience 1958), in the current edition of
"McCutcheon's Emulsifiers & Detergents" published by the
McCutcheon division of Manufacturing Confectioners
Company or in Tensid-Taschenburch", H. Stache, 2nd Edn.,
Carl Hanser Verlag, Munchen & Wien, 1981.
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.
Also possible is the use of salting out resistant active
materials, such as for example described in EP 328 177,
especially the use of alkyl poly glycoside surfactants,
such as for example disclosed in EP 70 074
SUaSTlTUTE SHEEr
7 8 1
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-C18) alcohols produced
for example from tallow or coconut oil, sodium and
potassium alkyl (Cg-C20) benzene sulphonates,
particularly sodium linear secondary alkyl (C10-Cl5)
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-C18) 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; sodium and potassium
salts of fatty acid amides of methyl taurine; alkane
monosulphonates such as those derived by reacting alpha-
olefins (C8-C20) with sodium bisulphite and those
derived from reacting paraffins with S02 and Cl2 and
then hydrolysing with a base to produce a random
sulponate; and olefin sulphonates, which term is used to
describe the material made by reacting olefins,
particularly Clo-C20 alpha-olefins, with S03 and'then
neutralising and hydrolysing the reaction product. The
preferred anionic detergent compounds are sodium (Cl1-
C15) alkyl benzene sulphonates and sodium or potassium
primary (C10-Cl8) alkyl sulphates.
It is also possible, and sometimes preferred, to include
an alkali metal soap of a fatty acid, especially a soap
of an acid having from 12 to 18 carbon atoms, for
SU~SrITUTE ~
206278~
example oleic acid, ricinoleic acid, and fatty acids
derived from castor oil, alkylsuccinic acid, rapeseed
oil, groundnut oil, coconut oil; palmkernel oil or
mixtures thereof. The sodium or potassium soaps of these
acids can be used.
~,
The total detergent active material may be present at
from 2% to 60~ by weight of the total composition, for
example from 5% to 40% and typically from 10% to 30% by
weight. However, one preferred class of compositions
comprises at least 20%, most preferably at least 25% and
especially at least 30% of detergent active material
based on the weight of the total composition.
oPtional ingredients
Compositions of the invention may be un-structured
(isotropic) or structured. Structured li~uids of the
invention may be internally structured whereby the
structure is formed by the detergent active materials in
the composition or externally structured, whereby the
structure is provided by an external structurant.
Preferably compositions of the invention are internally
structured.
Some of the different kinds of active-structuring which
are possible are described in the reference H.A. Barnes,
"Detergents", Ch.2. in K. Walters (Ed), "Rheometry:
Industrial Applications", J. Wiley & Sons, Letchworth
1980. In general, the degree of ordering of such systems
increases with increasing surfactant and/or electrolyte
concentrations. At very low concentrations, the
surfactant can exist as a molecular solution, or as a
solution of spherical micelles, both of these being
isotropic. With the addition of further surfactant
and/or electrolyte, structured (antisotropic) systems
can form. They are referred to respectively, by various
SUBSl-ITUTE ~
~6~;1&1
terms such as rod-micelles, planar lamellar structures,
lamellar droplets and liquid crystalline phases. Often,
different workers have used different terminology to
refer to the structures which are really the same. For
instance, in European patent specification EP-A-151
884, lame~lar droplets are called "spherulites". The
presence and identity of a surfactant structuring system
in a liquid may be determined by means known to those
skilled in the art for example, optical t~h~iques,
various rheometrical measurements, x-ray or neutron
diffraction, and sometimes, electron microscopy.
When the compositions are of lamellar structure then 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 nec~sc~rily dissolved but may be
suspended 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 surfàctants
and water, whether or not they are ionic, and this term
encompasses the sub-set of the electrolytes (water
soluble materials).
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
S~ tE S~tEE
W091/~2 PCT/E ~ /01~K
~v~
,_ 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 surfactant(s) comprise nonionic and/or a non-
alkoxylated anionic and/or an alkoxylated anionic
surfactant.
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 type(s) and
amount(s) of the electrolytes, as is the case with
conventional structured liquids.
Preferably though, the compositions contain from 1% to
60%, especially from 10 to 45% of a salting-out
electrolyte. Salting-out electrolyte has the meaning
ascribed to in specification EP-A-79 646, that is
salting-out electrolytes have a lyotropic number of less
than 9.5. Optionally, some salting-in electrolyte (as
defined in the latter specification) may also be
included, provided it is 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 25 the
generation of an alkaline pH, the suspension of soil
removed from the fabric and the dispersion of the fabric
softening clay material. Preferably the salting-out
electrolyte comprises citrate.
~ SU~:iTITUT~ lEET
WO91/~2 2 ~ ~ 2 ~ ~ ~ PCT/EP90/Ol~K
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 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 and polyhydroxysulphonates.
Specific examples include sodium, potassium, lithium,
ammonium and substituted ammonium salts of
ethylenediaminetetraacetic acid, nitrilitriacetic acid,
oxydisuccinic acid, CMOS, TMS, TDS, melitic acid,
benzene polycarboxylic acids and citric acid.
Preferably the level of non-soap builder material is
from 0-50% by weight of the composition, more preferred
from 5-40%, most preferred 10-35%.
SU~STITUTE SHEET
WO9l/~2 PCT/EP90/01
~3~
In the context of organic builders, it is also desirable
to incorporate polymers which are only partly dissolved,
in the aqueous continuous phase as described in EP
301.882. This allows a viscosity reduction (due 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. 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 100ml of a 5% by weight
aqueous solution of the polymer, said second polymer
also having a vapour pressure in 20% aqueous solution,
equal to or less than the vapour pressure of a reference
2% by weight or greater aqueous solution of polyethylene
glycol having an average molecular weight of 6000; said
con~ polymer having a molecular weight of at least
1000. Use of such polymers is generally described in our
EP 301,883. Typical levels are from 0.5 to 4.5% by
weight.
The viscosity of compositions according to the present
is preferably less than 1500 mPas, more preferred less
than 1000 mPas, especially preferred between 30 and 900
mPas at 21 s-1.
One way of regulating the viscosity and stability of
compositions according to the pres~nt invention is to
include viscosity regulating polymeric materials.
Viscosity and/or stability regulating polymers which are
preferred for incorporation in compositions according to
SUBSTITUTE SHEET
WO9l/00902 2 ~ PCT/E ~ /010~
the invention include deflocculating polymers having a
hydrophilic backbone and at least one hydrophobic side
chain. Such polymers are for instance described in our
copending European application EP 89201530.6
(EP 346 995).
Deflocculation polymers for use in detergent
formulations according to the present invention may be
of anionic, nonionic or cationic nature. Anionic
deflocculating polymers are preferred.
The hydrophilic backbone of the polymer is typically a
homo-, co- or ter-polymer containing carboxylic acid
groups (or more preferably) salt forms thereof), e.g.
maleate or acrylate polymers or co-polymers of these
together or with other monomer units such as vinyl
ethers, styrene etc. The hydrophobic chain or chains
typically are selected from saturated and unsaturated
alkyl chains, e.g. having from 5 to 24 carbon atoms and
are optionally bonded to the backbone via an alkoxylene
or polyalkoxylene linkage, for example a polyethoxy,
polypropoxy or butyloxy (or mixtures of same) linkage
having from 1 to 50 alkoxylene groups. Thus, in some
forms, the side chain(s) will essentially have the
character of a nonionic surfactant. Preferred anionic
polymers are disclosed in our copending European patent
application EP 89201530.6 (EP 346 995).
Preferably the amount of viscosity regulating polymer is
from 0.1 to 5% by weight of the total composition, more
preferred from 0.2 to 2~.
Compositions of the invention may advantageously
comprise a pQl~y-hydriC alcohol having from 1 to 5 carhon
atoms per molecule. Preferred C1_5 alcohols are di- or
tri- alcohols comprising three or four carbon atoms per
molecule. Especially preferred is the use of propylene
glycol and glycerol.
SUBSTITUTE SHEEl~
WO9l/~2 PCT/E ~ /01
2fi~2~S~
12
Preferably the level of C1_5 poly-hydric alcohols is
more than 1 % by weight of the composition, preferably
more than 2 %, especially preferred more than 3 %.
Generally compositions of the invention will comprise
less than 30 % by weight of the polyhydric alcohol, more
preferred less than 20 %, especially preferred less
than 15 %. Typical levels are from 4 to 10 % by weight
of the composition.
Compositions of the invention may also comprise
materials for adjusting the pH. For lowering the pH it
is preferred to use weak acids, especially the use of
organic acids is preferred, more preferred is the use of
C 1-8 carboxylic acids, most preferred is the use of
citric acid. The use of these pH lowering agents is
especially preferred when the compositions of the
invention contain enzymes such as amylases, proteases
and lipolases.
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, inorganic
salts such as sodium sulphate, and, usually present in
very minor amounts, fluorescent agents, perfumes,
germicides colourants and enzymes such as prote~s~C,
cellulases, amylases and lipases (including Lipolase
(Trade Mark) ex Novo). Suitable examples of protease
- enzymes are Savinase (ex Novo), Maxatal (gist-brocades),
Opticlean (ex MKC) or AP122 (ex Showa Denko), Alcalase,
Maxatase, Esperase, optimase, proteinase K and
subtilisin BPN. Suitable lipolases are for example
Lipolase (ex Novo), Amano lipases, Meito lipases,
Lipozym, SP 225, SP 285, Toyo Jozo lipase. Suitable
amylases are for example Termamyl (TM of Novo) and
Maxamyl. Suitable cellulases include Celluzym (ex Novo).
SUB~l 11 ~)TE SHEET
WO9l/~902 ~ 7 ~ ~ PCT/E ~ /OI~K
13
Amongst these optional ingredients, as mentioned
~- previously, are agents to which lamellar dispersions
without deflocculating polymer are highly stability-
sensitive and by virtue of the present invention,-can be
incorporated in higher, more useful amounts. These
agents cause a problem because they tend to promote
flocculation of the lamellar droplets. Examples of such
agents are fluorescers like Blankophor RKH, Tinopal LMS,
and Tinopal DNS-X and Blankophor BBM as well as metal
chelating agents, especially of the phosphonate type,
for example the Dequest range sold by Monsanto.
Compositions of the invention preferably comprise from
10 -80 % by weight of water, more preferably from 15-
60%, most preferably from 20-50 %.
Liquid detergent compositions according to the invention
are preferably physically stable in that they show less
than 2% by volume phase separation upon storage for 21
days after preparation at 25~C.
Liguid detergent compositions according to the invention
are preferably volume stable in that they show less than
25% preferably less than 10%, more preferably less than
5% volume increase during storage at a temperature
between 20 and 37~C for a period of three months after
preparation.
For obtaining good volume stability, preferably the
compositions according to the present invention also
comprise a second stabilising agent for the bleach
component. Suitable stabilisers are well-known in art
and include EDTA, Magnesium silicates and phosphonates
such as for instance the Deguest range ex Monsanto and
Naphthol ex Merck. Preferably the amoun~ of these
stabilising agents is from 0.05 to 5 % by weight of the
composition, more preferred from 0.05 to 1% of the
composition.
SUB~ TE SHE~
...
;~062 ~
Compositions o~ the present invention may comprise one
or more bleach precursor agents. A well-known example of
such an agent is TAED. Preferably the bleach precursor
agent is present in the system in at least partly
undissolved form. One way of ensuring that the precursor
is present in un~issolved form is to increase the amount
of electrolyte in the composition, therewith reducing
the solubility of the precursor in the system. Suitable
electrolytes for this purpose are for instance the at
least partially water soluble carbonate, sulphate and
halogenide salts.
In use the detergent compositions of the inventention
will be diluted with wash water to form a wash liquor
for instance fo~ use in a washing machine. The
concentration of liquid detergent composition in the
wash liquor is preferably from 0.05 to 10 %, more
preferred from 0.1 to 3% by weight.
To ensure effective detergency, the liquid detergent
compositions preferably are alkaline, and it is
preferred that they should provide a pH within the range
of about 7.0 to 12, preferably about 8 to about 11, when
used in aqueous solutions of the composition at the
recommended concentration. To meet this requirement, the
undiluted liguid composition should preferably be of a
pH above 7, for example about pH 8.0 to about 12.-5. It
should be noted that an excessively high pH, e.g. over
about pH 13, is less desirable for domestic safe'ty. If
hydrogen peroxide is present in the liquid composition,
then the pH is generally from 7.S to 10.5, preferably 8
to 10, and especially 8.5 to 10, to ensure the combined
effect of good detergency and good physical and chemical
stability. The ingredients in any such highly alkaline
detergent composition should, of course, be chosen for
alkaline stability, especially for pH-sensitive
materials such as enzymes, and a particularly suitable
SUBSTfTUTE S~T
~a~78 1
proteolytic enzyme. The pH may be adjusted by addition
of a suitable alkaline or acid material.
Compositions according to the invention may be prepared
by any mèthod for the preparation of liquid detergent
compositions. A preferred method involves the addition
of metaborate to water, which optionally comprises one
or more of the other ingredients of the formulation. The
bleach materials are preferably added as a pre-
dispersion .
The invention will now be illustrated by way of the
following Examples. In all Examples, unless stated to
the contrary, all percentages are by weight.
The following names may be registered trademarks:
Synperonic, Sokolan, Savinase, Maxatal, Opticlean,
Alcalase, Maxatase, Esperase, Optimase, Lipozym,
Maxamyl, Celluzym, Blankophor, Tinopal, Dequest and
Proxsol.
SU~S~UTE SHE~
2062781
ExamPle I
This example illustrates the stability of bleaches in
aqueous systems containing bleach in combination with
additive materials. The aqueous systems as used comprise
the same~relative amounts of ingredients that would be
present in a corresponding ready to use aqueous liquid
detergent composition. For example, composition A
comprises 20 parts of bleach materials and 40 parts of
water; a corresponding liquid detergent composition
would comprise 20 parts of bleach, 40 parts of water and
40 (up to 100) parts of detergent active materials in
combination with other ingredients. Although the
absolute stability of the bleach in the compositions
without the detergent active materials can differ from
the absolute stability of the bleach in the
corresponding detergent compositions, it is believed
that the comparison of systems without detergent active
materials provides a good indication of the relative
bleach stabilities of compositions with detergent active
materials.
Compositions A-D were prepared by adding the ingredients
to water in the listed order under stirring. The result
is a physically instable perborate dispersion from which
the undissolved bleach materials will sediment. The
continuous electrolyte phase containing the dissolved
ingredients was isolated and assessed for bleach content
and bleach stability. Since only the dissolved amount of
bleach will contribute to the decomposition of the
bleach, the results obtained for the separated
electrolyte phase are representative for the stability
of the total bleach stability in the system.
The amount of dissolved bleach in the separated
electrolyte phase was measured by iodometric titrations,
the half life time was determined on the basis of
SIJB~ 1 1 ~UTE ~
~06~78 1
measurements of the amount of solubilised bleach in the
separated electrolyte phase as a function of time.
The following results were obtained:
TABLE 1 Perborate solubility and solubility and
stability at 37 ~C.
COMPONENT (wt parts) COMPOSITION
A B C D
Na-metaborate l) -- 2.6 2.6 --
Glycerol -- -- 3.5 3.5
Na-perborate.4H2O 20 20 20 20
water 40 40 40 40
pH2) 9.8 11.0 10.2 9.6
dissolved perbotate3) 2.10 1.85 1.84 5.3
t(1/2) days <<1 164) 2 0.82
decomposed bleach5) >1.650.057 0.46 3.24
1) Na metaborate 4H20 ex BDH Chemicals
2) of total system at t=0
3) wt % of dissolved perborate in isolated electrolyte
phase at t=0.
4) extrapolated.~5 5) in weight % of the total bleach in the isolated
electrolyte phase after 1 day.
These results illustrate that composition A, comprising
the bleach material in water in the absence of
metaborate, results in a high level of dissolved bleach
in the separated electrolyte phase and in a very short
life time of the dissolved bleach material. Composition
D containing glycerol and bleach in water in the absence
of metaborate also provides a high level of dissolved
bleach which decomposes in less than 1 day. Composition
B contains metaborate in combination with bleach
materials, this results in a low level of dissolved
bleach and a long life-time of the dissolved bleach. The
~IJ~ I ~ I UTE SHEET
2n627~l
18
total amount of decomposed bleach is low. Composition C,
which additionally comprises Glycerol has the advantage
of a lower pH; this is especially preferred for enzyme
containing liquid detergent compositions. Also this
composition is more stable than the corresponding
composition without metaborate. These results indicate
that liquid detergent compositions corresponding to the
tested compositions would have a greater bleach
stability in the presence of metaborate.
Example 2
Compositions were prepared and the amount of dissolved
bleach and its stability was measured as in example 1.
The following results were obtained:
TABLE 2 Bleach stability at 37~C
COMPONENT (wt parts) COMPOSITION
E F G H I J
Na-metaborate.4H20 2.6 2.6 2.6 2.6 2.6 2.6
Glycerol -- -- -- -- -- 3.5
citric acid -- 0.93 1.53 -- -- 0.31
sulphuric acid -- -- -- 0.65 1.13 --
Na-perborate.4H2o 20 20 20 20 20 20
water 40 40 40 40 40 40
pH 11.0 9.0 8.0 9.08.0 9.0
dislvd bleach % 1.85 2.08 3.52 2.23.88 2.15-
t(1/2) days 16*) 15*) 6 1.2<<1 6
decomposed bleach ~ 0.057 0.069 0.29 0.95 >2.9 0.18
*) extrapoiated.
This example illustrates the effect of pH lowering
agents on bleach stability. Tests F-G and J show that
the pH of a bleach and metaborate composition can
advantageously be decreased by using citric acid; the
obtained compositions are of acceptable stability.
TUTE SHEET
2062781
Lowering the pH of the compositions with sulphuric acid
(tests H-I) leads to instability of the bleach
especially at low pH values.
Example 3
Compositions were prepared and assessed for bleach
stability as in example 1. The following results were
obtained
Table 3 Bleach stability at 37 ~C
COMPONENT (wt parts) COMPOSITION
K L M
Na-metaborate.4H20 5.0 5.0 5.0
DEQUEST 2066 -- 0.2 --
Mg-trisilicate -- -- 0.2
Na-perborate.4H2O 20 20 20
water 40 40 40
pH 11.1 11.1 11.1
disvld bleach % 1.83 1.71 2.03
t(l/2) days 52 80*) 65
decomposed bleach % 0.018 0.011 0.016
*) extrapolated.
These results show that the stability of bleach in the
presence of metaborate can even be further improved by
addition of a further stabiliser such as Dequest or Mg-
silicate.
S~ TUTE SHEEr
WO91/00902 PCT/EP90/010
~ple 4
The following liquid detergent compositions may beformulated by adding the ingredients to water in the
listed order:
Ingredient Basic formulation (% wt)
1 2 3 4 5
Na DOBS 8.5 8.5 7.5 7.5 ~ 4.3
Synperonic A7 2.0 2.0 3.0 3.0 6.0
Na Oleate 2.7 10.8 8.1 10.8 --
Glycerol 5.0 5.0 5.0 5.0 5.0
Na-metaborate 3.5 3.5 3.5 3.5 3.5
STP 22 22 22 22 22
Na-perborate.4H2O 15 10 12 10 20
Polymer *) 1.0 1.0 1.0 0.5 2.0
water ---up to 100---
*) Polymer A-2 as described in EP 89201530.6
(EP 346 995).
S~Bsr~ E S~
WO91/00902 . PCT/EP90/01~K
21
Example 5
the following formulations may be prepared as in example
4:
Table 5
Inqredient Com~osition %wt
1 2
Na DoBS 9.1 17.3
Synperonic A7 3.6 1.8
Na Stearate -- 0.9
Glycerol 8.1 3.0
NaOH 1.0 --
Na-metaborate 5.8 2.0
Na-perborate 20 10
Na-citrate -- 5.0
citric acid 1.5 --
Zeolite A4 25.3 30.0
NaCMC -- 0.3
Tinopal CBS-X -- 0.13
Perfume -- 0.22
Alcalase 2.34L -- 0.5
Polymer *) 0.5 0.5
water --to 100%
*) polymer A-11 as described in EP 89201530.6
(EP 346 995).
Sl~ J 1-~ ShcET
WO9l/00902 ~ PCT/EP90/01
Example 6 -
The f-llowing detergent compositions may be prepared as
in example 4.
Inqredient Composition % wt
1 2
NaDoBS 10.2 --
K DoBS -- 10.7
Synperonic A7 19.3 19.3
Na Oleate 10.3 --
K Oleate -- 10.3
Glycerol 5.0 5.0
Na-metaborate 3.5 3.5
Na-perborate.4H20 10.0 15.0
Na-citrate 2aq 10.0 --
Na2C~3 ~~ 4.0
Sokolan CP5 2.5 --
Dequest 2066 0.4 --
Mg-silicate -- 0.4
Silicon DB 100 0.3 0.3
Tinopal CBS-X 0.5 0.5
Savinase 0.1 0.1
Amylase 0.1 0.1
Perfume 0.1 0.1
Dye 0.3 0.3
Polymer *) 1.0 1.0
*) polymer A-ll as disclosed in EP 89201530.6
(EP 346 995).
S~B~ ~ E S~E~
'- 20627~31
23
Examples 7-12
The following compositions were prepared by adding the electrolyte together with the minor
ingredients except for the perfume and the enzymes to water of elevated temperature,
5 followed by the addition of the de~el~,ent active material as a premix under stirring and
thereafter cooling the mixture and adding the enzymes, perfumes and the bleach.
INGREDIENT(%WT) Z 8 2 10 11 12
Na-Dobs 21 21 23.3 21 21 21
Synperonic 7 9 9 10 9 9 9
Glycerol 3.5 - 3.9 3 5
Metaborate 2.62.62.9 2.6 2.62.6
Nacitrate/Citric Acidl) 9.89.811.19.89.89.8
Dequest 2060S (as 100%) 0.4 0.4 0.4 0.4 0.4 0.4
Na-perborate tetrahydrate3) 20 20 ~~ 20 20 --
Na-perborate monohydrate -- -- 7.2 -- -- 10
Enzyme, Alcalase 0.80.80.80.80.80.8
CaCl2-2H20 0.2 0.2 0.20.2 0.2 0.2
Fluorescer, Tinopal CBSX 0.1 0.1 0.10.1 0.1 0.1
Silicon, Dow Corning DB100 0.3 0.3 0.30.3 0.3 0.3
Perfume 0.3 0.3 0.30.3 0.3 0.3
deflocculating polymer4) 1 1 1.1
ethanol -- -- -- 2.5 2.5 --
water balancc
pH 9 9 9 9 9 9
1) This mixture is used to adjust the final pH
2) Expressed as % of analysed enzyme level in the fresh sample.
3) as 100 % perborate, added as a dispersion (Proxsol ex ICI, approximate 65% perborate
dispersion in water with an average perborate particle size of 40 micrometer).
4) Deflocculating polymer of formula I of EP 346 995, wherein X=50, y=0, R5=H, R6=CH3,
Rl= -CO-O, R2 and R3 are absent, R4= -Cl2H25, mW= 7,500.
X
206278 1
24
5) wt% -approximate- of total perborate, obtained by removal of the undissolved bleach
particles by mild centrifugation.
5 6) Not measured
The obtained products had the following characteristics:
7 8 9 10 11 12
Volume stability (% volume 4 3 0 0 0 0
increase, 3 months (25~C)
clearlayerseparation no no no no no no
(3 weeks 37~C)
solid sedimentation no no no no no no
(3 weeks 37~C)
Viscosity21 s-l 1,350 710 800 850 1330 760
Viscosity 104s-l 200,000 n.m6) n.m n.m n.m n.m
dissolved perborates5) 3 1.5 8 1.5 3 6
bleach activity 99 99 96 98 98 97
(2 months ambient T)
enzyme activity 65 62 76 83 70 n.m
(2 months ambient T)2)
,i Xj
206278 1
Exam~le 13
The composition of example 7 was prepared, while CaCl2
was used at a level of 1% in combination with 0.8% of
enzymes, whereby the following types of enzymes were
used.
Esperase liquid (Esperase L8.0 ex Novo)
Savinase liquid (Savinase 16.0 LDX ex Novo)
Savinase slurry (Savinase 16.0 SL ex Novo)
Alcalase liquid (Alcalase 2.34 LDX ex Novo)
It was found that the enzyme stability was dependant on
the type of enzyme used, whereby an increase in enzyme
stability was found in the following order:
Esperase > Savinase slurry > Savinase liquid > Alcalase
SUB~ I I I I~ITE SHEET
