Note: Descriptions are shown in the official language in which they were submitted.
~ W O 94/19444 215 6 8 2 9 PCTrUS94/01528
H~GH ACTIVE ENZYHE GRANULATES
Recently there has been considerable interest within the
detergent industry in the production of detergent powders
having relatively high bulk density, for example 600 g/litre
and more. Also consumers and sale centers prefer highly
concentrated detergent powder compositions. Furthermore the
need for detergent compositions which exhibit not only good
cleaning properties, but also good fabric-softening
performance, and other fabric care benefits, is well-
established in the art. The new generation of detergent
compositions is now being marketed, which can be best pictured
as "compact detergents". These so-called compact detergents
have been given a variety of trade names such as "Ultra",
"Supra", "Micro" etc. The particularity of such detergent
compositions is their relatively high density compared to
conventional detergent compositions, and their ability to
WO94/194~ PCT~S94/01528 _,~
'~56829
achieve the same efficiency than conventional detergent
compositions by using a considerably lesser amount of "compact"
detergent composition. This particularity is best reflected, in
terms of composition, by a relatively low amount of inorganic
filler salt. The efficiency of such "compact" detergent
compositions is best achieved by eliminating the pre-wash cycle
and by using dispersing and diffusing devices, which are put
directly in the drum of the washing machine at the start of the
main washing cycle.
The trends, begun in the last four years, are coming along in
the detergents industry with environmentalism and concentrated
detergents going hand in hand.
Some advantages of concentrated detergents powder
compositions are :
a. smaller containers or packs provide easier handling
b. smaller packs create space for placing more packs per
unit space
c. less packing material which is advantageous to the
environment
In order to achieve smaller packs with concentrated
powdered detergents in principle the following possibilities
exist :
a. using more active components
b. avoiding non-functional ingredients
c. minimizing the amount of air in the packet
Essential ingredients in the formulation of today's heavy
duty detergent compositions are :
a. surface-active agents
b. builders
c. enzymes
d. bleaching agents
~ W094/194~ 215 ~ ~ 2 9 PCT~S94/01528
The specific description of these components can be found
hereafter.
In addition to above-mentioned ingredien's the detergent
composition may also contain optical whitening agents, anti-
redeposition agents, polycarboxylate polymers, stabilizers,
anti-oxidants, sud-suppressors, perfume and the like.
Concentrated detergent powder compositions are described
for instance in EP 340,013 (Unilever) and EP 509,787
(Unilever).
In EP 340,013 is disclosed a granular detergent
composition which is preferably free of phosphate builders,
having a bulk density of at least 650 g/litre and comprises
a)from 17 to 35 wt% of non-soap detergent-active material
(consisting at least partially of anionic detergent-active
material) and
b)from 28 to 45 wt% (anhydrous basis) of crystalline or
amorphous sodium aluminosilicate, the weight ratio of (b) to
(a) being from 0.9:1 to 2.6:1. The particle porosity is
preferably less than 0.20. The composition may be prepared by
granulation and densification in a high-speed mixer/granulator.
In EP 509,787 is disclosed concentrated detergent powder
compositions having a bulk density of above 600 g/l, preferably
at least 610 g/l, more preferably around 850g/l as shown in
Examples III-VII, and comprising a surfactant, a detergency
builder, enzymes, a peroxygen compound bleach, and specific
manganese complex as effective bleach catalyst.
Use of these catalysts can make the detergent powder more
compact, i.e. reduce the pack volume.
Since nowadays powder detergent compositions are getting
more and more concentrated and more compact, as described in
the two above-mentioned publications, this results in much
WO94/194~ 21 S 6 8 ~ ~ PCT~S94/01528
lower recommended usages (gram detergent/wash) than with non-
compact or medium-compaCt detergent compositions. However, at
the same time the lower product usage has to deliver at least
the same wash performance. As a consequence thereof, the level
in finished product for some of the ingredients, especially for
the enzymes used, has to be drastically increased without
losing performance.
The amount of enzyme described in both mentioned
applications is substantial. For instance in EP 509,787 the
amount of proteolytic enzymes used, vary from 0.001% to 10% by
weight, but preferably from 0.01% to 5% by weight, depending
upon their activity.
The technical problem with these amounts in the finished
compact products is how to circumvent the negative impact of
the enzyme granulates on the whiteness of the detergent
composition. Such a clearly negative impact on the whiteness of
the detergent composition has never been distinguished in the
prior art.
The more concentrated the compact compositon will be hence
the lower the recommended usage, the more enzyme granulate has
to be added in order to achieve the same wash performance.
However higher levels of enzyme granulates have a clearly
negative impact on the whiteness of the finished product as
illustrated hereafter.
In order to show that using the same volume level, the
amount of granulates needed comprising an enzyme has to be
increased the following comparison is made between NON-compact,
MEDIUM-compact and HIGH-compact density powders.
NON compact detergent Compact MEDIUMCompact HIGH density
density
d = 600g/L d = 700g/L d = 850g/L
recommended usage: recommended usage:recommended usage:
1 80g/wash 1 26g/wash 95g/wash
WO94/194~ 21~ 82 9 PCT~S94/01528
To keep the protease concentration/L wash liquor constant, the following is
required for finished products when applying e.g. Savinase 4T granulates:
Savinase 4T
lg/100 9 detergent 1.49/100 9 detergent 1.99/100 9 detergent
OR: expressed in g enzyme granulates/L detergent composition:
69/ L detergent 9.89 / L detergent 15.89/ L detergent
This clearly illustrates how, on an equal volume basis, the level of enzyme
granulates has been increased by a factor 2.6x when moving from "fluffy" to
very compact detergents ( d at least equal to 800). But also within the segment
of compact detergents, increasing the density from 700 to 800 and higher and
at the same time reducing the recommended usage from 126 to 9S g/wash
requires an increase of 1.6X in the level of enzyme granulates/ L detergent
composition.
The following table with Hunter L,a,b values visualizes the huge difference in
whiteness between enzyme granulates and detergent, hence indicating the
clearly negative impact of the enzyme granulates on the whiteness of the
detergent composition:
Savinase 4T Savinase 10T reference
compact
detergent (d=
850)
L 73.8 71.3 88.0
a 2.1 1.5 1.7
b 3.8 1.6 -1.6
¦ Whiteness (~) ¦ 62.4 ¦ 66.5 ¦ 92.8
( ~ ~ ) Whiteness = L.-3b
The solution to above-mentioned problem is to use high
active enzyme granulates revealing that the negative impact on
the physical appearance of the detergent powder is no longer
noticeable. In order to keep the above-recognized negative
WO94/194~ PCT~S94/01528
2~ G82~ 6
impact on whiteness below the perceivable threshold it is
necessary according to our invention to limit the level of
enzyme granulates in powder detergent composition with a
density of about 800g/L and more preferably at ~east 850g/L to
a maximum of 20g per liter detergent composition. Preferably
the level of enzyme granulates/ L detergent composition is
15 g/L detergent composition, whereas the most preferred level
of enzyme granulates/L detergent composition is 10g/L detergent
composition.
The term "level of enzyme granulates" used herein refers
to the sum of enzymes used in detergents i.e. prot~AC~s,
lipases, amylases, cellulases, peroxidases, oxidases, etc. This
also includes single enzyme granulates and mixtures of single
enzyme granulates as well as so-called co-prills (e.g. protease
plus lipase in one single prill).
The term "high active enzyme granulate" means that an
enzyme is incorporated in the form of granules or so-called
prills, in an amount such that the final detergent composition
has a high enzymatic activity per liter of final product. When
applying high alkaline proteases, e.g. SAVINASETM, ~Y~r.TM,
OPT~C~EANTM, DU~AZYMTM or MAXAPEMTM etc, the concentration of
protease in the granulate has to be 2% or higher. Preferred
examples are the protease granulates Savinase 8T and Savinase
10T, wherein for instance Savinase 8T means 8 KNPU/g as 8 kilo
Novo protease units per gram of granulate. Savinase TM has a
specific activity of 395 KNPU/g.
According to our invention, a further improvement is
obtained by adding an extra amount of whitener, e.g. TiO2 to
the preferred enzyme granulates. As a result thereof the Hunter
L, a, b values (for using Savinase 10T) are 78.9, 0.0 and -0.01
respectively. The whiteness (L-3b) is therefore expressed as
78.9.
An additional advantage using high active enzymes as
described above is that the overall level of Tio2 in the
_ WO94/194~ PCT~S94/01528
2156~29
finished product is much lower. For instance in high active
enzyme granulates the TiO2 amount is 9.1% versus 5.2% for the
low active enzyme granulates by which the percentage Tio2 in
the finished product is 0.0~4% vs. 0.155%.
So substantial less TiO2 can be used in order to obtain
the same whiteness effect of the enzyme granulates. Using dyed
enzyme granulates, like green and/or blue coloured granulates
even the addition of the current low level of Tio2 can be
further decreased or even omitted.
The detergent composition of the invention may be
formulated in any convenient form, preferably as a powder.
Detergent compositions of the invention may contain as above-
mentioned other detergent ingredients known in the art as e.g.
builders, bleaching agents, bleach activators, anti soil
redeposition agents, perfumes, etc.
Additionally detergent compositions comprise surfactants
which may be of the anionic, non-ionic,amphoteric, cationic or
zwitteronic type as well as mixtures of these types.
A typical listing of these surfactants is given in US
Patent 3,664,961 issued to Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly suitable
herein, especially mixtures of sulphonate and sulphate
surfactants in a weight ratio of from 5:1 to 1:2, preferably
from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred
sulphonates include alkyl benzene sulphonates having from 9 to
15, especially 11 to 13 carbon atoms in the alkyl radical, and
alpha-sulphonated methyl fatty acid esters in which the fatty
acid is derived from a C12-C18 fatty source preferably from a
C16-C18 fatty source. In each instance the cation is an
alkali metal, preferably sodium. Preferred sulphate
surfactants are alkyl sulphates having from 12 to 18 carbon
atoms in the alkyl radical, optionally in admixture with
ethoxy sulphates having from 10 to 20, preferably 10 to 16
WO94/194~ ~15 6 82 9 PCT~S94/01528 ~
carbon atoms in the alkyl radical and an average degree of
ethoxylation of 1 to 6. Examples of preferred alkyl sulphates
herein are tallow alkyl sulphate, coconut alkyl sulphate, and
C14_~5 alkyl sulphates. An example of a preferred ethoxy
sulphate is the so-called AE3S (C12_1s alkyl 3 times
ethoxylated sulphate). The cation in each instance is again an
alkali metal cation, preferably sodium.
One class of nonionic surfactants useful in the present
invention are condensates of ethylene oxide with a hydrophobic
moiety to provide a surfactant having an average hydrophilic-
lipophilic balance (HLB) in the range from 8 to 17, preferably
from 9.5 to 13.5, more preferably from 10 to 12.5. The
hydrophobic (lipophilic) moiety may be aliphatic or aromatic
in nature and the length of the polyoxyethylene group which is
condensed with any particular hydrophobic group can be readily
adjusted to yield a water-soluble compound having the desired
degree of balance between hydrophilic and hydrophobic
elements.
Especially preferred nonionic surfactants of this type are
the Cg-Cl5 primary alcohol ethoxylates containing 3-8 moles of
ethylene oxide per mole of alcohol, particularly the C14-C15
primary alcohols containing 6-8 moles of ethylene oxide per
mole of alcohol and the C12-C14 primary alcohols containing 3-
5 moles of ethylene oxide per mole of alcohol.
Another c~ass of nonionic surfactants comprises alkyl
polyglucoside compounds of general formula
RO (cnH2no)tzx
wherein Z is a moiety derived from glucose; R is a saturated
hydrophobic alkyl group that contains from 12 to 18 carbon
atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4,
the compounds including less than 10% unreacted fatty alcohol
and less than 50% short chain alkyl polyglucosides. Compounds
of this type and their use in detergent are disclosed in EP-B
0 070 077, 0 075 996 and 0 094 118.
~_ W094/19~ 215 ~ 8 2 9 PCT~S94/01528
-
Also suitable as nonionic surfactants are poly hydroxy fatty
acid amide surfactants of the formula R2 - C - N - Z,
Il
O Rl
wherein R1 is H, C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl or a mixture thereof, R2 is C5_31 hydrocarbyl, and Z is
a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least 3 hydroxyls directly connected to the chain, or
an alkoxylated derivative thereof. Preferably, R1 is methyl,
R2 is a straight Cl1_15 alkyl or alkenyl chain such as coconut
alkyl or mixtures thereof, and Z is derived from a reducing
sugar such as glucose, fructose, maltose, lactose, in a
reductive amination reaction.
A further class of surfactants are the semi-polar
surfactants such as amine oxides. Suitable amine oxides are
selected from mono C8-C20, preferably C10-Cl4 N-alkyl or
alkenyl amine oxides and propylene-1,3-diamine dioxides
wherein the remaining N positions are substituted by methyl,
hydroxyethyl or hydroxypropyl groups.
Another class of surfactants are amphoteric surfactants,
such as polyamine-based species.
Cationic surfactants can also be used in the detergent
compositions herein and suitable quaternary ammonium
surfactants are selected from mono C8-C16, preferably C10-Cl4
N-alkyl or alkenyl ammonium surfactants wherein remaining N
positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups.
Mixtures of surfactant types are preferred, more especially
anionic-nonionic and also anionic-nonionic-cationic mixtures.
Particularly preferred mixtures are described in British
Patent No. 2040987 and European Published Application No. 0
087 914. The detergent compositions can comprise from 1%-70%
W094/194~ 2 15 6 8 2 9 PCT~S94/01528
by weight of surfactant, but usually the surfactant is present
in the compositions herein an amount of from 1% to 30%, more
preferably from 10-25~ by weight.
BUILDER
Builder materials will typically be present at from 10% to
60~ of the detergent compositions herein. The compositions
herein are free or substantially free of phosphate-containing
builders (substantially free being herein defined to
constitute less than l~ of the total detergent builder
system), and the builder system herein consists of water-
soluble builders, water-insoluble builders, or mixtures
thereof.
Water insoluble builders can be an inorganic ion exchange
material,commonly an inorganic hydrated aluminosilicate
material, more particularly a hydrated synthetic zeolite such
as hydrated Zeolite A, X, B or HS.
Preferred aluminosilicate ion-exchange materials have the
unit cell formula
Mz [(AlO2)Z (sio2)y] xH20
wherein M is a calcium-exchange cation, z and y are at least
6; the molar ratio of z to y is from l.0 to 0.5 and x is at
least 5, preferably from 7.5 to 276, more preferably from lO
to 264. The aluminosilicate materials are in hydrated form
and are preferably crystalline containing from 10% to 28%,
more preferably from 18% to 22% water.
The above aluminosilicate ion ~xchAnge materials are further
charaterized by a particle size diameter of from O.l to lO
micrometers, preferably from 0.2 to 4 micrometers. The term
"particle size diameter" herein represents the average
particle size diameter of a given ion exchange material as
determined by conventional analytical techniques such as, for
example, microscopic determination utilizing a scanning
electron microscope. The aluminosilicate ion exchange
_ WO94/194~ 215 6 ~ 2 9 PCT~S94/01528
11
materials are further characterized by their calcium ion
exchange capacity, which is at least 200 mg equivalent of
CaCO3 water hardness/g of aluminosilicate, calculated on an
anhydrous basis, and which generally is in the range of from
300 mg eq./g to 352 mg eq./g. The aluminosilicate ion
exchange materials herein are still further characterized by
their calcium ion exchange rate which is described in detail
in GB-1,429,143.
Aluminosilicate ion exchange materials useful in the
practice of this invention are commercially available and can
be naturally occurring materials, but are preferably
synthetically derived. A method for producing aluminosilicate
ion exchange materials is discussed in US Patent No.
3,985,669. Preferred synthetic crystalline aluminosilicate
ion exchange materials useful herein are available under the
designation Zeolite A, Zeolite B, 2eolite X, Zeolite HS and
mixtures thereof. In an especially preferred embodiment, the
crystalline aluminosilicate ion exchange material is Zeolite A
and has the formula
Nal2t(A1~2)12 tSio2)12] xH20
wherein x is from 20 to 30, especially 27. Zeolite X of
formula Na86 [(Alo2)g6(sio2)lo6] - 10
.276H20 is also suitable, as well as Zeolite HS of formula Na6
[(A102)6(SiO2)6] 7-5 H2O)-
Another suitable water-insoluble, inorganic builder material
is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a
crystalline layered silicate consisting of sodium silicate
(Na2Si2O5). The high Ca++/Mg++ binding capacity is mainly a
cation exchange mechanism. In hot water, the material becomes
more soluble.
The water-soluble builder can be a monomeric or oligomeric
carboxylate chelating agent.
wo 94/194~ ~568~9 12 PCT~S94/01528
Suitable carboxylates containing one carboxy group include
lactic acid, glycolic acid and ether derivatives thereof as
disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
Polycarboxylates containing two carboxy groups include the
water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, maleic acid, diglycollic acid,
tartaric acid, tartronic acid and fumaric acid, as well as the
ether carboxylates described in German Offenlegenschrift
2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the
sulfinyl carboxylates described in Belgian Patent No. 840,623.
Polycarboxylates containing three carboxy groups include, in
particular, water-soluble citrates, aconitrates and
citraconates as well as succinate derivatives such as the
carboxymethyloxysuccinates described in British Patent No.
1,379,241, lactoxysuccinates described in Netherlands
Application 7205873, and the oxypolycarboxylate materials such
as 2-oxa-1,1,3-propane tricarboxylates described in British
Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Patent No. 1,261,829,
1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarbQxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the
sulfosuccinate derivatives disclosed in British Patent Nos.
1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and
the sulfonated pyrolysed citrates described in British Patent
No. 1,082,179, while polycarboxylates containing phosphone
substituents are disclosed in British Patent No. 1,439,000.
Alicyclic and heterocyclic polycarboxylates include
cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide
pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-
tetracarboxylates, 2,5-tetrahydrofuran -cis - dicarboxylates,
2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-
hexane -hexacarboxylates and and carboxymethyl derivatives of
polyhydric alcohols such as sorbitol, mannitol and xylitol.
Aromatic polycarboxylates include mellitic acid, pyromellitic
CA 021~6829 1999-02-22
acid and the phthalic acid derivatives disclosed in British
Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxy-
carboxylates containing up to three carboxy groups per
molecule, more particularly citrates.
Preferred builder systems for use in the present compositions
include a mixture of a water-insoluble aluminosilicate builder
such as zeolite A, and a water-soluble carboxylate chelating
agent such as citric acid.
Other builder materials that can form part of the builder
system for the purposes of the invention include inorganic
materials such as alkali metal carbonates, bicarbonates,
silicates, and organic materials such as the organic
phosphonates, amino polyalkylene phosphonates and amino
polycarboxylates.
Other suitable water-soluble organic salts are the homo- or
co-polymeric acids or their salts, in which the polycarboxylic
acid comprises at least two carboxyl radicals separated from
each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000 and
their copolymers with maleic anhydride, such copolymers having
a molecular weight of from 20,000 to 70,000, especially about
40,000.
OPTIONAL INGREDIENTS
The present compositions will typically include optional
ingredients that normally form part of detergent compositions.
Antiredeposition and soil suspension agents, optical
brighteners, bleaches, bleach activators, suds suppressors,
anticracking agents, dyes and pigments are examples of such
optional ingredients and can be added in varying amounts as
desired.
, . . ... ,. . . ., . . .. . ._ . .... ..
WO941194~ 2 15 6 8 2 9 14 PCT~S94/01528
Antiredeposition and soil suspension agents suitable herein
include cellulose derivatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcellulose, and homo- or
co-polymeric polycarboxylic acids or their salts. Polymers of
this type include the polyacrylates and maleic anhydride-
acrylic acid copolymers previously mentioned as builders, as
well as copolymers of maleic anhydride with ethylene,
methylvinyl ether or methacrylic acid, the maleic anhydride
constituting at least 20 mole percent of the copolymer. These
materials are normally used at levels of from 0.5% to 10% by
weight, more preferably from 0.75~ to 8%, most preferably from
1% to 6% by weight of the composition.
Preferred optical brighteners are anionic in character,
examples of which are disodium 4,41-bis-(2-diethanolamino-4-
anilino -s- triazin-6-ylamino)stilbene-2:21 disulphonate,
disodium 4, - 41-bis-(2-morpholino-4-anilino-s-triazin-6-
ylaminostilbene-2:21 - disulphonate, disodium 4,41
- bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:21 -
disulphonate, monosodium 41,411 -bis-(2,4-dianilino-s-triazin-
6 ylamino)stilbene-2-sulphonate, disodium 4,41 -bis-(2-
anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-
ylamino)stilbene-2,21 - disulphonate, disodium 4,41 -bis-(4-
phenyl-2,1,3-triazol-2-yl)-stilbene-2,21 disulphonate,
disodium 4,41bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-
triazin-6-ylamino)stilbene-2,21disulphonate and sodium
2(stilbyl-411-(naphtho-11,21:4,5)-1,2,3 - triazole-211-
sulphonate.
Any particulate inorganic perhydrate bleach can be used, in
an amount of from 3% to 40% by weight, more preferably from 8%
to 25% by weight and most preferably from 12% to 20% by weight
of the compositions. Preferred examples of such bleaches are
sodium perborate monohydrate and tetrahydrate, percarbonate,
and mixtures thereof.
W0 94/19444 ~ 1 ~ 6 ~ 2 9 PCTJUS94/01528
Another preferred separately mixed ingredient is a peroxy
carboxylic acid bleaching agent and salts thereof, which is
preferably added in a prilled or agglomerated form.
Peroxygen bleaching agents are preferably combined with
bleach activators, which lead to the in situ production in
aqueous solution (i.e. during the washing process of the
peroxy acid corresponding to the bleach activator). Examples
of suitable compounds of this type are disclosed in British
Patent Nos. 1586769 and 2143231 and a method for their
formation into a prilled form is described in European
Published Patent Application No. 0 062 523. Preferred
examples of such compounds are tetracetyl ethylene diamine and
sodium 3, 5, 5 trimethyl hexanoyloxybenzene sulphonate.
Bleach activators are normally employed at levels of from
0.5% to 10% by weight, more frequently from 1% to 8% and
preferably from 2% to 6% by weight of the composition.
Another optional ingredient is a suds suppressor,
exemplified by silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated
polysiloxane materials while silica is normally used in finely
divided forms exemplified by silica aerogels and xerogels and
hydrophobic silicas of various types. These materials can be
incorporated as particulates in which the suds suppressor is
advantageously releasably incorporated in a water-soluble or
water-dispersible, substantially non-surface-active detergent
impermeable carrier. Alternatively the suds suppressor can be
dissolved or dispersed in a liquid carrier and applied by
spraying on to one or more of the other components.
As mentioned above, useful silicone suds controlling agents
can comprise a mixture of an alkylated siloxane, of the type
referred to hereinbefore, and solid silica. Such mixtures are
prepared by affixing the silicone to the surface of the solid
silica. A preferred silicone suds controlling agent is
- 2 ~ ~ 6 ~ 2 g 16 PCT~S94101528 ~-
represented by a hydrophobic silanated (most preferably
trimethyl-silanated) silica having a particle size in the
range from 10 millimicrons to 20 millimicrons and a specific
surface area above 50 m2/g intima'ely admixed with dimethyl
silicone fluid having a molecular weight in the range from
about 500 to about 200,000 at a weight ratio of silicone to
silanated silica of from about 1:1 to about 1:2.
A preferred silicone suds controlling agent is disclosed in
Bartollota et al. U.S. Patent 3,933,672. Other particularly
useful suds suppressors are the self-emulsifying silicone suds
suppressors, described in German Patent Application DTOS
2,646,126 published April 28, 1977. An example of such a
compound is DC-544, commercially availably from Dow Corning,
which is a siloxane/glycol copolymer.
The suds suppressors described above are normally employed
at levels of from 0.001% to 2% by weight of the composition,
preferably from 0.01% to 1% by weight. The incorporation of
the suds modifiers is preferably made as separate
particulates, and this permits the inclusion therein of other
suds controlling materials such as C20-C24 fatty acids,
microcrystalline waxes and high MW copolymers of ethylene
oxide and propylene oxide which would otherwise adversely
affect the dispersibility of the matrix. Techniques for
forming such suds modifying particulates are disclosed in the
previously mentioned Bartolotta et al U.S. Patent No.
3,933,672.
Other useful polymeric materials are the polyethylene
glycols, particularly those of molecular weight 1000-10000,
more particularly 2000 to 8000 and most preferably about 4000.
These are used at levels of from 0.20% to 5% more preferably
from 0.25% to 2.5% by weight. These polymers and the
previously mentioned homo- or co-polymeric polycarboxylate
salts are valuable for improving whiteness maintenance, fabric
ash deposition, and cleaning performance on clay,
~- WO94/194~ 2 1 ~ ~ 8 2 9 PCT~S94/01528
17
proteinaceous and oxidizable soils in the presence of
transition metal impurities.
Soil release agents useful in compositions of the present
invention are conventionally copolymers or terpolymers of
terephthalic acid with ethylene glycol and/or propylene glycol
units in various arrangements. Examples of such polymers are
disclosed in the commonly assigned US Patent Nos. 4116885 and
4711730 and European Published Patent Application No. 0 272
033. A particular preferred polymer in accordance with EP-A-0
272 033 has the formula
(CH3(pEG)43)o.7s(poH)o.2s[T-po)2.8(T-pEG)o.4]T(
H)0.2s((pEG)43cH3)o.75
where PEG is -(OC2H4)O-,PO is (OC3H6O) and T is (pcOC6H4CO).
Certain polymeric materials such as polyvinyl pyrrolidones
typically of MW 5000-20000, preferably 10000-15000, also form
useful agents in preventing the transfer of labile dyestuffs
between fabrics during the washing process.
Fabric softening agents can also be incorporated into
detergent compositions in accordance with the present
invention. These agents may be inorganic or organic in type.
Inorganic softening agents are exemplified by the smectite
clays disclosed in GB-A-1,400,898. Organic fabric softening
agents include the water-insoluble tertiary amines as
disclosed in GB-A-1514276 and EP-B-0 011 340 and their
combination with mono C12-C14 quaternary ammonium salts are
disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-
chain amides as disclosed in EP-B-0 242 919. Other useful
organic ingredients of fabric softening systems include high
molecular weight polyethylene oxide materials as disclosed in
EP-A-0 299 575 and 0 313 146.
Levels of smectite clay are normally in the range from 5% to
20%, more preferably from 8% to 15% by weight with the
material being added as a dry mixed component to the remainder
18 2 1 568 29
of the formulation. Organic fabric softening agents such as the
water-insoluble tertiary amines or di-long-chain amide materials
are incorporated at levels of from 0.5~ to 5~ by weight, normally
from 1~ to 3~ by weight whilst the high molecular weight
polyethylene oxide materials and the water-soluble cationic
materials are added at levels of from 0.1~ to 2~, normally from
0.15% to 1.5~ by weight. These materials are normally added to
the spray dried portion of the composition, although in some
instances it may be more convenient to add them as a dry mixed
particulate, or spray them as a molten liquid on to other solid
components of the composition.
In a particularly preferred embodiment the present invention
provides a highly concentrated granular detergent composition
comprising: (a) less than 20 g/L detergent composition of enzyme
granulates, wherein the enzyme granulates in said highly
concentrated detergent composition comprise enzyme granulates
having at least 2~ of protease enzyme; and (b) detergent
composition ingredients selected from the group consisting of
detersive surfactants, builders, bleaches, bleach activators, and
mixtures thereof; and wherein further said highly concentrated
detergent composition has a density of at least about 800 g/L and
a Hunter Whiteness value of greater than 66.5.
MAKING PROCESS
Compositions according to the present invention can be made
via a variety of methods including dry mixing, spray drying,
agglomeration and granulation and combinations of any of these
techniques.
PREFERRED MAKING PROCESS
A method of making the compositions herein involves a
combination of spray drying, agglomeration in a high speed mixer
and dry mixing.
A first granular component containing a relatively insoluble
anionic surfactant is spray dried and part of the spray dried
product is diverted and subjected to a low level of nonionic
surfactant spray on before being reblended with the remainder. A
second granular component is made by dry neutralisation of an
anionic surfactant acid using sodium carbonate as the
19 2~56829
neutralising agent in a continuous high speed blender such as a
Lodige KM mixer. The first and second components together with
other dry mix ingredients such as the carboxylate chelating
agent, inorganic peroxygen bleach, bleach activator, soil
suspension agent, silicate and enzyme are then fed to a conveyor
belt from which they are transferred to a horizontally rotating
drum in which perfume and silicone suds suppressor are sprayed on
to the product. In highly preferred compositions, a further drum
mixing step is employed in which a low (approx. 2~) level of
finely divided crystalline aluminosilicate is introduced to
increase density and improve granular flow characteristics.
A preferred method of making the compositions according to
the present invention is described in Applicants' copending
Canadian Patent Application No. 2,143,628, filed August 30, 1993.
The present detergent compositions are in granular form and
are characterized by their density, which is higher than the
density of conventional detergent compositions. The density of
the compositions herein ranges from 800 to llOOg/liter,
preferably 850 to lOOOg/liter of composition, measured at 20~C.
The "compact" form of the compositions herein is best
reflected, in terms of composition, by the amount of inorganic
filler salt; inorganic filler salts are conventional ingredients
of detergent compositions in powder form. In conventional
detergent compositions, the filler salts are present in
substantial amounts, typically 17-35% by weight of the total
composltion.
In the present compositions, filler salt is present in
amounts not exceeding 15~ of the total composition, preferably
not exceeding 10~, most preferably not exceeding 5~ by weight of
the composition.
Inorganic filler salts, such as meant in the present
compositions are selected from the alkali and alkaline-earth-
metal salts of sulphates and chlorides.
A preferred filler salt is sodium sulphate.
~B '
WO 94119444 PCT/US94/015Z8
_ 2 1S68~9 20
PROCESS OF WASHING
The compact detergent compositions herein have the ability
to achieve the same efficiency than conventional detergent
compositions, when a considerably lesser amount of composition
herein, is used in the main wash cycle of a washing machine.
Accordingly, in an other embodiment of the invention, it is
herewith provided for a process for washing fabrics in a
washing machine wherein an amount of from 15 to 170 g of a
detergent composition according to the present invention is
used for the main wash cycle.
Typically, under European conditions, the recommended usage
is from 80 to 140 g of detergent composition for the main wash
cycle, without the need of a pre-wash.
The detergent compositions herein are preferably delivered
directly to the drum and not indirectly via the outer casing
of the machine. This can most easily be achieved by
incorporation of the composition in a bag or container from
which it can be released at the start of the wash cycle in
response to agitation, a rise in temperature or immersion in
the wash water in the drum. Such a container will be placed
in the drum, together with the fabrics to be washed.
Alternatively the washing machine itself may be adapted to
permit direct addition of the composition to the drum e.g. by
a dispensing arrangement in the access door.
Products comprising a detergent composition enclosed in a
bag or container are usually designed in such a way that
container integrity is maintained in the dry state to prevent
egress of the contents when dry, but are adapted for release
of the container contents on exposure to a washing
environment, normally on immersion in an aqueous solution.
215~8~
WO94/194~ PCT~S94/01528
Usually the container will be flexible, such as a bag or
pouch. The bag may be of fibrous construction coated with a
water impermeable protective material so as to retain the
contents, such as is disclosed in European published Patent
Application No. 0 018 678. Alternatively it may be formed of
a water insoluble synthetic polymeric material provided with
an edge seal or closure designed to rupture in aqueous media
as disclosed in European published Patent Application Nos. 0
Oll 500, 0 Oll Sol, 0 Oll 502, and 0 Oll 968. A convenient
form of water frangible closure comprises a water soluble
adhesive disposed along and sealing one edge of a pouch formed
of a water impermeable polymeric film such as polyethylene or
polypropylene.
In a variant of the bag or container product form, laminated
sheet products can be employed in which a central flexible
layer is impregnated and/or coated with a composition and then
one or more outer layers are applied to produce a fabric-like
aesthetic effect. The layers may be sealed together so as to
remain attached during use or may separate on contact with
water to facilitate the release of the coated or impregnated
material.
An alternative laminate form comprises one layer embossed or
deformed to provide a series of pouch-like containers into
each of which the detergent components are deposited in
measured amounts, wi~h a second layer overlying the first
layer and sealted thereto in those areas between the pouch-
like containers where the two layers are in contact. The
components may be deposited in particulate, paste or molten
form and the laminate layers should prevent egress of the
contents of the pouch-like containers prior to their addition
to water. The layers may separate or may remain attached
together on contact with water, the only requirement being
that the structure should permit rapid release of the contents
of the pouch-like containers into solution. The number of
pouch-like containers per unit area of substrate is a matter
W094/194~ ~5~8~ 22 PCT~S94/01528
of choice but will normally vary between 500 and 25,000 per
square metre.
Suitable materials which can be used for the flexible
laminate layers in this aspect of the invention include, among
others, sponges, paper and woven and non-woven fabrics.
However the preferred means of carrying out the washing
process according to the present invention includes the use of
a reusable dispensing device having walls that are permeable
to liquid but impermeable to the solid composition.
Devices of this kind are disclosed in European Patent
Application Publication Nos. 0 343 069 and 0 344 070. The
latter Application discloses a device comprising a flexible
sheet in the form of a bag extending from a support ring
defining an orifice, the orifice being adapted to admit to the
bag sufficient product for one washing cycle in a washing
cycle. A portion of the washing medium flows through the
orifice into the bag, dissolves the product, and the solution
then passes outwardly through the orifice into the washing
medium. The support ring is provided with a masking
arrangement to prevent egress of wetted, undissolved, product,
this arrangement typically comprising radially extending walls
extending from a central boss in a spoked wheel configuration,
or a similar structure in which the walls have a helical form.
~15~829
'~ WO94/194~ PCT~S94101528
23
The following examples illustrate the invention and
facilitate its understanding.
,~
EXAMPLE I and II
The following compositions are made.
ComDact qranular deterqent : exampies I and II.
EXAMPI F I
Linear alkyl benzene sulphonate sodium salt 8.0
C45 alkyl sulphate sodium salt 2.5
C45 alcohol 7 times ethoxylated 6.0
Tallow alcohol 11 times ethoxylated 2.0
Layered silicate 15.0
Trisodium citrate 5.0
Carbonate sodium salt 6.5
Zeolite 1 5.0
Maleic acid acrylic acid copolymer 5.0
DETMPA 0.3
Savinase TM 1 OT 0.8
Lipolase TM 1 OOT 0.25
Sodium silicate 2.0
Sodium sulphate 3. 5
PVP 1.0
Perborate 1 5.0
TAED 6.0
Minors up to 100
WO 94/19444 PCT/US94/01528
21568~9 24
ExamDle 11
Surfactants
C45 alkyl sulphate sodium salt 8.0
Linear C12-15 3 times ethoxylated 6.0
Builders
Zeolite 20.0
Citrate 6.0
Buffer
Carbonate 1 6.0
Polvmer
CMC 0 4
Maleic acid acrylic acid copolymer 5.0
Enzvme
Savinase 10T 1.2
Lipolase 1 50T 0.10
Miscellaneous
perborate 20.0
TAED 6.0
Minors up to 100
