Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02346187 2001-04-03
WO 00/Z2091 PCT/US99I22474
Deter~,ent Compositions
Meld of the Invention
The present invention relates to detergent compositions, in particular,
laundry detergents
and their disintegration. In particular, the invention relates to detergent
particles or tablets
comprising water-swellable cationic polymers such as ion exchange resins.
Background
It is a particular requirement of detergent compositions that they should
deliver the
detergent actives to the wash water as soon as possible on contact with water.
In recent
years, detergent compositions have tended to have increased densities above
650g/l, or
above 700g/1 or even above 750g/1, or are even provided in the form of
tablets. This has
tended to inhibit dispensing andlor distribution and consequently rapid
delivery of the
detergent actives to the wash water.
Many methods have been described for improving detergent dissolution, for
example, EP-
A-466484 describes the use of disintegrants and their mechanisms. It is stated
that
disintegrants which act by swelling on contact with water are preferred.
Examples of
disintegrants given are cross-linked polyvinyl pyrrolidones, montmorillonite
or bentonite
clay, sodium carboxymethyl cellulose and acrylate / malefic anhydride
copolymers.
However, there is still a need for disintegrants which provide good break-up
of solid-form
detergent products thereby improving product dispensing and/or dissolution.
An additional problem for formulators of detergents is that soap, for example
from the
surface of soiled laundry, tends to bind to water hardness calcium ions and
precipitate.
The precipitate tends to adhere to items being washed and produce reduced
whiteness by
resoiling.
The present inventors have now found that the use of cationic polymeric
disintegrants can
assist in prevention of this effect by binding with the soap. However, in
order to ensure
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/22474
2
that the soap impurities can be removed from the wash liquor, prior to
complexation with
calcium ions, chelant or builder is needed to rapidly complex calcium ions. In
addition,
the cationic polymeric disintegrants have been found to be particularly useful
in the
disruption of coating layers on detergent components.
Summary of the Inver,~tion
In accordance with the present invention there is now provided a detergent
composition or
component thereof in a solid form comprising a disintegrant and a polyanionic
builder,
characterised in that said disintegrant comprises a water-swellable cationic
polymer. In a
further aspect of the invention, there is provided a detergent composition or
component
thereof in solid form at least partially coated with a coating layer,
characterised in that the
coating layer comprises a disintegrant comprising a water-swellable cationic
polymer.
Detailed DescriQt~on of the Invention
The Disintegrant
The disintegrant comprises a water-swellable cationic polymer. Suitable
disintegrants
include anion exchange resins such as IPR 88 (Rohm & Haas).
The disintegrant comprises a cationic polymer wherein the cationic groups may
be
pendent from the polymeric backbone or on side-chains to the polymeric
backbone.
Preferred cationic groups are pendent from the polymer backbone. Preferred
cationic
groups are quaternary anionic groups, such as -(N R, RZ R3)+wherein Rl, R2 and
R3 are
each individually selected from H and optionally substituted lower alkyl or
alkenyl
groups, such as methyl or ethyl groups.
Suitable polymeric backbones include for example polyacrylate and/or
polymethacrylate
homopolymers or copolymers and polyvinyl polymers such as polyvinyl pyridines.
Polyvinyl pyridines and polyacrylate polymers have been found to be
particularly
preferred.
CA 02346187 2001-04-03
WO 00/22091 PCT/US99I22474
3
The disintegrants for use in the present invention are water-swellable. Water-
swellability
is achieved by the conventional methods available to those skilled in the art,
for example,
by cross-linking and/or selection of substituents on the polymer backbone to
reduce
water-solubility and provide swellability. Cross-linking may be by a
conventional
method, for example by the use of from 0.5 to 20% by weight based on the
weight of
polymer, of a cross-linker such as divinylbenzene. Particularly preferred
cationic
polymers for use as disintegrants in the present invention are partially cross-
linked poly
(4-vinyl pyridine hydrochloride) and partially cross-linked polyacrylate
esterified with
partially quatenzised N,N dimethyl ethanolamine, cross-linked with 2% by
weight based
on the polymer, of divinyl benzene. Suitable polymers are commercially
available as ion
exchange resins, for example IPR88 and Amberlite CG-420.
Suitable polymers should be heat stable up to at least the temperature for the
appropriate
detergent processing.
The disintegrant is preferably added to the detergent composition in the form
of a dry
added particle. It has been found that the particle size of the disintegrant
may be selected
to give particularly beneficial disintegrating properties in use in a
detergent composition.
Disintegrants in particulate form preferably have a particle size of at least
100pm,
preferably at least 150~m. Preferred disintegrants have a particle size of no
greater than
2000pm, most preferably below 1700pm. In practice, the particles obtained may
have a
size distribution. Therefore, the particle size is preferably such that at
least 80 wt%,
preferably at least 90 wt% and most preferably at least 95 wt% of the
components of the
disintegrating component or a particulate disintegrants is at least 100pm,
more preferably
at least 150~m. Preferably at least 80 wt%, preferably at least 90 wt% and
most
preferably at least 95 wt% disintegrant particles are below 2000pm, most
preferably
below 1700~m, or even below 1500~tm, to obtain the maximum disintegrating
benefits.
The disintegrants are generally present in the detergent composition in
amounts from 1 to
20 wt%, preferably in amounst of 2 to 15 wt%, most preferably from 2 to 10 wt%
based
on the weight of the detergent composition.
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/22474
4
It may be particularly advantageous to use the water-swellable cationic
polymer in
combination with an additional disintegrant, such as any of those discussed in
EP-A-
466484. In such cases, it may be preferred to from a pre-mix of the water-
swellable
cationic polymer and additional disintegrant prior to incorporation into a
detergent
composition.
The disintegrants of the invention may also be used in combination with a
wicking agent.
Suitable wicking agents comprises a compound or mixture of compounds which
enables
fast water penetration into the detergent composition containing the
disintegrating
component, when the detergent composition is contacted with water in the wash.
The
wicking agent is generally substantially water-insoluble in cold water at
15°C. Preferably
also, the wicking agent has low compressibility and maintains porosity under
processing
conditions, particularly compaction.
Suitable wicking agents are generally cellulose-based. The cellulose-based
compounds
may optionally be microcrystalline or mechanically ground and processed
cellulose such
as ArbocelTM.
The wicking agent may be in the form of a powder, which may be obtained by
mechanical
grinding, a microcrystalline powder or it may be in the form of a granule e.g.
an
agglomerate of fine particle size wicking agent, or as a fibre, or mixtures
thereof.
Particularly preferred wicking agents are fibrous, for example, those having a
length to
diameter ratio of at least 3:1, preferably at least 5:1 or even at least 10:1.
Suitable fibres
include those having a length of at least O.lmm, or at least 0.2mm, or even at
least
0.4mm. Particularly preferred wicking agents are cross-linked.
Particularly preferred wicking agents are cross-linked cellulose fibres as
described in US
5 137 537, US 5 183 707, US 5 190 563, US 5 562 740, US 5 549 791, US 5 549
863, US
5 709 774 or US 5 716 703. These particularly preferred cellulosic fibres are
cross-linked
in substantially individualized form i.e. the cellulosic fibres have primarily
intrafibre
chemical cross-link bonds. That is, the cross-link bonds are primarily between
cellulose
CA 02346187 2001-04-03
WO OO/Z2091 PCT/US99/Z2474
molecules of a single fibre rather than between cellulose molecules of
separate fibres.
Processes for making such cross-linked fibres may be either dry cross-linking
processes
such as is described in US 3 224 926, or aqueous solution, as described in US
3 241 553
or non-aqueous solution cross-linking, as described in US 4 035 147.
When used in combination, the wicking agent and water-swellable cationic
polymer are
preferably present in weight ratios of less than 2:1, preferably less than
1:1. The weight
ratio is generally no less than 1:20, preferably no less than 1:10.
Preferably the water-swellable cationic polymer and any wicking agent are
mixed to form
an intimate mixture of the two components optionally with additional
components and/or
binder. By intimate mixture is meant that the at least two components are
mixed together
to form a pre-mix which is a substantially homogeneous mixture.
This may be achieved by dry mixing solid wicking agent and solid water-
swellable agent
with an optional binder. The pre-mix may be in the form of a particle and this
can be
achieved for example by granulation , such as by agglomeration, extrusion or
dry
compaction. However, it has been found that particularly effective results are
achieved if
the water-swellable agent is present as a coating on the wicking agent. This
is particularly
beneficial where the wicking agent is fibrous.
Providing a coating of the water-swellable agent on the wicking agent may be
achieved in
any convenient way, for example by mixing the wicking agent and water-
swellable
polymer with a solvent for the water-swellable agent, in any order of
addition, such that a
gel or solution is formed or a slurry comprising partially swollen water-
swellable agent.
Preferably mixing is continued until a substantially homogeneous mixture is
obtained.
The mixture of wicking agent and water-swellable agent is then recovered by
separating
out from the solvent by any conventional technique, such as by evaporating off
the
solvent or by addition of a non-solvent for the water-swellable agent to form
a precipitate
of the mixture, such mixture is then separated from the solvent by any
conventional
technique such as by subsequent filtration or decanting off the solvent.
CA 02346187 2001-04-03
wo oon2o91 rc~rnrs99n~,a~a
6
Polyanionic Builder
The term "builder" is intended to mean all materials which tend to remove
calcium ion
from solution. The polyanionic builder is present to rapidly build calcium
ions in the
wash liquor. Suitable polyanionic builders include water-soluble builders
selected from
water-soluble poly-carboxylates, phosphates, borates, polymeric
polycarboxylates,
chelants, or the corresponding acids of any of these, and mixtures thereof.
Preferably the water-soluble builder will be present in amounts of from 0.05%
to 50% by
weight , preferably from 0.1% to 40 % by weight, most preferably from 0.5% to
30% by
weight based on the weight of the detergent composition as a whole.
It may be preferred that the detergent composition is substantially free of
phosphate,
however, if present, suitable phosphate-containing detergent builders include,
but are not
limited to, the alkali metal, ammonium and alkanolammonium salts of
polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric
meta-
phosphates). Preferred phosphate builders are tetrasodium pyrophosphate or
more
preferably anhydrous or partially hydrated sodium tripolyphosphate at levels
of from
0.5% to 50%, more preferably from 5% to 45% by weight based on the detergent
composition as a whole.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
Suitable carboxylates containing two carboxy groups include the water-soluble
salts of
succinic acid, malonic acid, (ethylenedioxy) diacetic acid, malefic acid,
diglycolic acid,
tartaric acid, tartronic acid and fumaric acid, as well as the ether
carboxylates and the
sulfinyl carboxylates. Polycarboxylates or their acids 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 British Patent No. 1,389,732,
and
CA 02346187 2001-04-03
WO 00/22091 PGT/US99/22474
7
aminosuccinates 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. The most preferred polycarboxylic acid
containing three
carboxy groups is citric acid, preferably present at a level of from 0.1% to
15%, more
preferably from 0.5% to 8% by weight of the composition.
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
tetracarboxylates 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. 1,439,000. Preferred polycarboxylates
are
hydroxycarboxylates containing up to three carboxy groups per molecule, more
particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
It may be preferred that the polymeric or oligomeric polycarboxylates are
present at levels
of less than 5%, preferably less than 3% or even less than 2% or even 0% by
weight of the
compositions.
Borate builders, as well as builders containing borate-foaming materials that
can produce
borate under detergent storage or wash conditions are useful water-soluble
builders
herein.
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic 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 the latter type are disclosed in GB-A-1,596,756.
Examples of
such salts are polyacrylates of MWt 1000-5000 and their copolymers with
malefic
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/22474
8
anhydride, such copolymers having a molecular weight of from 2000 to 100,000,
especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from
aspartic acid
such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from malefic acid, acrylic acid,
polyaspartic acid and vinyl alcohol, particularly those having an average
molecular
weight of from 5,000 to 10,000, are also suitable herein.
Chelants are also useful as the polyanionic builder for use in the detergent
compositions
of the invention. By chelant is meant sequester (chelate) metal ions. These
components
are generally present at a level of from 0.005% to 10%, preferably from 0.1%
to 5%,
more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by
weight of
the compositions.
Suitable chelants for use herein include organic phosphonates, such as the
amino alkylene
poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates
and nitrilo
trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine tetra
(methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1
hydroxyethane
diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
Other suitable chelants for use herein include nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenediamine
disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine
disuccinic
acid or any salts thereof.
Other suitable chelants for use herein are iminodiacetic acid derivatives such
as 2-
hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-
317,542
CA 02346187 2001-04-03
WO 00/22091 PGT/US99/22474
9
and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and
aspartic
acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelants described in
EP-A-
516,102 are also suitable herein. The ~i-alanine-N,N'-diacetic acid, aspartic
acid-N,N'-
diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid
chelants
described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based chelants. EP-A-S 10,331 describes
suitable chelants derived from collagen, keratin or casein. EP-A-528,859
describes
a suitable alkyl iminodiacetic acid chelant. Dipicolinic acid and 2-
phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-
disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-
hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Diethylenetriamine pentacetic acid, ethylenediamine-N,N'-disuccinic acid
(EDDS)
and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth
metal,
ammonium, or substituted ammonium salts thereof, or mixtures thereof may also
be
used.
Form of the Gomnosition
The detergent composition or component thereof, according to the invention may
take a
variety of solid physical forms, such as tablet, flake, pastille and bar, and
preferably
granular or tablet forms. Preferably the detergent composition is in the form
of a tablet.
The detergent compositions may be made by a variety of methods, including dry-
mixing,
agglomerating, compaction, or spray-drying of the various compounds comprised
in the
detergent composition, or mixtures of these techniques.
The disintegrant is incorporated into the detergent composition in any
conventional way.
For example it may be added into any of the processing steps described above,
but is
preferably dry-added into a particulate detergent mix. The disintegrant may
alternatively
or additionally be provided in a coating for all or part of a detergent
composition. Thus
the disintegrant may be present in a detergent granule or may be intermixed
with other
detergent components as a discrete particle. For incorporation into a tablet,
the
CA 02346187 2001-04-03
WO 00/Z2091 PGT/US99/2247d
disintegrant may be incorporated into the granular detergent composition as
described
above, prior to compaction. When present as part of a coating, the
disintegrant is
particularly useful in a detergent tablet coating. The coating aspect of the
invention is
described below in the context of a detergent tablet coating where a core of
detergent
compostion is firstly fonmed and then coated. However, the coating could
equally well be
applied to a detergent particle or other solid detergent form.
Coatin Detergent Tablets
Where the detergent of the present invention is in the form of a tablet, these
can be
10 prepared simply by mixing the solid ingredients together and compressing
the mixture in
a conventional tablet press. Any liquid ingredients, for example the
surfactant or suds
suppressor, can be incorporated in a conventional manner into the solid
particulate
ingredients. Preferably the principal ingredients, are used in particulate
form.
In particular for laundry tablets, the ingredients such as builder and
surfactant can be
spray-dried in a conventional manner and then compacted at a suitable
pressure.
The detergent tablets can be made in any size or shape and can, if desired, be
surface
treated. In the core of the tablet is included a surfactant and a builder
which normally
provides a substantial part of the cleaning power of the tablet.
T'he particulate material used for making the tablet of this invention can be
made by any
particulation or granulation process. An example of such a process is spray
drying (in a
co-current or counter current spray drying tower) which typically gives low
bulk densities
600g/1 or lower. Particulate materials of higher density can be prepared by
granulation
and derisification in a high shear batch mixer/granulator or by a continuous
granulation
and densification process (e.g. using Lodige~ CB and/or Lodige~ KM mixers).
Other
suitable processes include fluid bed processes, compaction processes (e.g.
roll
compaction), extrusion, as well as any particulate material made by any
chemical process
like flocculation, crystallisation sentering, etc. Individual particles can
also be any other
particle, granule, sphere or grain.
CA 02346187 2001-04-03
WO 00/22091 PCTNS99lZZ474
11
The particulate materials may be mixed together by any conventional means.
Batch is
suitable in, for example, a concrete mixer, Nauta mixer, ribbon mixer or any
other.
Alternatively the mixing process may be carried out continuously by metering
each
component by weight on to a moving belt, and blending them in one or more
drums) or
mixer(s). A liquid spray-on to the mix of particulate materials (e.g. non-
ionic surfactants)
may be carried out. Other liquid ingredients may also be sprayed on to the mix
of
particulate materials either separately or premixed. For example perfume and
slurnes of
optical brighteners may be sprayed. A finely divided flow aid (dusting agent
such as
zeolites, carbonates, silicas) can be added to the particulate materials after
spraying the
non-ionic, preferably towards the end of the process, to make the mix less
sticky.
The tablets may be manufactured by using any compacting process, such as
tabletting,
briquetting, or extrusion, preferably tabletting. Suitable equipment includes
a standard
single stroke or a rotary press (such as Courtoy~, Korch~, Manesty~, or
Bonals~). The
tablets prepared according to this invention preferably have a diameter of
between 40mm
and SOmm, and a weight between 25 and 60 g. The compaction pressure used for
preparing these tablets need not exceed 5000 kN/m2, preferably not exceed 3000
kN/m2,
and most preferably not exceed 1000 kN/m2.
According to the present invention, the tablets are then coated with a coating
so that the
tablet does not absorb moisture, or absorbs moisture at only a very slow rate.
The coating
is also strong so that moderate mechanical shocks to which the tablets are
subjected
during handling, packing and shipping result in no more than very low levels
of breakage
or attrition. Finally the coating is preferably brittle so that the tablet
breaks up when
subjected to stronger mechanical shock. Furthermore it is advantageous if the
coating
material is dissolved under alkaline conditions, or is readily emulsified by
surfactants.
This avoids the deposition of undissolved particles or lumps of coating
material on the
laundry load. This may be important when the coating material is completely
insoluble
(for example less than 1 g/1) in water.
CA 02346187 2001-04-03
WO 00/Z2091 PGTNS99/22474
12
As defined herein "substantially insoluble" means having a very low solubility
in water.
This should be understood to mean having a solubility in water at 25°C
of less than 20
g/L, preferably less than 5 g/1, and more preferably less than 1 g/1. Water
solubility is
measured following the test protocol of ASTM E1148-87 entitled, "Standard Test
Method
for Measurements of Aqueous Solubility".
Suitable coating materials are fatty acids, C2-C13 dicarboxylic acids, fatty
alcohols, diols,
esters and ethers. Preferred fatty acids are those having a carbon chain
length of from C12
to C22 and most preferably from C 18 to C22. Preferred dicarboxylic acids are
oxalic acid
(C2), malonic acid (C3), succinic acid (C4), glutaric acid (C5), adipic acid
{C6), pimelic
acid (C7), suberic acid (C8), azelaic acid (C9), sebacic acid (C10),
undecanedioic acid
(C 11 ), dodecanedioic acid (C 12) and tridecanedioic acid (C 13). Preferred
fatty alcohols
are those having a carbon chain length of from C 12 to C22 and most preferably
from C 14
to C18. Preferred diols are 1,2-octadecanediol and 1,2-hexadecanediol.
Preferred esters
are tristearin, tripalmitin, methylbehenate, ethylstearate. Preferred ethers
are
diethyleneglycol mono hexadecylether, diethyleneglycol mono octadecylether,
diethyleneglycol mono Otetradecylether, phenylether, ethyl naphtyl ether, 2
methoxynaphtalene, beta naphtyl methyl ether and glycerol monooctadecylether.
Other
preferred coating materials include dimethyl 2,2 propanol, 2 hexadecanol, 2
octadecanone, 2 hexadecanone, 2, 15 hexadecanedione and 2 hydroxybenzyl
alcohol.
Pre-formed detergent tablet core may then be coated according to the present
invention.
The coating may be applied in a number of ways, but generally as a liquid,
either a) as a
melt, or b) as a solution. Preferred coating materials are applied in the form
of a melt.
Particularly preferred coating compositions have a melting point of from 40
°C to 200 °C.
In a), the coating material is applied at a temperature above its melting
point, and
solidifies on the tablet. In b), the coating is applied as a solution, the
solvent being
removed e.g. by drying dried to leave a coherent coating. The substantially
insoluble
material can be applied to the tablet by, for example, spraying or dipping.
Normally when
the molten material is sprayed on to the tablet, it will rapidly solidify to
form a coherent
coating. When tablets are dipped into the molten material and then removed,
the rapid
CA 02346187 2001-04-03
WO 00/22091 PCT/US99J22474
13
cooling again causes rapid solidification of the coating material. Clearly
substantially
insoluble materials having a melting point below 40 °C are not
sufficiently solid at
ambient temperatures and it has been found that materials having a melting
point above
about 200 °C are not practicable to use. Preferably, the materials melt
in the range from
60 °C to 160 °C, more preferably from 70 °C to 120
°C.
By "melting point" is meant the temperature at which the material when heated
slowly in,
for example, a capillary tube becomes a clear liquid.
A coating of any desired thiclrness can be applied according to the present
invention. For
most purposes, the coating forms from 1% to 10%, preferably from 1.5% to S%,
of the
tablet or detergent component weight.
The disintegrant will be present in the coating layer in an amount sufficient
to generate
the desired degree of disruption of the coating layer on contact with water in
the wash
liquor to promote delivery of the detergent composition to the wash and
improve
dissolution. Generally the disintegrant will be present in the finished
coating in a weight
ratio of coating material to disintegrant of from 1:1 to 50:1, preferably from
2:1 to 20:1,
most preferably from 5:1 to 15:1. Where the coating is applied as a melt, the
disintegrant
is generally suspended in the coating melt at a level of up to 30%, preferably
between 5
and 20%, and most preferably between 5 and 10% by weight.
Depending on the composition of the starting material, and the shape of the
tablets, the
used compaction force will be adjusted to not affect the strength (Diametral
Fracture
Stress), and the disintegration time in the washing machine. This process may
be used to
prepare homogenous or layered tablets of any size or shape.
Diametrical Fracture Stress (DFS) is a way to express the strength of a
tablet, it is
determined by the following equation
_ 2 F
w Dt
CA 02346187 2001-04-03
WO 00/Z2091 PCT/US99IZ2474
14
Where F is the maximum force (Newton) to cause tensile failure (fracture)
measured by a
VK 200 tablet hardness tester supplied by Van Kell industries, Inc. D is the
diameter of
the tablet (mm), and t the thickness of the tablet (mm).
{Method Pharmaceutical Dosage Forms : Tablets Volume 2 Page 213 to 217)
The rate of disintegration of a detergent tablet can be determined in two ways
a) In a "VAN KEL" Friabilator with "Vankel Type" drums.
- Put 2 tablets with a known weight and D.F.S in the Friabilator drum.
- Rotate the drum for 20 rotations.
- Collect all product and remaining tablet pieces from the Friabilator drum,
and screen it
on 5 mm, and through 1.7 mm
- Express as % residue on 5 mm and through 1.7 mm.
- The higher the % of material through 1.7 mm the better the disintegration.
b) In a washing machine according to the following method
- Take two tablets with a known weight and fracture stress, and put them at
the bottom of
a washing machine (i.e. a Bauknecht WA 950).
- Put a 3 kg mixed load on top of the tablets.
- Run a 30 °C short cycle (program 4) with city water.
- Stop the cycle after 5 min and check the wash load for undissolved tablet
pieces, collect
and weigh them, and record the percent residue left.
In another preferred embodiment of the present invention the detergent
compositions
further comprise an effervescent component. Effervescency as defined herein
means the
evolution of bubbles of gas from a liquid, as the result of a chemical
reaction between a
soluble acid source and an alkali metal carbonate {effervescent component) to
produce
carbon dioxide gas,
i.e. C6Hg07 + 3NaHC03 ~ Na3C6H507 + 3C02 T + 3H20
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/22474
Further examples of acid and carbonate sources and other effervescent systems
may be
found in : (Pharmaceutical Dosage Forms : Tablets Volume 1 Page 287 to 291 )
An effervescent may be added to the tablet mix in addition to the detergent
ingredients.
The addition of this effervescent to the detergent compositions or component
thereof, in
5 particular to detergent tablets of the invention, improves the
disintegration time. The
amount of effervescent component will preferably be between 5 and 20 % and
most
preferably between 10 and 20% by weight of the tablet. Preferably the
effervescent
should be added as an agglomerate of the different particles or as a compact,
and not as
separated particles. Due to the gas created by the effervescent component, the
detergent
10 tablets can have a higher D.F.S. and still have the same disintegration
time as a tablet
without effervescent component. When the D.F.S. of the tablet with
effervescent
component is kept the same as a tablet without, the disintegration of the
tablet with
effervescent component will be faster.
15 Other Detergent Components
Deter eg nt Ingredients
The composition or component thereof according to the present invention will
contain
additional detergent ingredients. The precise nature of these additional
ingredients, and
levels of incorporation thereof will depend on the application of the
component or
compositions and the physical form of the components and the compositions.
The detergent compositions of the invention preferably contain one or more
additional
detergent components selected from bleaches, bleach catalysts, alkalinity
systems,
additional builders, organic polymeric compounds, enzymes, suds suppressors,
lime soap,
dispersants, soil suspension and anti-redeposition agents soil releasing
agents, perfumes,
brighteners, photobleaching agents and additional corrosion inhibitors.
Detersive Surfactants
The compositions of the invention generally contain one or more surfactant.
The
surfactant may comprise any surfactant known in the art, selected from
anionic, nonionic,
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/22474
16
cationic, ampholytic, amphoteric and zwitterionic surfactants such as those
discussed
below and mixtures thereof.
Nonlimiting examples of surfactants useful herein typically at levels from
about 1 % to
about 55%, by weight, include the conventional C 11 _C 1 g alkyl benzene
sulfonates
("LAS") and primary, branched-chain and random C 10_C2p alkyl sulfates ("AS"),
the
C10_Clg secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOS03_M+) CH3
and CH3 (CH2)y(CHOS03_M+) CH2CH3 where x and (y + 1) are integers of at least
about 7, preferably at least about 9, and M is a water-solubilizing cation,
especially
sodium, unsaturated sulfates such as oleyl sulfate, the C 10_C 1 g alkyl
alkoxy sulfates
("AEXS"; especially EO 1-7 ethoxy sulfates), C 1 p_C 1 g alkyl alkoxy
carboxylates
(especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the
Clp_C18
alkyl polyglycosides and their corresponding sulfated polyglycosides, and C
12_C 18
alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and
amphoteric
surfactants such as the C 12_C 1 g alkyl ethoxylates ("AE") including the so-
called narrow
peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially
ethoxylates and
mixed ethoxy/propoxy), C 12_C 1 g betaines and sulfobetaines ("sultaines"), C
10_C 18
amine oxides, and the like, can also be included in the overall compositions.
The C10-
C 1 g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples
include
the C12-Clg N-methylglucamides. See WO 9,206,154. Other sugar-derived
surfactants
include the N-alkoxy polyhydroxy fatty acid amides, such as C 10-C 1 g N-(3-
methoxypropyl) glucamide. The N-propyl through N-hexyl C 12-C 1 g glucamides
can be
used for low sudsing. C 10-C2p conventional soaps may also be used. If high
sudsing is
desired, the branched-chain C 1 p-C 16 soaps may be used. Mixtures of anionic
and
nonionic surfactants are especially useful.
Suitable cationic surfactants for incorporation into the detergent composition
of the
invention include the quaternary ammonium surfactants. Preferably the
quaternary
CA 02346187 2001-04-03
WO 00/22091 PGT/US99/22474
17
ammonium surfactant is a mono C6-C 16, preferably C6-C 10 N-alkyl or alkenyl
ammonium surfactants wherein the remaining N positions are substituted by
methyl,
hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated
and bis-
alkoxylated amine surfactants.
Another suitable group of cationic surfactants which can be used in the
detergent
composition of the invention are cationic ester surfactants such as thoses
disclosed in US
Patents Nos. 4228042, 4239660 and 4260529.
Highly preferred cationic surfactants are cationic mono-alkoxylated amine
surfactant
preferably of the general formula I:
R~ /ApR4
\N+ X_
R2/ ~R3
wherein Rl is an alkyl or alkenyl moiety containing from about 6 to about 18
carbon
atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to
about 14
carbon atoms; R2 and R3 are each independently alkyl groups containing from
one to
about three carbon atoms, preferably methyl, most preferably both R2 and R3
are methyl
groups; R4 is selected from hydrogen (preferred), methyl and ethyl; X- is an
anion such as
chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical
neutrality; A is
a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0
to about
30, preferably 2 to about 15, most preferably 2 to about 8.
Preferably the ApR4 group in formula I has p=1 and is a hydroxyalkyl group,
having no
greater than 6 carbon atoms whereby the -OH group is separated from the
quaternary
ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred
ApR4
groups are -CH2CH20H, -CH2CH2CH20H, -CH2CH(CH3)OH and -
CA 02346187 2001-04-03
WO 00122091 PCT/US99/22474
18
CH(CH3)CH20H, with--CH2CH20H being particularly preferred. Preferred Rl groups
are linear alkyl groups. Linear R1 groups having from 8 to 14 carbon atoms are
preferred.
Other conventional useful surfactants are listed in standard texts.
Additional Builders
In addition to the polyanionic builders present in the detergent compositions
of the
invention, additional builders may be present to assist in controlling mineral
hardness.
Inorganic as well as organic builders can be used. Builders are typically used
in fabric
laundering compositions to assist in the removal of particulate soils. The
level of
additional builder can vary widely depending upon the end use of the
composition.
Examples of silicate builders which may be incorporated into the detergents of
the
invention are the alkali metal silicates, particularly those having a
Si02:Na20 ratio in the
range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium
silicates described in
U.S. Patent 4,664,839, issued May I2, 1987 to H. P. Rieck. NaSKS-6 is the
trademark
for a crystalline layered silicate marketed by Hoechst (commonly abbreviated
herein as
"SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not
contain
aluminum. NaSKS-6 has the delta-Na2Si05 morphology form of layered silicate.
It can
be prepared by methods such as those described in German DE-A-3,417,649 and DE-
A-
3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but
other such
layered silicates, such as those having the general formula NaMSix02x+1'YH20
wherein
M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a
number
from 0 to 20, preferably 0 can be used herein. Various other layered silicates
from
Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma
forms. As noted above, the delta-Na2Si05 (NaSKS-6 form) is most preferred for
use
herein. Other silicates may also be useful such as for example magnesium
silicate, which
can serve as a crispening agent in granular formulations, as a stabilizing
agent for oxygen
bleaches, and as a component of suds control systems. Examples of carbonate
builders are
the alkaline earth and alkali metal carbonates as disclosed in German Patent
Application
No. 2,321,001 published on November 15, 1973.
CA 02346187 2001-04-03
wo oonZO9i Pcnus99nza~a
19
Aluminosilicate builders may be useful in the present invention.
Aluminosilicate builders
are of great importance in most currently marketed heavy duty granular
detergent
compositions, and can also be a significant builder ingredient in liquid
detergent
formulations. Aluminosilicate builders include those having the empirical
formula:
Mz(zA102)yJ ~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0
to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous in structure and can be
naturally-
occurring aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669,
Krummel, et
al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate
ion exchange
materials useful herein are available under the designations Zeolite A,
Zeolite P (B),
Zeolite MAP and Zeolite X, zeolite MAP may be particularly useful. In an
especially
preferred embodiment, the crystalline aluminosilicate ion exchange material
has the
formula:
Nal2[(A102)12(Si02)12J'~20
wherein x is from about 20 to about 30, especially about 27. This material is
known as
Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably, the
aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Fatty acids, e.g., C12-Clg monocarboxylic acids, can also be incorporated into
the
compositions alone, or in combination with the aforesaid builders, especially
citrate
and/or the succinate builders, to provide additional builder activity. Such
use of fatty
acids will generally result in a diminution of sudsing, which should be taken
into account
by the formulator.
In situations where phosphorus-based builders can be used, and especially in
the for-
mulation of bars used for hand-laundering operations, the various alkali metal
phosphates
such as the well-known sodium tripolyphosphates, sodium pyrophosphate and
sodium
CA 02346187 2001-04-03
WO 00/22091 PCTNS99/22474
orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-
diphosphonate and other known phosphonates (see, for example, U.S. Patents
3,159,581;
3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
5 Ble c
The detergent compositions herein may optionally contain bleaching agents or
bleaching
compositions containing a bleaching agent and one or more bleach activators.
When
present, bleaching agents will typically be at levels of from about 1 % to
about 30%, more
typically from about 5% to about 20%, of the detergent composition, especially
for fabric
10 laundering. If present, the amount of bleach activators will typically be
from about 0.1
to about 60%, more typically from about 0.5% to about 40% of the bleaching
composition
comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for
detergent
15 compositions in textile cleaning, hard surface cleaning, or other cleaning
purposes that are
now known or become known. These include oxygen bleaches as well as other
bleaching
agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-
hydrate) can be
used herein. Further suitable peroxygen bleaching compounds include sodium
carbonate
peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate
20 peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach
(e.g.,
OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in
the range from about 500 micrometers to about 1,000 micrometers, not more than
about
10% by weight of said particles being smaller than about 200 micrometers and
not more
than about 10% by weight of said particles being larger than about 1,250
micrometers.
Optionally, the percarbonate can be coated with silicate, borate or water-
soluble
surfactants. Percarbonate is available from various commercial sources such as
FMC,
Solway and Tokai Denka.
Another category of bleaching agent that can be used without restriction
encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of
this class of
CA 02346187 2001-04-03
WO 00/Z2091 PCT/US99/22474
21
agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt
of
metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent
4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446,
Burns
et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al,
published
February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1,
1983.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid as
described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
Mixtures of
bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., 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.
Various nonlimiting examples of activators are disclosed in U.S. Patent
4,915,854, issued
April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene
sulfonate (HOBS) and tetraacetyl ethylene diamine (TAED) activators are
typical, and
mixtures thereof can also be used. See also U.S. 4,634,551 for other typical
bleaches and
activators useful herein. Highly preferred amido-derived bleach activators are
those of
the formulae:
R1N(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an
alkylene containing from 1 to about 6 carbon atoms, RS is H or alkyl, aryl, or
alkaryl
containing from about 1 to about 10 carbon atoms, and L is any suitable
leaving group. A
leaving group is any group that is displaced from the bleach activator as a
consequence of
the nucleophilic attack on the bleach activator by the perhydrolysis anion. A
preferred
leaving group is phenyl sulfonate. Preferred examples of bleach activators of
the above
formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamido-
caproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and
mixtures
thereof as described in U.S. Patent 4,634,551, incorporated herein by
reference.Another
class of bleach activators comprises the benzoxazin-type activators disclosed
by Hodge et
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/22474
22
al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by
reference. A
highly preferred activator of the benzoxazin-type is:
Still another class of preferred bleach activators includes the acyl lactam
activators,
especially acyl caprolactams and acyl valerolactams of the formulae:
O O
II II
O C-CH2-CH2 O C-CH2- ~ Hz
R6-C-NCH -CH ~CH2 Rfi-C-NCH -CH
2 2 2 2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to about
12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam,
octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactam,
decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam,
3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S.
Patent
4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by
reference, which
discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into
sodium
perborate. Bleaching agents other than oxygen bleaching agents are also known
in the art
and can be utilized herein. One type of non-oxygen bleaching agent of
particular interest
includes photoactivated bleaching agents such as the sulfonated zinc and/or
aluminum
phthalocyanines. See U.S. Patent 4,033,71$, issued July 5, 1977 to Holcombe et
al. If
used, detergent compositions will typically contain from about 0.025% to about
1.25%,
by weight, of such bleaches, especially sulfonate zinc phthalocyanine. If
desired, the
bleaching compounds can be catalyzed by means of a manganese compound. Such
compounds are well known in the art and include, for example, the manganese-
based
catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat.
5,194,416; U.S.
Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1,
544,440A2,
and 544,490A1; Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-
CA 02346187 2001-04-03
WO 00/Z2091 PCT/US99/22474
23
trimethyl-1,4,7-triazacyclononane)2(PF6)2, MnnI2(u-O)1(u-OAc)2(1,4,7-trimethyl-
1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,7-
triazacyclononane)4(C104)4,
MnInMnIV4(u-O)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3,
MnIV-
(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof.
Other
metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243
and U.S. Pat.
5,114,611. The use of manganese with various complex ligands to enhance
bleaching is
also reported in the following United States Patents: 4,728,455; 5,284,944;
5,246,612;
5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein
can be adjusted to provide on the order of at least one part per ten million
of the active
bleach catalyst species in the aqueous washing liquor, and will preferably
provide from
about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500
ppm, of
the catalyst species in the laundry liquor.
z s
Enzymes can be included in the formulations herein for a wide variety of
fabric
laundering purposes, including removal of protein-based, carbohydrate-based,
or
triglyceride-based stains, for example, and for the prevention of refugee dye
transfer, and
for fabric restoration. The enzymes to be incorporated include proteases,
amylases,
lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types
of enzymes
may also be included. They may be of any suitable origin, such as vegetable,
animal,
bacterial, fungal and yeast origin. However, their choice is governed by
several factors
such as pH-activity and/or stability optima, thermostability, stability versus
active
detergents, builders and so on. In this respect bacterial or fungal enzymes
are preferred,
such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to provide up to about
5 mg by
weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram
of the
composition. Stated otherwise, the compositions herein will typically comprise
from
about 0.001% to about 5%, preferably 0.01%-1% by weight of a commercial enzyme
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/Z2474
24
preparation. Protease enzymes are usually present in such commercial
preparations at
levels sufficient to provide from 0.005 to 0.1 Arson units (AU) of activity
per gram of
composition.
Suitable examples of proteases are the subtilisins which are obtained from
particular
strains of B. subtilis and B. licheniforms. Another suitable protease is
obtained from a
strain of Bacillus, having maximum activity throughout the pH range of 8-12,
developed
and sold by Novo Industries A/S under the registered trade name ESPERASE. The
preparation of this enzyme and analogous enzymes is described in British
Patent
Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing
protein-
based stains that are commercially available include those sold under the
tradenames
ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by
International Bio-Synthetics, Inc. (The Netherlands). Other proteases include
Protease A
(see European Patent Application 130,756, published January 9, 1985) and
Protease B
75 (see European Patent Application Serial No. 87303761.8, filed April 28,
1987, and
European Patent Application 130,756, Bott et al, published January 9, 1985).
Amylases
include, for example, a-amylases described in British Patent Specification No.
1,296,839
(Novo), RAPII7ASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo
Industries.
The cellulase usable in the present invention include both bacterial or fungal
cellulase.
Preferably, they will have a pH optimum of between S and 9.5. Suitable
cellulases are
disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984,
which
discloses fungal cellulase produced from Humicola insolens and Humicola strain
DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas,
and
cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella
Auricula
Solander). suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-
2.095.275
and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of
the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed
in
British Patent 1,372,034. See also lipases in Japanese Patent Application
53,20487, laid
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/22474
open to public inspection on February 24, 1978. This lipase is available from
Amano
Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"
hereinafter referred to as "Amano-P." Other commercial lipases include Amano-
CES,
lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum
NRRLB
5 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth
Co.,
The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme
derived
from Humicola lanuginosa and commercially available from Novo (see also EPO
341,947) is a preferred lipase for use herein.
Peroxidase enzymes are used in combination with oxygen sources, e.g.,
percarbonate,
perborate, persulfate, hydrogen peroxide, etc. They are used for "solution
bleaching," i.e.
to prevent transfer of dyes or pigments removed from substrates during wash
operations
to other substrates in the wash solution. Peroxidase enzymes are known in the
art, and
include, for example, horseradish peroxidase, ligninase, and haloperoxidase
such as
chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are
disclosed, for example, in PCT International Application WO 89/099813,
published
October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation into
synthetic
detergent compositions are also disclosed in U.S. Patent 3,553,139, issued
January 5,
1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457,
Place et
al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March
26, 1985,
both. Enzyme materials useful for liquid detergent formulations, and their
incorporation
into such formulations, are disclosed in U.S. Patent 4,261,868, Hora et al,
issued April 14,
1981. Enzymes for use in detergents can be stabilized by various techniques.
Enzyme
stabilization techniques are disclosed and exemplified in U.S. Patent
3,600,319, issued
August 17, 1971 to Gedge, et al, and European Patent Application Publication
No. 0199
405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme
stabilization systems are also described, for example, in U.S. Patent
3,519,570.
CA 02346187 2001-04-03
WO 00/22091 PCTNS99/22474
26
Other components which are commonly used in detergent compositions and which
may
be incorporated into the detergent tablets of the present invention include,
soil release
agents, soil antiredeposition agents, dispersing agents, brighteners, suds
suppressors,
fabric softeners, dye transfer inhibition agents and perfiunes.
The invention is now exemplified by way of the following examples.
xam le 1
Detergent tablets comprising surfactants, builder, enzymes, perfume and other
detergent
ingredients was formed by placing 42.75g of a commercially available granular
detergent
into a mould of circular shape with a diameter 54mm, and compressed using a
Lloyd
Instruments LR50 testing apparatus. The compression load was optimised so as
to obtain
a tablet with cylindrical tablet strength of l2kPa diametral fracture stress s
(expressed in
kPa) . Diametral fracture stress was calculated as set out above.
Adipic acid (du Pont ) was heated in a thermostatic bath to 163°C with
gentle stirring
until molten. The disintegrant was then added with continuous stirring so as
to obtain a
10% w/w homogeneous suspension in the adipic acid. The tablets prepared as
above were
then dipped into the liquid to give the final coated tablet.
In example 1, cationic polymer IPR 88 (ex. Rohm & Haas) was used as
disintegrant, a
tablet having a total weight of 46g and a diametral fracture stress of 28 kPa
was produced.
This tablet was immersed in de-ionised water at 20°C and the time taken
for the coating
to begin to disintegrate was measured to be 4 seconds.
Comparative Example A
When a celllulose disintegrant, Nymcel zsbl6~ (ex. Metsa Serla), was used as
disintegrant in the same proportion in the coating, a tablet having a total
weight of 46g
and a diametral fracture stress of 30 kPa was produced. This tablet was
immersed in de-
ionised water at 20°C and the time taken for the coating to begin to
disintegrate was
measured to be 25 seconds.
CA 02346187 2001-04-03
WO 00/22091 PCTNS99/Z2474
27
xam a 2
The following are examples of detergent compositions according to the
invention. They
may be particulate or may be compressed in a tablet press into tablets.
A B C D
Base Powder
STPP - 10.0 _
Zeolite A 16.0 - - 16.0
C45AS 4.0 - 4.0 5.0
AS I - 1.0 - -
MBAS 17, 2.1 2.0 4.0 - -
C25 ~3S - 1.0 - 1. 0
MA/AA 2.0 1.0 2.0 1.0
LAS 10.0 11.0 8.9 6.6
TAS - 4.0 - -
Silicate - 3.0 - 3.0
CMC 1.0 1.0 0.5 1.0
Bri htener 2 0.2 0.2 - -
Soa 1.0 - - 1.0
DTPMP 0.4 0.4 0.2 0.4
NaSKS-6 9.0 16.0 10.0 6.8
S ra On
C45E7 - 2.5 - -
C25E3 2.5 - - -
Silicone antifoam 0.3 0.3 0.3 0.3
Perfume 0.3 0.3 0.3 0.3
IPR 88 ohm & Haas 2.0 1.3 3.0 2.5
EA - 0.5 1.0 -
Carbonate 6.0 13.0 15.0 13.0
PB4 18.0 18.0 10.0 -
PB 1 4.0 4.0 - -
NOB S 3.0 4.2 1.0 -
Photoactivated bleach 0.02 0.02 0.02 0.02
Man anese catal st - - 0.5 -
Protease 1.0 1.0 1.0 1.0
Li ase 0.4 0.4 0.4 0.4
Am lace 0.25 0.30 0.15 0.3
D mixed sodium sulfate3.0 3.0 5.0 3.0
Balance (Moisture & 100.0 100.0 100.0 100.0
Miscellaneous
CA 02346187 2001-04-03
WO 00/22091 PCT/US99lZ2474
28
Density (g/litre) 630 670 670 670
E F G H
Base r duc
TAS - 1.0 4.0 -
MBAS 17 1.9 5.0 10.0 16.0 8.0
C45AS 4.0 4.0 6.0 6.0
MES 3.0 - - -
AS II 0.4 - 1.0 -
TFAA - 1.0 - -
C25E5/C45E7/C2 - 2.0 - 1.0
SE3
LAS - 18.0 - -
Zeolite 9.0 5.0 - 8.0
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5 - -
DTPMP 0.7 1.0 - -
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Am lase 0.8 0.4 - 0.25
Li ase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05 - -
Photoactivated 70ppm 45ppm - lOppm
bleach m
Bri tener 1 0.2 0.2 0.08 0.2
PB 1 6.0 2.0 - -
NACA - - - 3.0
NAC OBS 2.0 1.0 0.9 3.1
Amberlite CG420 4.0 6.0 3.0 2.0
A lomerate:
SKS-6 I 6.6 6.0 20.0 10.0
LAS 3.0 - 15.0 7.0
C45 AS 3.0 6.0 - -
Balance (Moisture 100 100 100 100
and
Miscellaneous
CA 02346187 2001-04-03
WO 00/22091 PCTNS99/22474
29
I J K
Base Powder -.
MBAS 17.5, 1.8 - - 2.0
Zeolite A - 22.0 6.0
Sodium sulfate 1.0 5.0 -
MA/AA 3.0 3.0 3.0
MES - 5.0 -
LAS - - 3.5
C45AS 3.0 4.0 7.0
Silicate - 1.0 5.0
Soa - - 2.0
Bri htener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 5.0
Citric acid 3.0 2.0 1.5
S ra On
C45E5 1.0 1.0 -
LASlMES 8.0 5.0 5.0
D additives
NaSKS-6 15.0 6.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
Li ase 0.4 0.4 0.4
Am lase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
NOBS - 6.1 -
NAC OB S - - 4.5
IPR 88 2.5 4.6 1.0
Sodium sulfate 6.0 -
Balance (Moisture 100 100 100
and
Miscellaneous
i ~ M
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/22474
30
Blown Powder Zeolite - - 15.0
A _ _
Sodium sulfate 0.0 5.0 0.0
LAS 9.0 7.0 7.0
C45AS 7.0 2.0 4.0
AS - - 1.5
DTPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerate 1.0 - -
AS
LAS - 11.0 7.0
TAS 2.0 2.0 1.0
Silicate 2.0 - 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 7.0 8.0 4.0
Spray On Encapsulated 0.3 0.3 0.3
Perfume
C25E3 2.0 - 2.0
Dry additives NaSKS-6 15.0 12.0 5.0
silicate
EA 1.0 0.5 0.5
Citric/Citrate 5.0 - 2.0
Bicarbonate - 3.0 -
Carbonate 8.0 15.0 7.0
NAC OBS 6.0 - 5.0
Man anese catal st - - 0.3
NOBS - 2.0 -
PB 1 14.0 7.0 10.0
Pol eth lene oxide of MW - - 0.2
5,000,000
Bentonite cla - - 10.0
Citric acid - - 0.5
Protease 1.0 1.0 1.0
Li ase 0.4~ 0.4 0.4
Am lase 0.6 0.6 0.6
Cellulase 0.6 O.b 0.6
Silicone antifoam S.0 5.0 5.0
IPR 88 ohm & Haas 5.0 2.0 3.0
Sodium sulfate 0.0 1.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous
Densit litre 850 850 850
CA 02346187 2001-04-03
WO 00l2Z091 PCTNS99lZ2474
31
O P Q R
A lomerate
AS 2.0 - 2.0
MES _ 2.0 - _
LAS 6.0 - - -
TAS - 2.0 - -
C45AS 6.0 4.0 2.0 -
MBAS 16.5, 1.9 4.0 - - -
Zeolite A 1 S.0 6.0 - -
Carbonate 4.0 8.0 4.0 8.0
MA/AA 4.0 2.0 - 2.0
CMC 0.5 0.5 - 0.5
DTPMP 0.4 0.4 - 0.5
S ra On
C25E3 1.0 1.0 - -
Perfume 0.5 0.5 0.5 0.5
A lomerate
NaSKS-6 7.0 13.0 20.0 9.0
LAS 5.8 9.0 15.0 9.0
Zeolite - 0.9 - -
C45 AS - 3.0 -
Water 0.08 0.1 - 0.2
D Adds
EDDS/HEDP 0.5 0.3 0.5 0.8
NaSKS 6 I or I 5.0 - - -
Citrate - 1.0 - -
Citric acid 2.0 - 2.0 4.0
NAC OB S 4.1 - 5.0 4.0
TAED 0.8 2.0 - 2.0
Percarbonate 14.0 18.0 13.0 16.0
SRP 1 0.3 0.3 - 0.3
Protease 1.4 1.4 1.0 0.5
Li ase 0.4 0.4 0.3 -
Cellulase 0.6 0.6 0.5 0.5
Am lase 0.6 0.6 - 0.3
EA 1.0 - 1.0 1.0
Silicone antifoam 1.0 0.5 0.5 1.5
Bri htener 1 0.2 0.2 - 6.2
Bri tener 2 0.2 - 0.2 -
IPR 88 Rohm & Haas 6.0 4.0 2.0 3.0
Densi litre 850 850 800 775
S T U V W X
CA 02346187 2001-04-03
WO 00122091 PCT/U599/22474
32
C45AS 11.0 5.0 4.6 6.5 4.1 9.0
C25AES 1.3 1.0 - 1.3 1.0 -
LAS 10.0 3.0 12.7 10.0 5.0 9.5
C25E3/ C25E5 1.5 4.7 3.3 - 4.7 3.3
MBAS 16.5, 1.7 15.0 12.0 10.0 10.2 7.0 i4.1
AS - 1.15 0.6 - 1.7 -
Zeolite A 5.0 16.7 - 7.0 16.7 11.2
Amberlite CG-420
Citric acid - 1.5 2.5 - 1.5 -
MA/AA - 0.6 - - 0.6 -
MA/AA 3 - - 7.03 - - 7.03
AA 2.3 - - 2.8 - -
EDDS - 0.3 - - 0.3 -
HEDP - 0.5 - - 0.5 -
Carbonate 6.0 12.5 14.5 6.0 12.5 14.0
SKS-6/silicate 10.58 0.8 20 10.58 4.8 20
PB 1 11.0 - 14.0 - - 4.0
NACA-OBS - 4.7 - - 2.7 -
PC - 17.3 - 20.0 17.3 -
NOBS - - 4.0 - - 4.0
TAED - 2.5 - - 3.5 2.0
Protease 0.25 0.36 0.2 0.26 0.36 0.2
Li ~e ____. - - _ _ _ _
Cellulase 0.3 0.26 - 0.3 0.26 -
Am lase - 0.36 - - 0.36 -
Bri tener 0.17 0.06 0.30 0.17 0.06 0.30
SRP1 0.4 0.2 0.5 0.4 0.2 0.5
PEG 1.6 - 0.19 1.6 - 0.19
Sulfate 5.5 6.4 3.5 5.5 6.4 3.5
CMC - 0.5 - - 0.5 -
M S04 - 0.13 - - 0.13 -
Photobleach - 0.0026- - 0.0026-
A lomerate of exam 3.5 3.0 2.0 3.0 4.0 3.0
le 3
Silicone anti-foam 0.02 0.21 0.17 0.02 0.21 0.17
Perfume 0.42 0.55 0.25 0.42 0.55 0.25
Abbreviations used in the Examples
In the detergent compositions exemplified above, the abbreviated component
identifications have the following meanings:
NYMCELTM: Carboxymethyl cellulose supplied by Metsa-Serla
CMF : Citric acid infra-cross-linked fibrous cellulose made
by Wayerhauser
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/2Z474
33
ArbocelTM: Micronised cellulose supplied by Rettesmeyer
LAS: Sodium linear C11-13 alkyl benzene sulfonate
MES: a-sulpho methylester of C,8 fatty acid
TAS: Sodium tallow alkyl sulfate
CxyAS : Sodium C 1 x - C 1 y alkyl sulfate
C46SAS: Sodium C14 - C16 secondary (2,3) alkyl sulfate
CxyEzS: Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene
oxide
CxyEz: C 1 x-C 1 y predominantly linear primary alcohol condensed with an
average of z moles of ethylene oxide
QAS: R2.N+(CH3)2(C2H4OH) with RZ = C 12 - C 14
QAS 1: R2.N+(CH3)2(C2H40H) with R2 = Cg.- C11
SADS: Sodium C,4 C22 alkyl disulfate of formula 2-(R).C4
H7.-1,4-(S04 )2
where R = C,~C,e
SADE2S: Sodium C,4 Cu alkyl disulfate of formula 2-(R).C4
H7.-1,4-(SO; )2 ,
R = C,o C,B, condensed with z mol ethylene oxide
APA: Cg - C10 amido propyl dimethyl amine
Soap: Sodium linear alkyl carboxylate derived from an
80/20 mixture of
tallow and coconut fatty acids
STS: Sodium toluene sulphonate
CFAA: C 12-C 14 (coco) alkyl N-methyl glucamide
TFAA: C 16-C 18 ~Yl N-methyl giucamide
TPKFA: C 16_C 1 g topped whole cut fatty acids
STPP: Anhydrous sodium tripolyphosphate
TSPP: Tetrasodium pyrophosphate
Zeolite A: Hydrated sodium aluminosilicate of formula
Nal2(A102Si02)12.27H20 having a primary particle size in the
range from 0.1 to 10 micrometers (weight expressed on an
anhydrous basis)
CA 02346187 2001-04-03
WO 00/22091 PCT/US99/22474
34
NaSKS-6 (I: Crystalline layered silicate of formula 8- Na2Si205 of Clariant
Citric acid: Anhydrous citric acid
Borate: Sodium borate
Carbonate: Anydrous sodium carbonate with a particle size between 200p,m and
900pm
Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution
between 400um and 1200~,m
Silicate: Amorphous sodium silicate (Si02:Na20 = 2.0:1)
Sulfate: Anhydrous sodium sulfate
Mg sulfate: Anhydrous magnesium sulfate
Citrate: Tri-sodium citrate dihydrate of activity 86.4% with a particle size
distribution between 425~m and 850~m
MA/AA: Copolymer of 1:4 maleic/acrylic acid, average molecular weight
about 70,000
MA/AA (1): Copolymer of 4:6 maleic/acrylic acid, average molecular weight
about 10,000
AA: Sodium polyacrylate polymer of average m. weight 4,500
CMC: Sodium carboxymethyl cellulose
Cellulose ether: Methyl cellulose ether with a degree of polymerization of 650
available from Shin Etsu Chemicals
Protease: Proteolytic enzyme, having 3.3% by weight of
active enzyme, sold
by NOVO Industries A/S under the tradename Savinase
Protease I: Proteolytic enzyme, having 4% by weight of active
enzyme, as
described in WO 95/10591, sold by Genencor Int.
Inc.
Alcalase: Proteolytic enzyme, having 5.3% by weight of
active enzyme, sold
by NOVO Industries A/S
Cellulase: Cellulytic enzyme, having 0.23% by weight of
active enzyme, sold
by NOVO Industries A/S under the tradename Carezyme
Amylase: Amylolytic enzyme, having 1.6% by weight of active
enzyme, sold
by NOVO Industries A/S tradename Termamyl 120T
Amylase II: Amylolytic enzyme, as disclosed in PCT/ US9703635
CA 02346187 2001-04-03
WO 00/Z209I PCTNS99/22474
Lipase: Lipolytic enzyme, having 2.0% by weight of active enzyme, sold
by NOVO Industries A/S under the tradename Lipolase
Lipase (1): Lipolytic enzyme, having 2.0% by weight of active enzyme, sold
by NOVO Industries A/S tradename Lipolase Ultra
5 Endolase: Endoglucanase enzyme, having 1.5% by weight of active enzyme,
sold by NOVO Industries A/S
PB4: Sodium perborate tetrahydrate of nominal formula
NaB02.3H20.H202
PB 1: Anhydrous sodium perborate bleach of nominal formula
10 NaB02.H202
Percarbonate: Sodium percarbonate of nominal formula 2Na2C03.3H202
DOBS: Decanoyl oxybenzene sulfonate in the form of the sodium salt
DPDA: Diperoxydodecanedioc acid
NOBS: Nonanoyloxybenzene sulfonate in the form of the sodium salt
15 NACA-OBS: (6-nonamidocaproyl) oxybenzene sulfonate
LOBS: Dodecanoyloxybenzene sulfonate in the form of the sodium salt
DOBS: Decanoyloxybenzene sulfonate in the form of the sodium salt
DOBA: Decanoyl oxybenzoic acid
TAED Tetraacetylethylenediamine
20 DTPA: Diethylene triamine pentaacetic acid
DTPMP:: Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under the Tradename bequest 2060
EDDS: Ethylenediamine-N,N-disuccinic acid, (S,S) isomer in the form of
its sodium salt.
25 Photoactivated: Sulfonated zinc phthlocyanine encapsulated in bleach (1)
dextrin
soluble polymer
Photoactivated Sulfonated alumino phthlocyanine encapsulated in bleach (2)
dextrin soluble polymer
Brightener 1: Disodium 4,4'-bis(2-sulphostyryl)biphenyl
30 Brightener 2: Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-
yl)amino)
stilbene-2:2'-disulfonate
CA 02346187 2001-04-03
WO 00/22091 PCT/US991Z2474
36
HEDP: 1,1-hydroxyethane diphosphonic acid
PEGx: Polyethylene glycol, with a m. weight of x (typically
4,000)
PEO: Polyethylene oxide, with an average m. weight
of 50,000
TEPAE: Tetraethylenepentaamine ethoxylate
PVI: Polyvinyl imidosole, with an average m. weight
of 20,000
PVP: Polyvinylpyrolidone polymer, av.molecular wt
of 60,000
PVNO: Polyvinylpyridine N-oxide polymer, av. M. weight
of 50,000
PVPVI: Copolymer of polyvinylpyrolidone and vinylimidazole,
with an
average molecular weight of 20,000
QEA: bis((C2H50)(C2H40~)(CH3) -N+-C6H12-N+-{CH3)
bis((C2H50)-{C2H40))n, wherein n = from 20 to 30
SRP 1: Anionically end capped poly esters
SRP 2: Diethoxylated poly (l, 2 propylene terephtalate) short block
polymer
PEI: Polyethyleneimine with an average molecular weight of 1800 and
an average ethoxylation degree of 7 ethyleneoxy residues
per nitrogen
Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-
oxyalkylene
copolymer as dispersing agent with a ratio of foam
controller to said dispersing agent of 10:1 to 100:1
Opacifier: Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft under the tradename Lytron 621
Wax: Paraffin wax
