Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Performance-enhanced Particulate Dishwasher Detergents
Field of the Invention
This invention relates generally to enzyme-containing detergents
and, more particularly, to performance-enhanced multi-component deter-
gents in which advantages in regard to detersive performance are obtained
through division into several different ingredients. Detergents such as
these include, in particular, powder-form or granular dishwasher
detergents.
Background of the Invention
Dishwasher detergents are at present marketed as powder-form or
granular products, as tablets or as liquid products, each of these supply
forms having technical and aesthetic advantages, but also disadvantages.
Compact detergent tablets have the largest market share and are enjoying
increasing popularity among consumers by virtue of their simple dosing. In
addition, tablets - through regions of different composition - enable certain
ingredients only to be released under defined conditions in the washing/
cleaning process which improves the cleaning result. Besides the
core/jacket tablets and ring/core tablets well known from the
pharmaceutical field, multi-layer tablets in particular have been successful
in this regard and are now available for use in many areas of washing,
cleaning and hygiene.
The controlled release aspect of ingredients has been, and is still
being, intensively investigated inter alia in the field of detergents, so that
several publications are also available on the subject. In powder-form
detersive products, this controlled release of certain ingredients can be
achieved by coating individual particles which is both technically
complicated and expensive.
Earlier German patent application DE 198 51 426.3 (Henkel KGaA)
describes a process for the production of multi-phase detergent tablets in
which a particulate premix is compressed to form tablets comprising a
cavity which is subsequently filled with a separately prepared melt
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suspension or emulsion of a coating material and one or more active
substances) dispersed or suspended therein. The coating materials
mentioned in this document include paraffins and polyethylene glycols
while the active substances mentioned include enzymes, bleaching agents,
bleach activators, surfactants, corrosion inhibitors, scale inhibitors, co-
builders and/or perfumes. Liquid enzyme preparations are not mentioned
in this document. The teaching of this document is also confined to tablets.
Powder-form detergents containing a "second phase", which obtain certain
effects through the controlled release of ingredients, are not disclosed.
Earlier German patent application DE 199 14 364.1 (Henkel KGaA)
describes rinse aid particles for obtaining a clear rinse effect in domestic
dishwashers which contain 30 to 90% by weight of one or more carrier
materials, 5 to 40% by weight of one or more coating materials with a
melting point above 30°C, 5 to 40% by weight of one or more active
substances and 0 to 10% by weight of other active substances and
auxiliaries. The rinse aid particles are advantageously produced by press
agglomeration processes and are suitable for incorporation in powder-form
dishwasher detergents. According to the teaching of this document, the
coating materials ensure that the rinse aid particles are only significantly
dissolved in the final rinse cycle and withstand the main wash cycle
undamaged and without releasing any active ingredients. The accelerated
and relatively long-lasting release of active substances is not mentioned in
this document.
Dishwasher detergents producing a clear rinse effect in domestic
dishwashers are also described in earlier German patent application DE
199 14 363.3 (Henkel KGaA). These powder-form detergents contain rinse
aid particles which in turn contain 20 to 80% by weight of one or more
coating materials with a melting point above 30°C, 20 to 80% by weight
of
one or more active substances and 0 to 20% by weight of other active
substances and auxiliaries. The rinse aid particles are preferably
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incorporated in the detergents according to the invention in quantities of 0.5
to 30% by weight. According to this document, the problem addressed by
the invention was again to ensure that the rinse aid particles would only
dissolve significantly in the final rinse cycle and would withstand the main
wash cycle undamaged and without releasing any active ingredients. The
accelerated and relatively long-lasting release of active ingredients is not
mentioned in this document either.
The problem addressed by the present invention was to make the
advantages of the controlled release of ingredients available to powder-
form detergents without any need for expensive process steps, such as
single or multiple coating. The particulate detergents to be provided by the
invention would be superior to conventional detergents above all in regard
to stability in storage and in regard to the performance of enzymes.
Summary of the Invention
It has now been found that particulate dishwasher detergents with
the requisite properties can be obtained in a flexible and simple manner by
processing liquid enzyme preparations with coating materials and optionally
carrier materials and/or other ingredients to form melt dispersions which
are then processed by forming/shaping and incorporated in particulate
dishwasher detergents.
The present invention relates on the one hand to enzyme particles
for dishwashing machines which contain
a) 5 to 99.5% by weight of one or more coating materials with a melting
point above 30°C,
b) 0.5 to 60% by weight of one or more liquid enzyme preparations)
dispersed in the coating materials) and
c) 0 to 5% by weight of other active substances and auxiliaries,
d) 0 to 90% by weight of one or more carrier materials.
Description of the Invention
According to the present invention, commercially available liquid
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enzyme preparations are embedded in a matrix or coating material(s),
optionally together with carrier materials and other auxiliaries and/or active
substances, and form enzyme particles. The enzymes are released from
this matrix on the one hand more quickly and, on the other hand,
surprisingly over a longer period so that a rapid and continuing release of
the enzymes is achieved. By adopting the procedure according to the
invention, the maximum enzyme activity is achieved at a much earlier stage
in the wash cycle, enzyme activity remaining at a fairly high level
throughout the remainder of the wash cycle.
The enzyme particles according to the invention may be formulated
to contain carrier materials. The release kinetics can be influenced through
the type and quantity of carrier material used. However, the most important
aspect of using carrier materials lies in the increase in the bulk density of
the enzyme particles. If particles with relatively high bulk densities are to
be produced, carrier materials should be used in relatively large quantities.
Suitable carrier materials a) are any substances which are solid at
room temperature. Substances which develop an additional effect in the
wash cycle will normally be selected, builders being particularly appropriate
in this regard. In preferred enzyme particles, substances from the group of
water-soluble detergent ingredients, preferably carbonates, hydrogen
carbonates, sulfates, phosphates and the organic oligocarboxylic acids
solid at room temperature are present as carrier materials in quantities of
10 to 85% by weight, preferably 20 to 80% by weight and more preferably
to 75% by weight, based on the weight of the particles.
25 The preferred carrier materials mentioned are described in detail
hereinafter.
The enzyme particles according to the invention may also be
produced without any carrier materials or substantially free from carrier
materials. In this case, the enzyme particles according to the invention
30 preferably contain
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a) 40 to 99.5% by weight, preferably 50 to 97.5% by weight, more
preferably 60 to 95% by weight and most preferably 70 to 90% by
weight of one or more coating materials) with a melting point above
30°C,
5 b) 0.5 to 60% by weight, preferably 1 to 40% by weight, more preferably
2.5 to 30% by weight and most preferably 5 to 25% by weight of one or
more liquid enzyme preparations) dispersed in the coating materials)
and
c) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0
to 10% by weight and most preferably 0 to 5% by weight of optionally
other carrier materials, auxiliaries and/or active substances.
Besides the carrier materials and other auxiliaries optionally used,
coating materials and liquid enzyme preparations are present as essential
ingredients in the enzyme particles according to the invention. Preferred
coating materials have a melting range of 45 to 75°C. This melting
range
ensures the advantageous release of enzymes in the standard programs of
dishwashing machines. According to the invention, the coating material is
advantageously soluble in water.
Particularly preferred enzyme particles are those in which the
coating material of the region contains at least one substance from the
group of polyethylene glycols (PEGs) and/or polypropylene glycols (PPGs),
polyethylene glycols with molecular weights of 1500 to 36,000 being
preferred, those with molecular weights of 2000 to 6000 being particularly
preferred and those with molecular weights of 3000 to 5000 being most
particularly preferred.
Enzyme particles containing propylene glycols (PPGs) and/or
polyethylene glycols (PEGs) as sole coating material are particularly
preferred. Polypropylene glycols (PPGs) suitable for use in accordance
with the invention are polymers of propylene glycol corresponding to
general formula I:
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H-(O- i H-CHZ)~-OH (I)
CH3
where n may assume a value of 10 to 2000. Preferred PPGs have
molecular weights of 1000 to 10,000 corresponding to values for n of 17 to
about 170.
Polyethylene glycols (PEGs) preferably used in accordance with the
invention are polymers of ethylene glycol corresponding to general formula
(II):
H-(O-CH2-CH2)~-OH (I I)
in which m may assume a value of 20 to about 1000. The preferred
molecular weight ranges mentioned above correspond to preferred ranges
for the value of n in formula II of about 30 to about 820 (exactly: 34 to
818),
more preferably of about 40 to about 150 (exactly: 45 to 136) and, most
preferably, of about 70 to about 120 (exactly: 68 to 113).
Besides the essential ingredients (coating material and liquid
enzyme preparation), the enzyme particles according to the invention may
contain other active substances and/or auxiliaries, for example those from
the groups of anti-sedimenting agents, anti-settling agents, anti-floating
agents, thixotropicizing agents and dispersants. Thus, certain enzyme
particles according to the invention may contain other auxiliaries from the
group of anti-sedimenting agents, anti-settling agents, anti-floating agents,
thixotropicizing agents and dispersants in quantities of 0.5 to 8.0% by
weight, preferably in quantities of 1.0 to 5.0% by weight and more
preferably in quantities of 1.5 to 3.0% by weight, based on the weight of the
enzyme particles.
According to the invention, the region may also contain emulsifiers
from the group of fatty alcohols, fatty acids, polyglycerol esters and/or
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polyoxyalkylene siloxanes in quantities of 1 to 20% by weight, preferably in
quantities of 2 to 15% by weight and more preferably in quantities of 2.5 to
10% by weight, based on the weight of the enzyme particles.
However, preferred enzyme particles are characterized in that, apart
from the coating material(s), the constituents of the liquid enzyme prepara
tions and optionally carrier materials, they contain no other ingredients.
The enzymes most commonly used in detergents include lipases,
cellulases, amylases and proteases. In addition, hemicellulases, peroxi-
dases and pectinases are used in special products. Proteases, amylases
and lipases are of particular importance in dishwasher detergents. The
enzymes are normally produced in a granulated an encapsulated form for
use in powder products and are added to the detergent in that form. In
water-containing liquid detergents, these granulated and encapsulated
enzymes would partly dissolve so that, in general, liquid enzyme
concentrates are preferably used in their case. Such liquid enzyme
concentrates are based either homogeneously on propylene glycol/water or
heterogeneously on a slurry or are present in microencapsulated form. The
use of liquid enzyme products in solid detergents has never been
described before.
Preferred liquid proteases are, for example, Savinase~ L,
Durazym~ L, Esperase~ L and Everlase~ (Novo Nordisk); Optimase~ L,
Purafect~ L, Purafect~ OX L, Properase~ L (Genencor International) and
BLAP~ L (Biozym GmbH). Preferred amylases are Termamyl~ L,
Duramyl~ L and BAN~ (Novo Nordisk) and Maxamyl~ WL and Purafect~
HPAm L (Genencor International). Preferred lipases are Lipolase~ L,
Lipolase~ ultra L and Lipoprime~ L (Novo Nordisk) and Lipomax~ L
(Genencor International).
The Novo Nordisk products SL and LCC, for example, may be used
as slurries or microencapsulated liquid products. The commercially
available liquid enzyme preparations mentioned contain, for example, 20 to
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90% by weight of propylene glycol or mixtures of propylene glycol and
water. According to the present invention, preferred enzyme particles are
characterized in that they contain one or more liquid amylase preparations
and/or one or more liquid protease preparations.
The enzyme particles according to the invention can be produced in
different ways, the processes for producing the enzyme particles differing
slightly from one another according to whether or not the enzyme particles
contain carrier materials. The present invention also relates to a process
for the production of enzyme particles in which a melt dispersion of
a) 5 to 99.5% by weight of one or more coating materials with a melting
point above 30°C,
b) 0.5 to 60% by weight of one or more liquid enzyme preparations)
dispersed in the coating materials) and
c) 0 to 5% by weight of other active substances and auxiliaries
is processed by forming/shaping in the solidification range of the melt or is
applied to one or more carrier materials and the mixture is processed by
forming/shaping.
A melt dispersion of the enzyme particle ingredients (for a descrip
tion see above) is initially prepared. It may either be directly processed by
forming/shaping or may be applied to one or more carrier materials and
then processed by forming/shaping.
There are no process-related restrictions on the forming/shaping
process step for the melt dispersion or the mixture of melt and carrier
material so that here, too, the expert may chose from the processes
familiar to him. In tests conducted by applicants, processes in which the
forming/shaping process step is carried out by granulation, compacting,
pelleting, extrusion or tabletting have proved to be preferable. The
granules, compactates, pellets, prills, extrudates, beads, flakes, tablets
etc.
obtained in this way may then be added to powder-form or granular
dishwasher detergents. The particle size of the enzyme particles may be
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adapted to the particle size of the "basic powder". According to the
invention, the enzyme particles preferably have particle sizes of 200 to
2000 Nm, more preferably in the range from 400 to 1800 Nm and most
preferably in the range from 600 to 1600 Nm, at least 90% by weight of the
particles having sizes within these ranges.
In the process variant for the production of carrier-containing
enzyme particles, a melt dispersion which may contain other active
substances and auxiliaries is initially prepared. The melt dispersion is
applied to a carrier material and is then processed by forming/shaping in
admixture with that carrier material. The melt suspension or emulsion may
be applied to the carrier material in any standard mixers. This variant of
the process according to the invention comprises applying melts of coating
materials and liquid enzyme preparations to carrier materials. In principle,
melts and carrier materials) may be present in the resulting enzyme
particles in varying quantities. Preferred processes are characterized in
that a mixture of 5 to 50% by weight, preferably 10 to 45% by weight, more
preferably 15 to 40% by weight and most preferably 20 to 35% by weight of
a melt dispersion and 50 to 95% by weight, preferably 55 to 90% by weight,
more preferably 60 to 85% by weight and most preferably 65 to 80% by
weight of carrier materials) is processed by forming/shaping.
Preferred variants of both the above-mentioned processes for
producing the enzyme particles according to the invention are charac
terized in that the coating material makes up from 25 to 85% by weight,
preferably from 30 to 70% by weight and more preferably from 40 to 50%
by weight of the melt dispersion.
As already mentioned in the description of the enzyme particles
according to the invention, polyethylene glycols are particularly suitable
coating materials. Accordingly, preferred processes according to the
invention are characterized in that the melt dispersion contains
polyethylene glycols with molecular weights of 1500 to 36,000, preferably
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those with molecular weights in the range from 2000 to 6000 and more
preferably those with molecular weights in the range from 3000 to 5000 as
the coating material.
The foregoing observations apply in regard to the ingredients which
5 are used in the process according to the invention and processed to form
the enzyme particles according to the invention. The melt suspension or
emulsion to be prepared preferably satisfies certain criteria which were also
described in the foregoing.
In principle, the enzyme particles according to the invention may be
10 directly placed in the hands of the consumer so that the consumer may add
them to the detergent as required in order to obtain better cleaning results
in the case of heavily soiled tableware. However, this option is often
undesirable to the consumer because of the additional dosing step
involved. Accordingly, the enzyme particles according to the invention are
preferably incorporated in particulate dishwasher detergents.
Accordingly, the present invention also relates to a particulate
dishwasher detergent containing builders and optionally other ingredients
from the groups of surfactants, enzymes, bleaching agents, bleach
activators, corrosion inhibitors, polymers, dyes and perfumes and, in
addition, enzyme particles which contain
a) 5 to 99.5% by weight of one or more coating materials with a melting
point above 30°C,
b) 0.5 to 60% by weight of one or more liquid enzyme preparations)
dispersed in the coating materials) and
c) 0 to 5% by weight of other active substances and auxiliaries,
d) 0 to 90% by weight of one or more carrier materials,
based on the weight of the enzyme particles.
As already mentioned in reference to the enzyme particles according
to the invention, the composition of the enzyme particles is preferably
within a relatively narrow range so that preferred particulate dishwasher
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detergents are also characterized in that the enzyme particles consist of
a) 40 to 99.5% by weight, preferably 50 to 97.5% by weight, more
preferably 60 to 95% by weight and most preferably 70 to 90% by
weight of one or more coating materials with a melting point above
30°C,
b) 0.5 to 60% by weight, preferably 1 to 40% by weight, more preferably
2.5 to 30% by weight and most preferably 5 to 25% by weight or one or
more liquid enzyme preparations) dispersed in the coating materials)
and
c) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0
to 10% by weight and most preferably 0 to 5% by weight of optionally
other carrier materials, auxiliaries and/or active substances.
The ingredients of the dishwasher detergents are described herein
after. They may also be partly present as carrier materials in the enzyme
particles according to the invention.
The most important ingredients of dishwasher detergents are
builders. The dishwasher detergents according to the invention may
contain any of the builders typically used in detergents, i.e. in particular
zeolites, silicates, carbonates, organic co-builders and - as an important
builder in dishwasher detergents - also phosphates. All the builders
mentioned in the following are suitable as carrier materials for the enzyme
particles according to the invention, as mentioned in the foregoing.
Suitable crystalline layered sodium silicates correspond to the
general formula NaMSiXOZX+~y H20, where M is sodium or hydrogen, x is a
number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x
being 2, 3 or 4. Crystalline layered silicates such as these are described,
for example, in European patent application EP-A-0 164 514. Preferred
crystalline layered silicates corresponding to the above formula are those in
which M is sodium and x assumes the value 2 or 3. Both Vii- and 8-sodium
disilicates Na2Si205y H20 are particularly preferred, ~i-sodium disilicate
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being obtainable, for example, by the process described in International
patent application WO-A- 91108171.
Other useful builders are amorphous sodium silicates with a
modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more
preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash
cycle properties. The delay in dissolution in relation to conventional
amorphous sodium silicates can have been obtained in various ways, for
example by surface treatment, compounding, compacting or by overdrying.
In the context of the invention, the term "amorphous" is also understood to
encompass "X-ray amorphous". In other words, the silicates do not
produce any of the sharp X-ray reflexes typical of crystalline substances in
X-ray diffraction experiments, but at best one or more maxima of the
scattered X-radiation which have a width of several degrees of the
diffraction angle. However, particularly good builder properties may even
be achieved where the silicate particles produce crooked or even sharp
diffraction maxima in electron diffraction experiments. This may be
interpreted to mean that the products have microcrystalline regions
between 10 and a few hundred nm in size, values of up to at most 50 nm
and, more particularly, up to at most 20 nm being preferred. So-called X-
ray amorphous silicates such as these, which also dissolve with delay in
relation to conventional waterglasses, are described for example in
German patent application DE-A-44 00 024. Compacted amorphous
silicates, compounded amorphous silicates and overdried X-ray-amorphous
silicates are particularly preferred.
The finely crystalline, synthetic zeolite containing bound water used
in accordance with the invention is preferably zeolite A and/or zeolite P.
Zeolite MAP~ (Crosfield) is a particularly preferred P-type zeolite.
However, zeolite X and mixtures of A, X and/or P are also suitable.
According to the invention, it is also preferred to use, for example, a co-
crystallizate of zeolite X and zeolite A (ca. 80% by weight zeolite X) which
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is marketed by CONDEA Augusta S.p.A. under the name of VEGOBOND
AX~ and which may be described by the following formula:
nNa20 - (1-n)K20 - AI203 ~ (2 - 2.5)Si02 - (3.5 - 5.5) H20.
Suitable zeolites have a mean particle size of less than 10 ~m (volume
distribution, as measured by the Coulter Counter Method) and contain
preferably 18 to 22% by weight and more preferably 20 to 22% by weight of
bound water.
The generally known phosphates may of course also be used as
builders providing their use should not be avoided on ecological grounds.
Among the large number of commercially available phosphates, alkali
metal phosphates have the greatest importance in the detergent industry,
pentasodium triphosphate and pentapotassium triphosphate (sodium and
potassium tripolyphosphate) being particularly preferred.
"Alkali metal phosphates" is the collective term for the alkali metal
(more particularly sodium and potassium) salts of the various phosphoric
acids, including metaphosphoric acids (HP03)~ and orthophosphoric acid
(H3P04) and representatives of higher molecular weight. The phosphates
combine several advantages: they act as alkalinity sources, prevent lime
deposits on machine parts and lime incrustations in fabrics and, in addition,
contribute towards the cleaning effect.
Sodium dihydrogen phosphate (NaH2P04) exists as the dehydrate
(density 1.91 gcm~, melting point 60°) and as the monohydrate (density
2.04 gcm-3). Both salts are white readily water-soluble powders which, on
heating, lose the water of crystallization and, at 200°, are converted
into the
weakly acidic diphosphate (disodium hydrogen diphosphate, Na2H2P20~)
and, at higher temperatures, into sodium trimetaphosphate (Na3P309) and
Maddrell's salt (see below). NaH2P04 shows an acidic reaction. It is
formed by adjusting phosphoric acid with sodium hydroxide to a pH value
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of 4.5 and spraying the resulting "mash". Potassium dihydrogen phosphate
(primary or monobasic potassium phosphate, potassium biphosphate,
KDP), KH2P04, is a white salt with a density of 2.33 gcm~, has a melting
point of 253° [decomposition with formation of potassium polyphosphate
(KP03)X] and is readily soluble in water.
Disodium hydrogen phosphate (secondary sodium phosphate),
Na2HP04, is a colorless, readily water-soluble crystalline salt. It exists in
water-free form and with 2 moles (density 2.066 gcm-3, water loss at
95°), 7
moles (density 1.68 gcm-3, melting point 48° with loss of 5 H20) and 12
moles of water (density 1.52 gcm~, melting point 35° with loss of 5
H20),
becomes water-free at 100° and, on fairly intensive heating, is
converted
into the diphosphate Na4P20~. Disodium hydrogen phosphate is prepared
by neutralization of phosphoric acid with soda solution using phenol-
phthalein as indicator. Dipotassium hydrogen phosphate (secondary or
dibasic potassium phosphate), K2HP04, is an amorphous white salt which
is readily soluble in water.
Trisodium phosphate, tertiary sodium phosphate, Na3P04, consists
of colorless crystals which have a density of 1.62 gcm~ and a melting point
of 73-76° (decomposition) as the dodecahydrate, a melting point of
100° as
the decahydrate (corresponding to 19-20% P205) and a density of 2.536
gcm-3 in water-free form (corresponding to 39-4.0% Pz05). Trisodium
phosphate is readily soluble in water through an alkaline reaction and is
prepared by concentrating a solution of exactly 1 mole of disodium
phosphate and 1 mole of NaOH by evaporation. Tripotassium phosphate
(tertiary or tribasic potassium phosphate), K3P04, is a white deliquescent
granular powder with a density of 2.56 gcm~, has a melting of 1340° and
is
readily soluble in water through an alkaline reaction. It is formed, for
example, when Thomas slag is heated with coal and potassium sulfate.
Despite their higher price, the more readily soluble and therefore highly
effective potassium phosphates are often preferred to corresponding
CA 02306388 2000-04-20
sodium compounds in the detergent industry.
Tetrasodium diphosphate (sodium pyrophosphate), Na4P20~, exists
in water-free form (density 2.534 gcm-3, melting point 988°, a figure
of 880°
has also been mentioned) and as the decahydrate (density 1.815 - 1.836
5 gcm-3, melting point 94° with loss of water). Both substances are
colorless
crystals which dissolve in water through an alkaline reaction. Na4P20~ is
formed when disodium phosphate is heated to >200° or by reacting
phosphoric acid with soda in a stoichiometric ratio and spray-drying the
solution. The decahydrate complexes heavy metal salts and hardness
10 salts and, hence, reduces the hardness of water. Potassium diphosphate
(potassium pyrophosphate), K4P20~, exists in the form of the trihydrate and
is a colorless hygroscopic powder with a density of 2.33 gcm-3 which is
soluble in water, the pH value of a 1 % solution at 25° being 10.4.
Relatively high molecular weight sodium and potassium phosphates
15 are formed by condensation of NaH2P04 or KH2P04. They may be divided
into cyclic types, namely the sodium and potassium metaphosphates, and
chain types, the sodium and potassium polyphosphates. The chain types
in particular are known by various different names: fused or calcined
phosphates, Graham's salt, Kurrol's salt and Maddrell's salt. All higher
sodium and potassium phosphates are known collectively as condensed
phosphates.
The industrially important pentasodium triphosphate, Na5P30~o
(sodium tripolyphosphate), is a non-hygroscopic white water-soluble salt
which crystallizes without water or with 6 H20 and which has the general
formula Na0-[P(O)(ONa)-O]~-Na where n = 3. Around 17 g of the salt free
from water of crystallization dissolve in 100 g of water at room temperature,
around 20 g at 60° and around 32 g at 100°. After heating of the
solution
for 2 hours to 100°, around 8% orthophosphate and 15% diphosphate are
formed by hydrolysis. In the preparation of pentasodium triphosphate,
phosphoric acid is reacted with soda solution or sodium hydroxide in a
CA 02306388 2000-04-20
16
stoichiometric ratio and the solution is spray-dried. Similarly to Graham's
salt and sodium diphosphate, pentasodium triphosphate dissolves many
insoluble metal compounds (including lime soaps, etc.). Pentapotassium
triphosphate, K5P30~o (potassium tripolyphosphate), is marketed for
example in the form of a 50% by weight solution (> 23% P205, 25% K20).
The potassium polyphosphates are widely used in the detergent industry.
Sodium potassium tripolyphosphates, which may also be used in
accordance with the invention, also exist. They are formed for example
when sodium trimetaphosphate is hydrolyzed with KOH:
(NaP03)3 + 2 KOH -~ Na3K2P30~o + H20
According to the invention, they may be used in exactly the same
way as sodium tripolyphosphate, potassium tripolyphosphate or mixtures
thereof. Mixtures of sodium tripolyphosphate and sodium potassium
tripolyphosphate or mixtures of potassium tripolyphosphate and sodium
potassium tripolyphosphate or mixtures of sodium tripolyphosphate and
potassium tripolyphosphate and sodium potassium tripolyphosphate may
also be used in accordance with the invention.
The particulate dishwashers according to the invention are
preferably characterized in that they contain builders in quantities of 20 to
80% by weight, preferably in quantities of 25 to 75% by weight and more
preferably in quantities of 30 to 70% by weight, based on the weight of the
detergent.
Organic cobuilders suitable for use in the dishwasher detergents
according to the invention are, in particular, polycarboxylates/polycarboxylic
acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins,
other organic cobuilders (see below) and phosphonates. These classes of
substances are described in the following.
Useful organic builders are, for example, the polycarboxylic acids
CA 02306388 2000-04-20
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usable in the form of their sodium salts, polycarboxylic acids in this context
being understood to be carboxylic acids which bear more than one acid
function. Examples of such carboxylic acids are citric acid, adipic acid,
succinic acid, glutaric acid, malic acid, tartaric acid, malefic acid, fumaric
acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA),
providing their use is not ecologically unsafe, and mixtures thereof.
Preferred salts are the salts of the polycarboxylic acids, such as citric
acid,
adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and
mixtures thereof.
The acids per se may also be used. Besides their builder effect, the
acids also typically have the property of an acidifying component and,
hence, also serve to establish a relatively low and mild pH value in
detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic
acid and mixtures thereof are particularly mentioned in this regard.
Other suitable builders are polymeric polycarboxylates such as, for
example, the alkali metal salts of polyacrylic or polymethacrylic acid, for
example those with a relative molecular weight of 500 to 70,000 g/mole.
The molecular weights mentioned in this specification for polymeric
polycarboxylates are weight-average molecular weights MW of the particular
acid form which, basically, were determined by gel permeation
chromatography (GPC) using a UV detector. The measurement was
carried out against an external polyacrylic acid standard which provides
realistic molecular weight values by virtue of its structural similarity to
the
polymers investigated. These values differ distinctly from the molecular
weights measured against polystyrene sulfonic acids as standard. The
molecular weights measured against polystyrene sulfonic acids are
generally higher than the molecular weights mentioned in this specification.
Particularly suitable polymers are polyacrylates which preferably
have a molecular weight of 2,000 to 20,000 g/mole. By virtue of their
superior solubility, preferred representatives of this group are the short
CA 02306388 2000-04-20
18
chain polyacrylates which have molecular weights of 2,000 to 10,000
g/mole and, more particularly, 3,000 to 5,000 g/mole.
Also suitable are copolymeric polycarboxylates, particularly those of
acrylic acid with methacrylic acid and those of acrylic acid or methacrylic
acid with malefic acid. Acrylic acid/maleic acid copolymers containing 50 to
90% by weight of acrylic acid and 50 to 10% by weight of malefic acid have
proved to be particularly suitable. Their relative molecular weights, based
on the free acids, are generally in the range from 2,000 to 70,000 g/mole,
preferably in the range from 20,000 to 50,000 g/mole and more preferably
in the range from 30,000 to 40,000 g/mole.
The (co)polymeric polycarboxylates may be used either in powder
form or in the form of an aqueous solution. The content of (co)polymeric
polycarboxylates in the detergent is preferably from 0.5 to 20% by weight
and more preferably from 3 to 10% by weight.
In order to improve solubility in water, the polymers may also contain
allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl
sulfonic acid, as monomer.
Other particularly preferred polymers are biodegradable polymers of
more than two different monomer units, for example those which contain
salts of acrylic acid and malefic acid and vinyl alcohol or vinyl alcohol
derivatives as monomers or those which contain salts of acrylic acid and 2-
alkylallyl sulfonic acid and sugar derivatives as monomers.
Other preferred copolymers are those which are described in
German patent applications DE-A-43 03 320 and DE-A-44 17 734 and
which preferably contain acrolein and acrylic acid/acrylic acid salts or
acrolein and vinyl acetate as monomers.
Other preferred builders are polymeric aminodicarboxylic acids, salts
or precursors thereof. Particular preference is attributed to polyaspartic
acids or salts and derivatives thereof which, according to German patent
application DE-A-195 40 086, are also said to have a bleach-stabilizing
CA 02306388 2000-04-20
19
effect in addition to their co-builder properties.
Other suitable builders are polyacetals which may be obtained by
reaction of dialdehydes with polyol carboxylic acids containing 5 to 7
carbon atoms and at least three hydroxyl groups. Preferred polyacetals
are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthal-
aldehyde and mixtures thereof and from polyol carboxylic acids, such as
gluconic acid and/or glucoheptonic acid.
Other suitable organic builders are dextrins, for example oligomers
or polymers of carbohydrates which may be obtained by partial hydrolysis
of starches. The hydrolysis may be carried out by standard methods, for
example acid- or enzyme-catalyzed methods. The end products are
preferably hydrolysis products with average molecular weights of 400 to
500,000 g/mol. A polysaccharide with a dextrose equivalent (DE) of 0.5 to
40 and, more particularly, 2 to 30 is preferred, the DE being an accepted
measure of the reducing effect of a polysaccharide by comparison with
dextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20
and dry glucose sirups with a DE of 20 to 37 and also so-called yellow
dextrins and white dextrins with relatively high molecular weights of 2,000
to 30,000 g/mole may be used.
The oxidized derivatives of such dextrins are their reaction products
with oxidizing agents which are capable of oxidizing at least one alcohol
function of the saccharide ring to the carboxylic acid function. Dextrins thus
oxidized and processes for their production are known, for example, from
European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0
472 042 and EP-A-0 542 496 and from International patent applications
WO 92/18542, WO 93108251, WO 93116110, WO 94/28030, WO 95/07303,
WO 95112619 and WO 95!20608. An oxidized oligosaccharide
corresponding to German patent application DE-A-196 00 018 is also
suitable. A product oxidized at C6 of the saccharide ring can be particularly
advantageous.
CA 02306388 2000-04-20
Other suitable co-builders are oxydisuccinates and other derivatives
of disuccinates, preferably ethylenediamine disuccinate. Ethylenediamine-
N,N'-disuccinate (EDDS) is preferably used in the form of its sodium or
magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also
5 preferred in this connection. The quantities used in zeolite-containing
and/or silicate-containing formulations are from 3 to 15% by weight.
Other useful organic co-builders are, for example, acetylated
hydroxycarboxylic acids and salts thereof which may optionally be present
in lactone form and which contain at least 4 carbon atoms, at least one
10 hydroxy group and at most two acid groups. Co-builders such as these are
described, for example, in International patent application WO-A-95120029.
Another class of substances with co-builder properties are the
phosphonates, more particularly hydroxyalkane and aminoalkane phos
phonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1
15 diphosphonate (HEDP) is particularly important as a co-builder. It is
preferably used in the form of the sodium salt, the disodium salt showing a
neutral reaction and the tetrasodium salt an alkaline reaction (pH 9).
Preferred aminoalkane phosphonates are ethylenediamine tetramethylene
phosphonate (EDTMP), diethylenetriamine pentamethylenephosphonate
20 (DTPMP) and higher homologs thereof. They are preferably used in the
form of the neutrally reacting sodium salts, for example as the hexasodium
salt of EDTMP or as the hepta- and octasodium salts of DTPMP. Of the
phosphonates, HEDP is preferably used as a builder. In addition, the
aminoalkane phosphonates have a pronounced heavy metal binding
capacity. Accordingly, it can be of advantage, particularly where the
detergents also contain bleach, to use aminoalkane phosphonates, more
particularly DTPMP, or mixtures of the phosphonates mentioned.
In addition, any compounds capable of forming complexes with
alkaline earth metal ions may be used as co-builders.
Besides the builders, substances from the groups of surfactants,
CA 02306388 2000-04-20
21
bleaching agents, bleach activators, corrosion inhibitors and dyes and
perfumes are important ingredients of detergents. Important
representatives of the classes of compounds mentioned are described in
the following.
Besides the builders, substances from the groups of surfactants,
bleaching agents, bleach activators, enzymes, polymers and dyes and
perfumes are important ingredients of detergents. Accordingly, preferred
particulate dishwasher detergents contain one or more substances from the
groups of bleaching agents, bleach activators, bleach catalysts,
surfactants, corrosion inhibitors, polymers, dyes and perfumes, pH
regulators and enzymes. Important representatives of the classes of
compounds mentioned are described in the following.
Normally, the only surfactants used in dishwasher detergents are
low-foaming nonionic surfactants. Representatives from the groups of
anionic, cationic or amphoteric surfactants are of lesser importance. In one
particularly preferred embodiment, the dishwasher detergent tablets
according to the invention contain nonionic surfactants.
In particularly preferred embodiments of the present invention, the
detergent tablets according to the invention contain nonionic surfactants,
more particularly nonionic surfactants from the group of alkoxylated
alcohols. Preferred nonionic surfactants are alkoxylated, advantageously
ethoxylated, more especially primary alcohols preferably containing 8 to 18
carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per
mole of alcohol, in which the alcohol radical may be linear or, preferably,
methyl-branched in the 2-position or may contain linear and methyl-
branched radicals in the form of the mixtures typically present in oxoalcohol
radicals. However, alcohol ethoxylates containing linear radicals of
alcohols of native origin with 12 to 18 carbon atoms, for example coconut
oil, palm oil, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of
alcohol are particularly preferred. Preferred ethoxylated alcohols include,
CA 02306388 2000-04-20
22
for example, C~2_~4 alcohols containing 3 EO or 4 EO, C9_» alcohol
containing 7 EO, C~3_~5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO,
C~2_~S alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such
as mixtures of C~2_~a alcohol containing 3 EO and C~2_~$ alcohol containing
5 EO. The degrees of ethoxylation mentioned represent statistical mean
values which, for a special product, can be a whole number or a broken
number. Preferred alcohol ethoxylates have a narrow homolog distribution
(narrow range ethoxylates, NRE). In addition to these nonionic surfactants,
fatty alcohols containing more than 12 EO may also be used, examples
including tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
Suitable other nonionic surfactants are alkyl glycosides with the
general formula RO(G)X where R is a primary, linear or methyl-branched,
more particularly 2-methyl-branched, aliphatic radical containing 8 to 22
and preferably 12 to 18 carbon atoms and G stands for a glycose unit
containing 5 or 6 carbon atoms, preferably glucose. The degree of
oligomerization x, which indicates the distribution of monoglycosides and
oligoglycosides, is a number of 1 to 10 and preferably 1.2 to 1.4.
Another class of preferred nonionic surfactants which may be used
either as sole nonionic surfactant or in combination with other nonionic
surfactants are alkoxylated, preferably ethoxylated or ethoxylated and
propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon
atoms in the alkyl chain, more especially the fatty acid methyl esters which
are described, for example, in Japanese patent application JP 581217598
or which are preferably produced by the process described in International
patent application WO-A-90113533.
Nonionic surfactants of the amine oxide type, for example N-
coconutalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxy-
ethylamine oxide, and the fatty acid alkanolamide type are also suitable.
The quantity in which these nonionic surfactants are used is preferably no
more than the quantity in which the ethoxylated fatty alcohols are used
CA 02306388 2000-04-20
23
and, more preferably, no more than half that quantity.
Other suitable surfactants are polyhydroxyfatty acid amides
corresponding to formula (III):
R'
R-CO-N-[Z] (I I I)
in which RCO is an aliphatic acyl group containing 6 to 22 carbon atoms,
R' is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon
atoms and [Z] is a linear or branched polyhydroxyalkyl group containing 3
to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid
amides are known substances which may normally be obtained by
reductive amination of a reducing sugar with ammonia, an alkylamine or an
alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl
ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds
corresponding to formula (lU):
R~-O-R2
R-CO-N-[Z] (IV)
in which R is a linear or branched alkyl or alkenyl group containing 7 to 12
carbon atoms, R' is a linear, branched or cyclic alkyl group or an aryl group
containing 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl
group or an aryl group or an oxyalkyl group containing 1 to 8 carbon atoms,
C» alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxy-
alkyl group, of which the alkyl chain is substituted by at least two hydroxyl
groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives
of that group.
[Z] is preferably obtained by reductive amination of a reduced sugar,
for example glucose, fructose, maltose, lactose, galactose, mannose or -
CA 02306388 2000-04-20
24
xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be
converted into the required polyhydroxyfatty acid amides by reaction with
fatty acid methyl esters in the presence of an alkoxide as catalyst, for
example in accordance with the teaching of International patent application
WO-A-95107331.
Besides pure nonionic surfactants, other substances from the group
of ionic surfactants, for example anionic or cationic surfactants, may of
course also be present in the dishwasher detergents according to the
invention.
According to the invention, preferred particulate dishwasher
detergents contain surfactant(s), preferably nonionic surfactant(s), in
quantities of 0.5 to 10% by weight, preferably in quantities of 0.75 to 7.5%
by weight and more preferably in quantities of 1.0 to 5% by weight, based
on the detergent as a whole.
Among the compounds yielding H202 in water which serve as
bleaching agents, sodium perborate tetrahydrate and sodium perborate
monohydrate are particularly important. Other useful bleaching agents are,
for example, sodium percarbonate, peroxypyrophosphates, citrate perhy-
drates and H202-yielding peracidic salts or peracids, such as
perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or
diperdodecane dioic acid. Detergents according to the invention may also
contain bleaching agents from the group of organic bleaching agents.
Typical organic bleaching agents are the diacyl peroxides, such as
dibenzoyl peroxide for example. Other typical organic bleaching agents are
the peroxy acids, of which alkyl peroxy acids and aryl peroxy acids are
particularly mentioned as examples. Preferred representatives are (a)
peroxybenzoic acid and ring-substituted derivatives thereof, such as alkyl
peroxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium
monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such
as peroxylauric acid, peroxystearic acid, ~-phthalimidoperoxycaproic acid
CA 02306388 2000-04-20
[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxy-
caproic acid, N-nonenylamidoperadipic acid and N-nonenylamido-
persuccinates. and (c) aliphatic and araliphatic peroxydicarboxylic acids,
such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid,
5 diperoxysebacic acid, diperoxybrassylic acid, diperoxyphthalic acids, 2-
decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyl-di(6-amino-
percaproic acid).
Other suitable bleaching agents in the dishwasher detergents
acording to the invention are chlorine- and bromine-releasing substances.
10 Suitable chlorine- or bromine-releasing materials are, for example,
heterocyclic N-bromamides and N-chloramides, for example
trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid
and/or dichloroisocyanuric acid (DICA) and/or salts thereof with cations,
such as potassium and sodium. Hydantoin compounds, such as 1,3-
15 dichloro-5,5-dimethyl hydantoin, are also suitable.
The bleaching agents are normally used in dishwasher detergents in
quantities of 1 to 30% by weight, preferably in quantities of 2.5 to 20% by
weight and more preferably in quantities of 5 to 15% by weight, based on
the detergent. In the context of the present invention, the quantities
20 mentioned are based on the weight of the basic powder, i.e. the detergent
without the added enzyme particles according to the invention.
Bleach activators which support the effect of the bleaching agents
can also be part of the basic powder. Known bleach activators are
compounds which contain one or more N- or O-acyl groups, such as
25 substances from the class of anhydrides, esters, imides and acylated
imidazoles or oximes. Examples are tetraacetyl ethylenediamine (TAED),
tetraacetyl methylenediamine (TAMD) and tetraacetyl hexylenediamine
(TAHD) and also pentaacetyl glucose (PAG), 1,5-diacetyl-2,2-
dioxohexaydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).
Suitable bleach activators are compounds which form aliphatic
CA 02306388 2000-04-20
26
peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and
more preferably 2 to 4 carbon atoms and/or optionally substituted
perbenzoic acid under perhydrolysis conditions. Substances bearing O-
and/or N-acyl groups with the number of carbon atoms mentioned and/or
optionally substituted benzoyl groups are suitable. Preferred bleach
activators are polyacylated alkylenediamines, more particularly tetraacetyl
ethylenediamine (TAED), acylated triazine derivatives, more particularly
1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycol-
urils, more particularly tetraacetyl glycoluril (TAGU), N-acylimides, more
particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates,
more particularly n-nonanoyl- or isononanoyl-oxybenzenesulfonate (n- or
iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride,
acylated polyhydric alcohols, more particularly triacetin, ethylene glycol
diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl morpholinium
acetonitrile methyl sulfate (MMA) and the enol esters known from German
patent applications DE 196 16 693 and DE 196 16 767, acetylated sorbitol
and mannitol and the mixtures thereof (SORMAN), acylated sugar
derivatives, more particularly pentaacetyl glucose (PAG), pentaacetyl
fructose, tetraacetyl xylose and octaacetyl lactose, and acetylated,
optionally N-alkylated glucamine and gluconolactone, and/or N-acylated
lactams, for example N-benzoyl caprolactam. Substituted hydrophilic acyl
acetals are also preferably used. Combinations of conventional bleach
activators may also be used. The bleach activators are normally used in
dishwasher detergents in quantities of 0.1 to 20% by weight, preferably in
quantities of 0.25 to 15% by weight and most preferably in quantities of 1 to
10% by weight, based on the detergent as a whole. In the context of the
invention, the quantities mentioned are based on the weight of the basic
powder.
In addition to or instead of the conventional bleach activators
mentioned above, so-called bleach catalysts may also be incorporated in
CA 02306388 2000-04-20
27
the basic powder. These substances are bleach-boosting transition metal
salts or transition metal complexes such as, for example, manganese-,
iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes.
Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and
copper complexes with nitrogen-containing tripod ligands and cobalt-, iron-,
copper- and ruthenium-ammine complexes may also be used as bleach
catalysts.
Bleach activators from the group of polyacylated alkylenediamines,
more particularly tetraacetyl ethylenediamine (TAED), N-acyl imides, more
particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates,
more particularly n-nonanoyl- or isononanoyl-oxybenzenesulfonate (n- or
iso-NOBS), n-methyl morpholinium acetonitrile methyl sulfate (MMA) are
preferably used, preferably in quantities of up to 10% by weight, more
preferably in quantities of 0.1% by weight to 8% by weight, most preferably
in quantities of 2 to 8% by weight and, with particular advantage, in
quantities of 2 to 6% by weight, based on the detergent as a whole.
Bleach-boosting transition metal complexes, more particularly
containing the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru,
preferably selected from the group of manganese and/or cobalt salts and/or
complexes, more preferably the cobalt (ammine) complexes, cobalt
(acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or
manganese and manganese sulfate, are also present in typical quantities,
preferably in a quantity of up to 5% by weight, more preferably in a quantity
of 0.0025% by weight to 1 % by weight and most preferably in a quantity of
0.01 % by weight to 0.25% by weight, based on the detergent as a whole.
In special cases, however, more bleach activator may even be used.
The basic powder may of course also contain enzymes so that a
conventional enzyme release and effect is achieved and is supported by
the enzyme release and effect from the enzyme particles according to the
invention. Corresponding detergents have as it were a "booster enzyme
CA 02306388 2000-04-20
28
effect". The enzymes optionally used in the basic powder are preferably
commercially available solid enzyme preparations.
Suitable enzymes in the basic powders are, in particular, those from
the classes of hydrolases, such as proteases, esterases, lipases or lipolytic
enzymes, amylases, glycosyl hydrolases and mixtures thereof. All these
hydrolases contribute to the removal of stains, such as protein-containing,
fat-containing or starch-containing stains. Oxidoreductases may also be
used for bleaching. Enzymes obtained from bacterial strains or fungi, such
as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus
cinereus and Humicola insolens and from genetically modified variants are
particularly suitable. Proteases of the subtilisin type are preferably used,
proteases obtained from Bacillus lentus being particularly preferred. Of
particular interest in this regard are enzyme mixtures, for example of
protease and amylase or protease and lipase or lipolytic enzymes or of
protease, amylase and lipase or lipolytic enzymes or protease, lipase or
lipolytic enzymes, but especially protease- and/or lipase-containing
mixtures or mixtures with lipolytic enzymes. Examples of such lipolytic
enzymes are the known cutinases. Peroxidases or oxidases have also
been successfully used in some cases. Suitable amylases include in
particular a-amylases, isoamylases, pullanases and pectinases.
The enzymes may be adsorbed to supports and/or encapsulated in
shell-forming substances to protect them against premature decomposition.
The percentage content of the enzymes, enzyme mixtures or enzyme
granules may be, for example, from about 0.1 to 5% by weight and is
preferably from 0.5 to about 4.5% by weight. Preferred detergents
according to the invention are characterized in that the basic powder
contains protease and/or amylase.
By virtue of the fact that the detergents according to the invention
may contain the enzymes) in two basically different regions, it is possible
to provide detergents characterized by a very precisely defined enzyme
CA 02306388 2000-04-20
29
release and effect. The following Table provides an overview of possible
enzyme distributions in detergents according to the invention:
Basic powder Enzyme particles
- Amylase
- Protease
- Lipase
- Amylase + Protease
- Amylase + Lipase
- Protease + Lipase
- Amylase + Protease
+
Lipase
Amylase Amylase
Protease Amylase
Amylase + Protease Amylase
Amylase Protease
Protease Protease
Amylase + Protease Protease
Amylase Amylase + Protease
Protease Amylase + Protease
Amylase + Protease Amylase + Protease
Lipase Amylase
Amylase + Lipase Amylase
Protease + Lipase Amylase
Amylase + Protease + Amylase
Lipase
Lipase Protease
Amylase + Lipase Protease
Protease + Lipase Protease
Amylase + Protease + Protease
Lipase
Lipase Amylase + Protease
Amylase + Lipase Amylase + Protease
Protease + Lipase Amylase + Protease
amylase + Protease+ Lipase~ Amylase + Protease
Dyes and perfumes may be added to the dishwasher detergents
according to the invention both in the basic powder and in the enzyme
particles according to the invention in order to improve the aesthetic
impression created by the products and to provide the consumer not only
with the required performance but also with a visually and sensorially
CA 02306388 2000-04-20
"typical and unmistakable" product. Suitable perfume oils or perfumes
include individual perfume compounds, for example synthetic products of
the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Perfume
compounds of the ester type are, for example, benzyl acetate,
5 phenoxyethyl isobutyrate, p-tert.butyl cyclohexyl acetate, linalyl acetate,
dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate,
benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate,
styrallyl propionate and benzyl salicylate. The ethers include, for example,
benzyl ethyl ether; the aldehydes include, for example, the linear alkanals
10 containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetal-
dehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the
ketones include, for example, the ionones, a-isomethyl ionone and methyl
cedryl ketone; the alcohols include anethol, citronellol, eugenol, geraniol,
linalool, phenyl ethyl alcohol and terpineol and the hydrocarbons include,
15 above all, the terpenes, such as limonene and pinene. However, mixtures
of various perfumes which together produce an attractive perfume note are
preferably used. Perfume oils such as these may also contain natural
perfume mixtures obtainable from vegetable sources, for example pine,
citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary
20 oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil,
lime
blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and
labdanum oil and orange blossom oil, neroli oil, orange peel oil and
sandalwood oil.
The perfumes may be directly incorporated in the detergents
25 according to the invention, although it can also be of advantage to apply
the perfumes to supports.
In order to improve their aesthetic impression, the detergents
according to the invention (or parts thereof) may be colored with suitable
dyes. Preferred dyes, which are not difficult for the expert to choose, have
30 high stability in storage, are not affected by the other ingredients of the
CA 02306388 2000-04-20
31
detergents or by light and do not have any pronounced substantivity for the
substrates treated with the detergents, such as glass, ceramics or plastic
tableware, so as not to color them.
To protect the tableware or the machine itself, the detergents
according to the invention may contain corrosion inhibitors, especially in the
basic powder, silver protectors being particularly important for dishwashing
machines. Known corrosion inhibitors may be used. Above all, silver
protectors selected from the group of triazoles, benzotriazoles,
bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition
metal salts or complexes may generally be used. Benzotriazole and/or
alkylaminotriazole is/are particularly preferred. In addition, dishwashing
formulations often contain corrosion inhibitors containing active chlorine
which are capable of distinctly reducing the corrosion of silver surfaces.
Chlorine-free dishwashing detergents contain in particular oxygen- and
nitrogen-containing organic redox-active compounds, such as dihydric and
trihydric phenols, for example hydroquinone, pyrocatechol, hydroxy-
hydroquinone, gallic acid, phloroglucinol, pyrogallol and derivatives of
these compounds. Salt-like and complex-like inorganic compounds, such
as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are also frequently used.
Of these, the transition metal salts selected from the group of manganese
and/or cobalt salts and/or complexes are preferred, cobalt(ammine)
complexes, cobalt(acetate) complexes, cobalt(carbonyl) complexes,
chlorides of cobalt or manganese and manganese sulfate being particularly
preferred. Zinc compounds may also be used to prevent corrosion of
tableware.
The enzyme particles according to the invention have clear
advantages over conventional products when used in dishwasher
detergents. Accordingly, the present invention also relates to the use of
enzyme particles of
a) 5 to 99.5% by weight of one or more coating materials with a melting
CA 02306388 2000-04-20
32
point above 30°C,
b) 0.5 to 60% by weight of one or more liquid enzyme preparations)
dispersed in the coating materials) and
c) 0 to 5% by weight of other active substances and auxiliaries,
d) 0 to 90% by weight of one or more carrier materials
in particulate dishwasher detergents.
The use of enzymes dispersed in polyethylene glycols with
molecular weights of 1500 to 36,000, preferably in the range from 2000 to
6000 and more preferably in the range from 3000 to 5000 in dishwasher
detergents is particularly preferred.
As the following Examples show, the enzyme particles according to
the invention release the enzymes more quickly and for longer periods than
conventional detergents. Accordingly, the present invention also relates to
the use of enzyme particles of
a) 5 to 99.5% by weight of one or more coating materials with a melting
point above 30°C,
b) 0.5 to 60% by weight of one or more liquid enzyme preparations)
dispersed in the coating materials) and
c) 0 to 5% by weight of other active substances and auxiliaries,
d) 0 to 90% by weight of one or more carrier materials
for the rapid and long-lasting release of enzymes from detergents
containing these enzyme particles.
Specific embodiments of the present invention are described in the
following examples which are not to be construed as limiting.
Examples
Spherical particles between 500 and 700 Nm in diameter were
prepared by prilling from melt dispersions with the composition shown in
the following Table:
CA 02306388 2000-04-20
33
Enzyme particles Enzyme particles
1 2
Protease (BLAP~ S 260 15.0 -
LD)
Amylase (Termamyl~ 300 - 15.0
L)
PEG 4000 85.0 85.0
These enzyme particles were incorporated as "boosters" in powder
form dishwasher detergents with the following composition:
Detergent powder Detergent powder
1 2
Protease-containingProtease-free
Sodium carbonate 16.5 18.0
Sodium tripolyphosphate50.0 50.0
Sodium disilicate 5.0 5.0
Polycarboxylate 5.0 5.0
HEDP* 1.0 1.0
Sodium perborate 10.0 10.0
Tetraacetyl ethylenediamine2.0 2.0
C~2 fatty alcohol + 2.0 2.0
3 EO
Protease (BLAP~ 200 1.5 -
S)
Amylase (Duramyl~ 60 2.0 2.0
T)
Balance** 5.0 5.0
* Hydroxyethane-1,1-diphosphonicacid, tetrasodium salt
** Perfume, dye, salts, binder
The protease-containing detergent 1 was mixed with the enzyme
particles 1, 24 g powder being mixed with 1 g enzyme particles. The
protease-free detergent 2 was similarly mixed with the enzyme particles 1.
The cleaning performance of the powders containing the enzyme
particles according to the invention was evaluated against the additive-free
detergent powders 1 and 2 (Comparison Examples C1 and C2). To this
end, soiled tableware was cleaned in the main wash cycle of a 55°C
program (water hardness 16°d) of a Miele G 590 with universal program,
the detergent being used in a quantity of 25 g. The following Table shows
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34
the cleaning performance of the individual powders against various
protease-sensitive soils. It is pointed out in this connection that detergent
powder 2 is protease-free while detergent powder 1 contains protease.
Powder E1 according to the invention (protease-containing detergent 1 with
the enzyme particles 1 ) contains the protease both in the powder and in the
enzyme particles whereas powder E2 according to the invention contains
the protease in the enzyme particles only. The cleaning performance of the
detergents against the soils was visually evaluated by experts and scored
on a scale of 0 to 10 where a score of "0" signifies no cleaning while a
score of "10" signifies complete removal of the stains. The results of the
cleaning tests are set out in the following Table. In the interests of
clarity,
the presence of protease in the basic powder is indicated by the letter "B"
while the presence of protease in enzyme particles is indicated by the letter
"P".
Protease in B + p B
p
E1 E2 C1 C2
Minced meat on glass (burnt-on)9.0 - 8.0 -
Minced meat on china (dried-on)10.0 - 9.0 -
Egg yolk (dried-on) 10.0 8.0 8.9 1.0
Egg/milk (dried-on) 10.0 10.0 10.0 1.0
In order further to illustrate the "booster effect" of the enzyme core,
detergent powders C1 and E1 were compared in a 40°C program:
C1 E1
Minced meat on glass (burnt-on)5.2 6.0
Minced meat on china (dried-on)5.7 6.5
Egg yolk (dried-on) 3.2 5.8
Egg/milk (dried-on) 5.0 8.8
The results show that the presence of protease on its own in the
enzyme particles according to the invention is equivalent to a multiple dose
CA 02306388 2000-04-20
of protease in the basic powder against certain soils (comparison E2-C1).
If the protease is used both in the powder and in enzyme particles,
cleaning performance against all soils can be distinctly improved, even in
low-temperature programs.
Effectiveness against amylase-sensitive soils can be similarly
demonstrated. To this end, detergent powder 2 was mixed with the
enzyme particles 2 (E3) and compared for performance with additive-free
detergent powder 2 (C3).
C3 E3
40C 55C 40C 55C
Oat flakes (dried-on)7.2 8.2 8.4 9.5
Rice starch (dried-on)2.8 - 8.3 -
Starch mix (dried-on)5.7 10.0 9.1 10.0
Spaghetti 7.0 - 7.6 -
It can again be seen that cleaning performance against all soils is
distinctly improved, even in low-temperature programs, where amylase is
used both in the detergent powder and in enzyme particles.
Release kinetics
In an enzyme release test, the protease-containing basic powder 1
(C4) was compared with a protease-free basic powder 2 which contained
the same quantity of protease in the form of the enzyme particles 1
according to the invention with the composition mentioned above (85%
PEG, 15% protease) (E4). Both detergents were subjected to the main
wash cycle of a dishwashing machine, enzyme activity being measured as
a function of time. The results are set out in the following Table:
Time [mins.j 2.5 5 6.75 7.5 10 15 20 25
Protease activity 2 5 10 25 100 60 10 6
C4
Protease activity 0 60 100 80 70 70 66 50
E4
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The Table shows that the detergent according to the invention
reaches its maximum activity after only 6.75 minutes while the comparison
detergent takes 10 minutes. In addition, enzyme activity in the wash liquor
remains at a high level throughout the main wash cycle whereas, in the
Comparison Example, it falls dramatically only shortly after the maximum.
