Note: Descriptions are shown in the official language in which they were submitted.
CA 02317030 2000-09-08
METHOD FUR PRODUCING DETERGENT FORMS
Field of the Invention
The present invention relate;s to a process for the production of formed
bodies having
active washing and cleaning properties. In particular, the invention relates
to a
process for the production of detergent and cleaning agent formed bodies for
washing
of textiles in a domestic washing machine, which are, in brief, called
detergent tablets.
Background of the Invention
Nowadays, commercial detergents and cleaning agents are available in the form
of
liquid products or solids. .As regards the latter type, a distinction is made
between
conventional powf~ers and concentrates which may be obtained by granulation or
extrusion, for example. (:ompared with the conventional powders, concentrated
detergents and cleaning agents have the advantage of a reduced amount of
packaging
having to be dealt with and quantitatively less product has to be metered per
wash
cycle. Moreover, as a result of the reduced packet sizes, transport and
storage costs
are reduced. The most highly concentrated form in which detergents and
cleaning
agents are at present on offer on the market in some countries consist of
compressed
detergent and cleaning agent formed bodies. Whereas water softeners and
dishwashing agents for dishwashers are widely available in this form, numerous
problems have occurred in detergents for textiles, which have so far prevented
wide
distribution and acceptance by the consumers. As a result of the substantially
higher
surfactant contents, the problems, which usually occur in the case of the
formed body
form available, are: further increased. Particular problems are posed by
detergents
tablets containing alkoxylated non-ionic surfactants since these types of
surfactant
have a negative effect on the solubility of the tablets - whereas, on the
other hand, it
is these surfactants which are specifically desired because of their high
level of
detergency.
The dichotomy between a sufficiently hard formed body and a sufficiently rapid
decomposition time, in parl;icular, presents a central problem in this
respect. Since
sufficiently stable, i.e. dimensionally stable formed bodies resistant to
fracturing can
1
CA 02317030 2000-09-08
be produced only by way of relatively high compression pressures, a strong
compaction of the formed body components and consequently a delayed
disintegration of the formed body in the aqueous liquor and thus an
excessively slow
liberation of the active substances in the washing and cleaning process
occurs. In
addition, the delayed disintegration of the formed body has a disadvantage
that the
usual detergent and cleaning agent formed bodies cannot be flushed into
domestic
washing machines through the dispenser chamber since the tablets do not break
down
sufficiently rapidly into secondary particles small enough to be flushed from
the
dispenser chamber into the washing machine drum.
To solve this problem, various approaches have been made in the state of the
art.
Apart from using special constituents intended to promote disintegration,
coating
individual constituents and sieving of the pre-mixtures to be compressed have
been
suggested.
Thus, EP-A-0 466 484 (Unilever) discloses detergent tablets in the case of
which the
pre-mixture to be compressed has particle sizes of between 200 and 1200 Vim,
the
upper and lower limits of the particle sizes differing by no more than 700
p,m.
Compressing substantially coarser particles into tablets is not suggested in
this
specification.
EP-A-0 522 766 (Unilever) also relates to formed bodies of a compacted,
particulate
detergent composition containing surfactants, builders and disintegration aids
(e.g.
those based on cellulose), at least part of the particles being coated with
the
disintegration aid which exhibits both a binding and a disintegration effect
during
dissolution of the formed 'bodies in water. This specification also points out
the
general problems involved in producing formed bodies of adequate stability and
a
simultaneous satisfactory solubility. The particle size in the mixture to be
compressed
should in this case. be above 200 Vim, the upper and lower limit of the
individual
particle sizes not differing by more than 700 p,m. In this specification, to,
it is
explicitly stated that the parl:icles should not be coarser than 1200 pm.
2
CA 02317030 2000-09-08
DE 40 10 533 (Henkel KGaA) discloses a process for the production of
compressed
bodies made from pre-compacted granules. In this case, the granules previously
produced in a first operating stage by extrusion moulding and comminution are,
if
S necessary, mixed with further constituents and auxiliary agents and
tableted. The
proportion of pre-compacted granules in the compressed bodies is as much as
100%
in this specificatior.~. A pretreatment of the optionally used components to
be admixed
is not disclosed.
Although the detergent tables produced according to the above documents have a
sufficient hardness., they exhibit decomposition rates which do not allow
metering via
a dispenser chamber in a domestic washing machine. In the above-mentioned
specifications of the state of the art, dissolution times of less than 10
minutes and
residual values of less than 50% are considered satisfactory, such values
being
completely unsatisfactory for the use of detergent tablets via the dispenser
chamber.
A further disadvantage of the formed bodies produced according to the state of
the art
consists of their unsatisfactory resistance to shock type impact. The tablets
are
sufficiently stable vis-a-vis pressure which is exerted on them on a slowly
increasing
scale but burst when being dropped onto a hard substrate, for example. When
being
dropped or transported, it is also possible for edge breakage phenomena to
occur on
the tablets against which conventional tablets are insufficiently resistant.
In addition,
the usual detergent and cleaning agent formed bodies have the disadvantage of
hardening further ~or becoming deliquescent during storage, so that they must
be
protected against the surrounding air - something that is usually achieved by
individual packaging.
Summary of the Invention
Consequently, the present invention was based on the task of providing a
process for
the production of detergent and cleaning agent formed bodies, which process
makes it
possible to produce formed bodies which are free from the above-mentioned
disadvantages. In this process, it should be possible to produce detergent and
3
CA 02317030 2000-09-08
cleaning agent formed bodies in a simple and highly reproducible manner, which
formed bodies have a high level of hardness, are characterised by a rapid rate
of
dissolution and car. be used via the dispenser chamber in domestic washing
machines.
In this respect, the hardness should be restricted not only to a high
diametral fracture
stress, the stability of the formed bodies should be guaranteed during
transportation
(friction/vibration ;>tress) and while being dropped.
In addition, the formed bodies to be produced according to the process to be
provided
should not undergo any changes to their advantageous property profile during
open
storage so that air-tight packaging of the individual tablets becomes
necessary.
It has now been found that detergent and cleaning agent formed bodies with the
above-mentioned advantages can be produced by compressing pre-mixtures which
contain both pourable and flowable high density granules produced via the
plasticised
state as well as agglomerates of further optional constituents which have
particle sizes
of between 800 and 2000 pm and are essentially free from fines.
The subject matter of the invention is a process for the production of
detergent and
cleaning agent formed bodies, which process comprises the steps
2.0 a) Processing of at least mainly solid, finely particulate constituents in
the
plasticised state to form pourable and flowable high density granules.
b) The production of one or several agglomerates from further constituents to
be
optionally used.
c) Combining the granules of steps a) and b) to form compressed pre-mixtures
and
d) Compressing the pre-mixtures to form single or multiple phase formed bodies
the granules produced in steps a) and b) being essentially free from fines and
having
particle sizes of between 800 and 2000 pm.
Within the framework of the present invention, the term "essentially free from
fines"
characterises particle mixtures which exhibit less than 20% by weight of
particles of a
size of less than 800 pm. In particular, particle mixtures are preferred whose
content
4
CA 02317030 2000-09-08
of particles of a size of less than 600 p,m is below 10% by weight, mixtures
being
preferred which contain a maximum of 3% by weight of particles with a size of
less
400 Vim. Overall, i.t is preferred to keep the proportion of particles with
particle sizes
of less than 800 pnn even lower, for example below 15% by weight, preferably
below
10% by weight and. in particular below 5% by weight.
The particles of the pre-mixture which, in step d) of the process according to
the
invention, are compressed to form detergent and cleaning agent formed bodies
have
particle sizes of between 800 and 2000 pm. In this respect, it is preferred
for at least
75% by weight of these particles to have a particle size of between 800 and
1600 p,m.
Mixtures of the granules produced in steps a) and b), at least 60% by weight
which
consists of particles with a particle size of between 1200 and 15 Vim, are
again
preferred.
1 S Detailed Description of the Invention
The process according to the invention is broken down into four steps: in the
first
step, at least predominantly solid, finely particulate constituents are
processed in the
plasticised state to form pourable and flowable high density granules. The
second
step comprises the production of one or more agglomerates from further
constituents
2.0 to be optionally used, the production process being here - as in the first
step -
adjusted such as to achieve the desired particle size range. The
granules/agglomerates
produced in the first two steps a) and b) are mixed together in the third step
and
subsequently compressed to form detergent and cleaning agent formed bodies.
f,5 Process step al:
The production of the high density pourable and flowable granules in step a)
is
effected by processing in l;he plasticised state. The production processes for
such
granules are described in the state of the art and can be used within the
framework of
partial step a) of the process according to the invention.
3~0
5
CA 02317030 2000-09-08
A process to be preferably used for the production of pourable and flowable
high
density granules via the plasticised state is described in the earlier German
patent
application 196 :38 599.7 (Henkel KGaA). According to the theorem of this
application, the production of the pourable and flowable high density granules
in step
a) is effected by joining deaergent or cleaning agent compounds and/or
detergent or
cleaning agent raw materials with simultaneous or subsequent forming, a solid
pre-
mixture being initially produced which contains individual raw materials
and/or
compounds which are present as a solid at room temperature and a pressure of 1
bar
and exhibit a melting point or softening point of not less than 45°C
and also contains,
if necessary, up t~o 10% by weight of non-ionic surfactants which are liquid
at
temperatures below 45°C a~ld a pressure of 1 bar and which, by applying
compaction
forces at temperatures of at least 45°C, and are converted into a grain
and, if
necessary, subsequently processed or treated further with the proviso that
- the pre-mixture is essentially anhydrous and
- at least one raw material or compound, which is solid at a pressure of 1 bar
and temperatures below 45°C, is present under the processing conditions
as a
melt, this smelt serving as a polyfunctional, water- soluble binder which,
during the production of the agents, operates as a slip and as an adhesive for
the solid dc;tergent ~or cleaning agent compounds or raw materials but has a
2.0 disintegrating effect during the re-dissolution of the agent in the
aqueous
liquor.
Within the framework of t:he disclosure of this specification, the term
"essentially
anhydrous" should be understood to refer to a state in which the content of
liquid
f,5 water, i.e. water not present in the form of water of hydration and/or
constitutional
water, is below 5°/. by weight, preferably below 3% by weight and in
particular even
below 0.5% by weight, based on the pre-mixture. Consequently, water can be
introduced into the: process for the production of the pre-mixture essentially
only in
the chemically and/or physically combined form or as a component of the raw
3~0 materials or compounds present as solids at temperatures below 45°C
and at pressure
of 1 bar but not as a liquid, aolution or dispersion.
6
CA 02317030 2000-09-08
In the above-mem:ioned specification, the term particulate detergents or
cleaning
agents is understood to mean those agents which do not contain dust-type
fractions
and, in particular, do not have particle sizes of less than 200 pm. In a
particularly
preferred embodirr~ent of the invention disclosed therein, the detergents or
cleaning
agents produced, the compounds or the treated raw materials consist - in a
proportion
of at least 70% by weight, preferably at least 80% by weight and particularly
preferably a higher proportion of up to 100% by weight - of spherical (bead
type)
particles with a paa-ticle size distribution in the case of which at least 80%
by weight
of the particles are between 0.8 and 2.0 mm.
The term detergents or cleaning agents should be understood to mean those
compositions which can be used for washing and cleaning without commonly other
constituents having to be admixed. A compound, on the other hand, consists of
at
least 2 components usually used in detergents or cleaning agents; however,
compounds are normally used only in mixture with other components, preferably
together with other compounds. Within the framework of this invention, a
treated raw
material is a relatively finely particulate raw material which is converted by
the
process according to the invention into coarser particles. Strictly speaking,
a treated
raw material is a compound within the framework of the invention if the
treatment
2;0 agent is a constituent usually used in detergents or cleaning agents.
The constituents used in the above-mentioned process - with the exception of
the non-
ionic surfactants liquid at temperatures below 45°C and a pressure of 1
bar, which
may be present if r,~ecessary - may consist of compounds produced separately
but also
2;5 of raw materials v~~hich are present in powder or particulate form (finely
divided to
coarse) and are, in any case, solid at room temperature and a pressure of 1
bar.
Suitable particulate; particles which can be used are, for example, beads or
(fluid bed)
granules etc produced by spray drying. The composition of the compounds as
such is
unimportant for the invention with the exception of the water content which
must be
3'.0 such that the pre-mixture, as defined above, is essentially free from
water and
contains preferably not more than 10% by weight of water of hydration and/or
constitutional water. It is also possible to use solid compounds in the pre-
mixture
7
CA 02317030 2000-09-08
which compounds serve as earners for liquids, for example for liquid non-ionic
surfactants or silicone oil and/or paraffins. These compounds may contain
water to
the extent as indicated above, the compounds being flowable and remaining
flowable
or at least conveyable even at higher temperatures of at least 45°C. In
particular,
however, it is preferable that compounds with maximum 10% by weight and
particularly preferentially v~rith maximum 7% by weight of water, based on the
pre-
mixture, are used in the pre-mixture. Free water, i.e. water which is not
combined in
any form with a solid and consequently is present "in the liquid form" is
preferably
not contained in the pre-mixture since even very small quantities, e.g.
approximately
0.2 or 0.5% by weight, ba:>ed on the pre-mixture, are already sufficient to
partially
dissolve the binder which is. water-soluble as such. This would have the
consequence
of reducing the melting point or the softening point and causing the end
product to
lose both some of its flowable properties and some of its bulk density.
It has been found that it is in no way irrelevant to which solid raw material
or in
which solid compound the water is bound. Thus, water which is bound to builder
substances such zeolite and silicates (details of the description of the
substances are
given below), in particular if the water is bound to zeolite A, zeolite P or
MAP and/or
zeolite X, can be considered as being less critical. On the other hand, it is
preferred
2.0 that water which is bound to solid components other than the above-
mentioned
builder substances should preferably be present in the pre-mixture in
quantities of less
than 3% by weight. In one embodiment of the invention, it is therefore
preferred for
the content of bound water in the pre-mixture to be no more than 10% by weight
and/or the content ~of water not bound to zeolite and/or silicates to be less
than 7% by
f,5 weight and in particular maximum 2-5% by weight. In this connection, it is
particularly advantageous if the pre-mixture contains no water that is not
bound to the
builder substances. However, this is difficult to achieve technically since,
as a rule, at
least traces of water are always entrained by the raw materials and compounds.
3~0 The content of liquids which are non aqueous at temperatures below
45°C present in
the solid compounds used in the pre-mixture amounts preferably also or
additionally
to up to 10% by weight, preferably to as much as 6% by weight, again based on
the
8
CA 02317030 2000-09-08
pre-mixture. In particular, solid compounds are used in the pre-mixture, which
compounds contained usual non-ionic surfactants liquid at temperatures below
45°C
and a pressure of 1 bar, wluch compounds can be produced separately according
to
any of the known types of production - e.g. by spray draying, granulation or
atomisation treatment of c~~rrier beads. In this way, pre-mixtures can be
produced
which allow, for example, up to approximately 10% by weight, preferably less,
in
particular up to maximum 8% by weight and, for example, between 1 and 5% by
weight of non-ionic surfactants, based on the finished agent.
Compounds which contain water in the form as indicated above and/or serve as
carrier for liquids, in particular for non-ionic surfactants which are liquid
at room
temperature, i.e. contain these constituents which are liquid at room
temperature and
can be used according to the theorem of the above-mentioned application, have
under
no circumstance ,~ softening point below 45°C. Similarly, the
individual raw
materials used separately :have a melting point of at least 45°C.
Preferably, the
melting point and/or the softening point of all the individual raw materials
and
compounds used in the pre-mixture is above 45°G and advantageously at
least 50°C.
In a preferred embodiment of the invention, at least 80% by weight, in
particular at
least 85% by weight and particularly preferably at least 90% by weight of the
compounds and individual raw materials used in the pre-mixture have a much
higher
softening point and/or melting point than those that can be reached under the
process
conditions. In practise, the process temperatures will not be above
150°C, preferably
not above 120°C, for economic reasons alone. Thus, at least 80% by
weight of the
compounds and individual raw materials used will have a softening point and/or
melting point above 150°C',. As a rule, the softening point or the
melting point is
substantially above; this terr~perature. If constituents are used which
decompose under
the effect of the temperature, e.g. peroxy bleaching agents such as perborate
or
percarbonate, the decomposition temperature of these constituents at a
pressure of 1
bar and in particular at higher pressures which are present in the preferred
extrusion
processes according to the invention, is also significantly above 45°C.
9
CA 02317030 2000-09-08
Apart from the solid components, the pre-mixture can additionally contain up
to 10%
by weight of non-ionic surfactants liquid at temperatures below 45°C
and a pressure
of 1 bar, in particular the alkoxylate alcohols usually used in detergents or
cleaning
agents such as fatty alcohols or oxy alcohols with a C chain length of between
8 and
20 and in particular on average 3 to 7 ethylene oxide units per mole alcohol
(a
detailed description is given below). The addition of the liquid non-ionic
surfactants
can be effected in quantities which are such as to ensure that the pre-mixture
is still
present in the flowable form. If such liquid nio-ionic surfactants are
introduced into
the pre-mixture it is preferable that liquid nio-ionic surfactants and the
binder having
a disintegrating effect are introduced separately into the process. In such a
preferred
embodiment of the invention, the liquid nio-ionic surfactants are applied by
means of
nozzles in a continuous production process onto the powder stream and absorbed
by
the latter.
However, the pre-mixture also contains at least one raw material or at least
one
compound which serves as a binder and which is solid at room temperature but
present as a liquid or in the form of a melt during compaction under the
conditions of
the process. The binder itself can be atomised onto the pre-mixture once it
has melted
or added dropwise; to the pre-mixture; on the other hand, however, it has
proved
2:0 advantageous to introduce the binder in the solid form as a powder into
the pre-
mixture. The melting point or the softening point at a pressure of 1 bar is at
least
45°C and (in particular for economic reasons) preferably below
200°C, in particular
below 150°C. If tlhe binder is introduced into the pre-mixture in the
form of a melt,
the temperature in the melting vessel is also more than 45°C to maximum
2;5 approximately 200''C, the temperature in the melting vessel being able to
significantly
exceed the melting temperature or the temperature of the softening point of
the binder
or the binder mixture.
The type of suitable binder and the temperature in the process step of
compaction are
?~0 dependent upon each other. As it has proved advantageous for the binder in
the
process step of compaction to be as homogeneously distributed in the compacted
substance as possible, temperatures must be present during the process step of
CA 02317030 2000-09-08
compaction at which the binder softens at least and is preferably present in
the
completely, and not merely the partially, molten form. If, consequently, a
binder with
a high melting point or a high softening point is chosen, a temperature must
be
adjusted during the process step of compaction at which melting of the binder
is
guaranteed. In addition, it should be possible to process also temperature-
sensitive
raw materials, depending on the desired composition of the end product. The
upper
temperature limit in this respect is set by the decomposition temperature of
the
sensitive raw material, it being preferable to operate significantly below the
decomposition temperature of this raw material. On the other hand, the lower
limit
with respect to the melting point or the softening point is of great
importance because,
as a rule, an end product is obtained at melting points or softening points
below 45°C
which tends to agglutinate at temperatures as low as room temperature and at
slightly
elevated temperatures around 30°C, i.e. at summer temperature and under
storage and
transport conditions. It has proved to be particularly advantageous to work at
a
1 S temperature a few degrees, e.g. 2 to 20°C, above the melting point
or above the
softening point.
Preferred binders which can be used as such or in mixture with other binders
are
polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene
glycols
f,0 and polypropylene glycols. The modified polyalkylene glycols include in
particular
the sulphates and/or disulphates of polyethylene glycols or polypropylene
glycols
with a molecular weight between 600 and 12000 and, in particular, between 1000
and
4000. A further ,group consists of mono and/or disuccinates of the
polyalkylene
glycols which, again, have molecular weights of between 600 and 6000,
preferably
2;5 between 1000 and 4000. For a more detailed description of the modified
polyalkylene glycol ethers, reference should be made to the disclosure of the
International Patent Application WO-A-93/02176. Within the framework of this
invention, polyeth~,~lene glycols include those polymers for the production of
which
not only ethylene glycol but also C3-CS glycols as well as glycerine and
mixtures of
?'~0 these are used as starting molecules. They also comprise ethoxylated
derivatives such
as trimethylol propane with 5 to 30 EO.
11
CA 02317030 2000-09-08
The polyethylene glycols preferably used may have a linear or branched
structure,
linear polyethylene glycols being preferred in particular.
The polyethylene glycols which are preferred, in particular, include those
with
molecular weights between 2000 and 12000, advantageously around 4000, it being
possible to use polyethylene glycols with molecular weights of less 3500 and
above
5000, in particular in combination with polyethylene glycols with a molecular
weight
of around 4000, such combinations advantageously containing, in a proportion
of
more than 50% by weight based on the total quantity of the polyethylene
glycols,
polyethylene glycols with a molecular weight of between 3500 and 5000.
However, it
is also possible to use polyethylene glycols as binders which, as such, are
present in
the liquid state at room temperature and a pressure of 1 bar; this involves
above all
polyethylene glycol with a molecular weight of 200, 400 and 600. However,
these
polyethylene glycols which are liquid as such, should be used only in mixture
with at
least one further binder, this mixture having to satisfy again the
requirements of the
invention, i.e. having a melting point and/or softening point of at least more
than
45°C.
Low molecular wc;ight polyvinyl pyrrolidones and their derivatives with
molecular
~;0 weights of maximum 30000 are also suitable as binders. In this respect,
molecular
weight ranges of between 3000 and 30000, preferably around 10000 are
preferred.
Preferably, polyvinyl pyrro lidones are used not as sole binder but in
combination with
others, in particular in combination with polyethylene glycols.
Suitable further binders have proved to consist of raw materials with active
detergent
or cleaning agent properties, i.e., for example, non-ionic surfactants with
melting
points of at least ~45°C or mixtures of non-ionic surfactants and other
binders. The
preferred non-ionic surfactants include alkoxylated fatty or oxoalcohols, in
particular
C12-CIg-alcohols. In this respect, alkoxylation levels, in particular
ethoxylation levels
of, on average, 18 to 80 A(J, in particular EO per mole alcohol, and mixtures
thereof
have proved to be: particularly advantageous. In particular, fatty alcohols
with an
average of 18 to 35 EO, in particular with an average of 20 to 25 EO, exhibit
12
CA 02317030 2000-09-08
advantageous bindc;r properties according to the meaning of the present
invention. If
necessary, the binder mixtures can also contain ethoxylated alcohols with, on
average,
fewer EO units per mole alcohol, such as tallow fatty alcohol with 14 EO.
However,
it is preferable to use these alcohols with a relatively low ethoxylation
level only in
mixture with alcohols with a higher ethoxylation level. Preferably, the
content of
binder in these alcohols with a relatively low ethoxylation level is less than
50% by
weight, in particular less than 40% by weight, based on the total quantity of
binder
used. In particular, non-ionic surfactants commonly used in detergents or
cleaning
agents, such as C,Z-C18-alcohols with a average of 3 to 7 EO, which are liquid
at room
temperature, are preferably present in the binder mixtures merely in
quantities such
that less than 2% by weight of these non-ionic surfactants, based on the end
product
of the process, are thus provided. As described above, it is, however, less
preferable
to use non-ionic surfactants liquid at room temperature in the binder
mixtures. In a
particularly advantageous embodiment, such non-ionic surfactants do not form
part of
1 S the binder mixture since they reduce not only the softening point of the
mixture but
may also contribute to the 'tackiness of the end product and, moreover, as a
result of
their tendency to undergo gel formation on contact with water do not satisfy
the
requirements regarding rapid dissolution of the binder/the separation wall in
the end
product to the desired extent. Similarly, it is not preferable for anion
surfactants or
their precursors, namely the anionic surfactant acids, which are commonly used
in
detergents or cleaning agents, to be present in the binder mixture.
Other non-ionic surfactants which are suitable as binders consist of the fatty
acid
methyl ester ethoxylates which have no gelling tendency, in particular those
with an
:?5 average of 10 to 25 EO (a. more accurate description of this group of
substances is
given below). Particularly preferred representatives of this group of
substances
consist predominantly of methylesters based on C16-C18 fatty acids, for
example
hardened beef tallow methyl esters with an average of 12 EO or an average of
20 EO.
:30 In a preferred embodiment of the invention, a mixture is used as binder
which
employs Cl2-C~8 fatty alcohol based on coconut or tallow with an average of 20
EO
and polyethylene glycol with a molecular weight of 400 to 4000.
13
CA 02317030 2000-09-08
In a further preferred embodiment of the invention, a mixture is used as
binder which
contains predominantly methylesters based on C16-C~8 fatty acids with an
average of
to 25 EO, in particular hardened beef tallow methyl esters with an average of
12
5 EO or an average of 20 EO and a C12-C1g fatty alcohol based on coconut or
tallow
with an average of 20 EO and/or polyethylene glycol with a molecular weight of
400
to 4000.
Particularly prefewed embodiments of the invention have proved to consist of
binders
10 which are either based on polyethylene glycols with a molecular weight of
around
4000 alone or on a mixture of C1z-C~8 fatty alcohol based on coconut or tallow
with an
average of 20 EO and one of the fatty acid methyl ester ethoxylates described
above
or on a mixture of C12-C~g fatty alcohol based on coconut or tallow with an
average of
EO, one of the fatty acid methyl ester ethoxylates described above and a
1.5 polyethylene glycol, in particular one with a molecular weight of around
4000.
In addition, it is possible to use, as further binder, as such or in
combination with
other binders, also alkyl glycides with the general formula RO(G)X in which R
represents a primary, straight-chain or methyl-branched aliphatic radical, in
particular
:'0 one methyl- branched in position 2, with 8 to 22, preferably 12 to 18 C
atoms and G is
the symbol which represents a glycose unit with 5 or 6 C atoms, preferably
glucose.
The degree oligornerisatior~ x which indicates the distribution of
monoglycosides and
oligoglycosides is any desired number between 1 and 10; preferably, x is 1.2
to 1.4.
Those alkyl glyco:>ides are suitable, in particular, which have a softening
point above
:?5 80°C and a melting point above 140°C. Highly concentrated
compounds with
contents of at least: 70% by weight alkyl glycosides, preferably at least 80%
by weight
alkyl glycosides a~-e also suitable. By applying high shear forces, melt
agglomeration
and, in particular, melt extrusion can be brought about with such highly
concentrated
compounds even at temperatures which are above the softening point but still
below
:30 the melting tempE:rature. Although alkyl glycosides can also be used as
the sole
binder, it is preferable to use mixtures of alkyl glycosides and other
binders. In
14
CA 02317030 2000-09-08
particular, mixtures of polyethylene glycol and alkyl glycosides are used
here,
preferably in weigr~t ratios crf 25:1 to 1:5, 10:1 to 2:1 being particularly
preferred.
Polyhydroxy fatty acid amides with formula (I) are also suitable as binders,
in
particular in combination with polyethylene glycols and/or alkyl glycosides,
in which
formula RICO represents an aliphatic acyl radical with 6 to 22 carbon atoms,
R3
represents hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
and
[Z] represents a linear or branched polyhydroxalkyl radical with 3 to 10
carbon atoms
and 3 to 10 hydroxyl groups.
R3
R2-CO-N-[Z] (I)
Preferably, the polyhydroxy fatty acid amides are derived from reducing sugars
with 5
or 6 carbon atoms, in particular from glucose.
The group of polyhydroxy fatty acid amides also includes compounds with
formula
(II)
Ra0_Rs
(II)
R3-CO-N-[Z]
in which R3 represents a linear or branched alkyl or alkenyl radical with 7 to
12
l5 carbon atoms, R4 represents a linear, branched or cyclic alkyl radical or
an aryl radical
with 2 to 8 carbon atoms arid RS represents a linear, branched or cyclic alkyl
radical or
an aryl radical or a~n oxy alkyl radical with 1 to 8 carbon atoms, C1-Ca alkyl
or phenyl
radicals being preferred, arid [Z] represents a linear polyhydroxy alkyl
radical whose
alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated,
preferably
ethoxylated or propoxylated derivatives of this radical. In this case, too,
[Z] is
preferably obtained by the reductive amination of a sugar such as glucose,
fructose,
maltose, lactose, ;;alactose, mannose or xylose. According to the theorem of
the
CA 02317030 2000-09-08
International Patent Application WO-A-95/07331, for example, it is possible in
this
case to convert the N-alkoxy substituted or N-aryloxy substituted compounds by
reaction with fatty acid methyl esters in the presence of an alkoxide as
catalyst into
the desired polyhydroxy fatay acid amides. Particularly preferred glucamides
melt at
temperatures of onlly 95 to 1.05°C. However, in this case, too, - as in
the case of alkyl
glycosides - normal operating temperatures above the softening but below the
melting
temperature are sufficient in the process according to the invention.
The content of binder or binders in the pre-mixture is preferably at least 2%
by weight
but less than 1 S% by weight, in particular less than 10% by weight, 3 to 6%
by
weight, based on the pre-mixture, being particularly preferred.
In a preferred embodiment of the process according to the invention, the
solids for the
production of solid flowable pre-mixture are first mixed at a temperature
between
room temperature and a slightly elevated temperature, preferably below the
melting
temperature or the softening point of the binder and in particular at
temperatures of up
to 35°C in a usual mixing and/or granulating device. These solids
include those
which, according to European Patent EP-B-0 486 592, can be used as
plasticisers
and/or slip additives. These include in particular anionic surfactants such as
alkyl
benzene sulphonates and/or (fatty) alkyl sulphates, but also polymers such as
polymeric polycarboxylates. A more accurate description of the possible
anionic
surfactants and polymers is provided in the list of possible constituents. The
function
of slip agent can also be provided by the binder or the binders or the binder
mixtures.
1.5 The binders are preferably admixed as the last component. As detailed
above, they
can be added as a solid, i.e. at a processing temperature which is below their
melting
point and/or their softening point, or in the form of a melt. Preferably,
however, the
admixing operation take;. place under conditions such that as uniform and
homogeneous a distribution of the binder as possible is achieved in the
mixture of
:30 solids. In the case of highly finely particulate binders, this can be
effected at
temperatures below 40°C, e.g. at temperatures of the binder between 15
and 30°C.
Preferably, however, the binder has a temperature at which it is present in
the form of
16
CA 02317030 2000-09-08
a melt, i.e. above the melting point, in particular in the form of a complete
melt.
Preferred temperat~.ues of the melt are between 60 and 150°C, the
temperature range
between 80 and 120°C being particularly preferred. During the mixing
process which
takes place at room temperature to slightly elevated temperatures, the melt
solidifies
almost instantaneously and the pre-mixture is present according to the
invention in a
solid, flowable form.
Joining the detergent or cleaning agent compounds and/or detergent or cleaning
agent
raw materials with simultaneous or subsequent forming can be effected by the
usual
processes in which compacting forces are applied, such as granulating,
compacting,
e.g. roller compacting or extruding or tableting and pelletising.
The actual granulating, compacting, tableting, pelletising or extrusion
process
according to the invention takes place at processing temperatures which
correspond,
at least in the compacting step, at least to the temperature of the softening
point, or
event to the temperature of the melting point. In a preferred embodiment of
the
invention, the pro<;ess temperature is significantly above the melting point
or above
the temperature at which the binder is present as a melt. In particular,
however, it is
preferable for the process temperature in the compacting step to be not more
than
~!0 20°C above the melting temperature or the upper limit of the
melting range of the
binder. Although it is technically altogether possible to set even higher
temperatures,
it has been found that a temperature difference of 20°C with respect to
the melting
temperature and/or the softening temperature of the binder is generally
altogether
sufficient and higher temperatures do not provide any additional advantages.
For this
:~S reason - and in particular for energy reasons - it is particularly
preferable to operate
above but as closely as possible to the melting point and/or the upper
temperature
limit of the melting range of the binder. Such a temperature control has the
further
advantage that thermally sensitive raw materials such as peroxy bleaching
agents such
as perborate and/or percarbonate but also enzymes can also be increasingly
processed
:30 without serious losses of active substance. The possibility of an accurate
temperature
control of the binder in particular during the decisive step of compaction,
i.e. between
mixing / homogenising o~F the pre-mixture and foaming, allows a process
control
17
CA 02317030 2000-09-08
which is highly advantageous from the energy point of view and extremely
gentle for
temperature-sensitive components of the pre-mixture since the pre-mixture is
exposed
to the higher temperatures only for a brief period. Preferably, the duration
of the
temperature exposure is between 10 seconds and maximum 5 minutes; in
particular, it
amounts to maximum 3 minutes.
In a preferred embodiment of the invention, the process according to the
invention is
carried out by e~,;trusion as described in European Patent EP-B-0 486 592 or
International Patent Applications WO-A-93/02176 and WO-A-94/09111 (all filed
by
Henkel KGaA), for example. In these processes, a solid pre-mixture is
compressed in
the form of a strand and, after leaving the die, the strand is cut to the
predeterminable
granule dimension. by me;~ns of a cutting device. The homogeneous, solid pre-
mixture contains a plasticisers and/or slip agent which causes the pre-mixture
to be
softened in a plastiic manner under the pressure or the effect of specific
operations to
1S become extrudable. Preferred plasticisers and/or slip agents consist of
surfactants
and/or polymers which, within the framework of the invention as it is now
present and
with the exception of the above-mentioned non-ionic surfactants, are
introduced into
the pre-mixture not in the liquid, and in particular not in the aqueous but in
the solid
form.
To explain the extrusion process, express reference is herewith made to the
above-
mentioned patents and patent applications. In a preferred embodiment of the
invention, the pre-mixture is in this case preferably continuously fed to a
double
screw extruder with synchronised or counter-current screw operation, it being
''<?5 possible for the housing and the extruder granulation head to be heated
to the
predetermined extrusion temperature. Under the shearing effect of the extruder
screws, the pre-mixture is compacted at a pressure, which, preferably, amounts
to at
least 25 bar but :may be below this level at extremely high rates of
throughput,
depending on the equipment used, as well as plasticised, extruded through the
die
:30 plate in the extruder head in the form of fme strands, and the extrudate
being finally
comminuted by means of a rotating guillotine-type knife to form preferably
approximately spherical to cylindrical granular grains. The aperture diameter
of the
18
CA 02317030 2000-09-08
die and the length of the ;>trands are chosen such as to correspond to the
granule
dimensions selected. In this embodiment, the production of granules with an
essentially homogeneous p:redeterminable particle size is possible, it being
possible
for the individual absolute particle sizes to be adjusted to the intended
application
purpose. In general, particle diameters of maximum 0.8 cm are preferred.
Important
embodiments provide here for the production of uniform granules in the mm
range,
for example in the range. of 0.5 to S mm and in particular in the range of
approximately 0.8 to 3 mm. The ratio of length to diameter of the cut-off
primary
granules in an important embodiment in this respect is within the region of
approximately 1:1 to approximately 3:1. Moreover, it is preferable for the
still elastic
primary granules t~o be passed to a further forming processing step; during
this step,
edges present on the crude extrudate are rounded off so that, in the end,
spherical to
near spherical extrudate gxains can be obtained. If desired, small quantities
of
desiccant powder e.g. zc~olite powder such as zeolite NaA powder can be
l.5 simultaneously usc;d in this stage. Forming can be carried out in rounding
devices
widely available on the market. In this connection, care should be taken to
ensure that
only small quantities of fine granular fractions are formed in this stage.
However,
drying which is described in the above-mentioned documents of the state or the
art as
being the preferred embodiment is unnecessary within the framework of the
present
:?0 invention since thc; process according to the invention is essentially
free from water,
i.e. is effected without the addition of free, non-combined water.
In a particularly advantageous embodiment of the invention, the binder used
has a
melting temperatw~e or a melting range of up to 75°C; process
temperatures which are
25 maximum 10°C and in particular maximum 5°C above the melting
temperature or the
upper temperature; limit of the melting range of the binder have proved to be
particularly advanl:ageous.
Under these process conditions, the binder has the effect of a slip agent, in
addition to
:30 the above-mentioned effects, and prevents or at least reduces the
occurrence of
agglutinations to equipment walls and compacting tools. This applies not only
to
19
CA 02317030 2000-09-08
processing in the extruder but equally to processing in continuously operating
mixers/granulators or rollers, for example.
Immediately after leaving the manufacturing equipment, the compacted substance
S preferably has a temperature of not more than 60°C, temperatures
between 35 and
65°C being particularly preferred. It has been found that discharge
temperatures -
particularly in the extrusion process - of 40 to 55°C are particularly
advantageous.
As in the extrusion process, it is equally preferably in the other
manufacturing
processes to pass the primary granules/compacted substances thus formed to a
further
forming processing; step, in particular a rounding off process, so that,
finally, spherical
to near spherical (bead shaped) grains can be obtained.
It is the essence of a preferred embodiment of the invention that the particle
size
distribution of the pre-mixture is considerably wider than that of the end
product
produced according to the invention and corresponding to the invention. In
this
connection, the pre-mixture can contain considerably coarser fines, and even
dust
fractions, if nece:osary also more coarse- grained fractions, it being
preferable,
however, for a pne mixture with a relatively wide particle size distribution
and a
2:0 relatively high proportion of fines to be converted into an end product
with a
relatively narrow particle size distribution and relatively small proportions
of fines.
Due to the fact that the process according to the invention is earned out
essentially
free from water - i.e. it is free from water with the exception of the water
contents
2 5 ("impurities") of the solid raw materials used - not only the risk of gel
formation by
the surfactant raw materials in the manufacturing process itself is minimised
or even
eliminated, an ecologically valuable process is additionally made available
since, by
doing away with a. subsequent drying step, it is possible not only to save
energy but
also to avoid emissions such as those occurring mainly in the case of
conventional
a0 types of drying.
CA 02317030 2000-09-08
According to the theorem of the above-mentioned application, it is, for
example,
possible to produce; builder granules (bulider granule extrudates), bleaching
activator
granules (bleach activator l;ranule extrudates) or enzyme granules (enzyme
granule
extrudates), base granules, compounds and treated raw materials having a
spherical or
bead form being particularly preferably made available.
The process end products produced according to the theorem of the above-
mentioned
application have a very high bulk density. Preferably, the bulk density is
above 700
g/l, in particular between 750 and 1000 g/1.
The process descrilbed in the above-mentioned earlier German patent
application 196
38 599.7 is highly suitable for carrying out process step a) within the
framework of
the present invention. Another process preferably used as process step a) is
described
in the earlier German patent application 197 53 310.8 (Henkel KGaA). According
to
the theorem of this specification, the production of the pourable and flowable
high
density granules t;~kes places in step a) by initially producing a solid pre-
mixture
which contains at least one non-aqueous binder and a solid raw material or
solid raw
materials from a raw material class, which is or are present as a solid at
room
temperature and a 'pressure of 1 bar and has or have a melting point or
softening point
of not less 45°C, in quantities of at least 50% by weight and
converting the pre-
mixture by applying compacting forces at temperatures of at least 45°C
into a grain
and, if necessary, processing or further treating it with the proviso that
- the pre-mixaure is essentially anhydrous and
- the pre-mi~;ture contains at least one non-aqueous binder which is present
in
;?5 the solid firm at a pressure of 1 bar and temperatures below 45°C
but is
present as a melt under the processing conditions, this melt serving as a
multifunctional, water-soluble binder, which melt has the function not only of
a slip agent but also an adhesive function for the raw materials during the
manufactwe of the agent but has a disintegrating effect during the re-
:30 dissolution of the agent in an aqueous liquor,
- and a bulk density of at least 600 g/1 is adjusted.
21
CA 02317030 2000-09-08
According to the theorem of this application it is possible to use as non-
aqueous
binders not only the binder:. mentioned in 196 38 599.7 but also polymers
swollen in
non-aqueous solution.
Anhydrous, swollen polymers which can also be used as binders according to the
meaning of the above-mentioned application are those which lead to gel-type
states in
non-aqueous liquids or low water liquid mixtures (maximum water content, based
on
the liquid mixture: 20%). In particular, those systems of non-aqueous liquids
and
polymers are suitable which, at room temperature in the presence of the
polymer,
exhibit a viscosity at least 2.0 times, in particular 300 times to 5000 times
that of non-
aqueous liquids as such. The viscosity of the binder, i.e. in this case the
combination
of non-aqueous liquid and polymer at room temperature is preferably in the
region of
200 mPas to 10000 mPas, in particular of 400 mPas to 6000 mPas, measured by
means of a Brookiield rotation viscosimeter (Brookfield DV2, spindle 2 at 20
rmp),
for example. At :higher temperatures, for example at 60°C, the
viscosity deviates
preferably only rc;latively slightly from the values at room temperature and
is
preferably in the region of 250 mPas to 2500 mPas. Suitable liquids include
liquid
monohydric, dihyd.ric or trihydric alcohols with boiling points (at 1 bar)
above 80°C,
in particular above. 120°C such as, for example, n-propanol, iso-
propanol, n-butanol,
s-butanol, iso-butanol, ethylene glycol, 1,2 or 1,3-propylene glycol,
glycerine, di or
triethylene glycol or di or t~-ipropylene glycol or their mixtures, in
particular glycerine
and/or ethylene glycol and the representatives of the above-mentioned non-
ionic
surfactants which are liquid at room temperature. It is possible to add water
as
"swelling aid" to the organic solvent in small quantities, namely maximum 1.5%
by
:? 5 weight, based on the end product of the swelling process. However, only
so much
water is preferably added t:o the solvent that the water content of the end
product is
less than 1 % by v~reight. Although it is well known that such non-ionic
surfactants
tend to gel on contact with water, no tackiness of the end product occurs when
they
are used as non-aqueous solvents for the polymer in the binder used according
to the
:30 invention. Suitable polymers leading to swollen systems in such anhydrous
liquids
are polyvinyl pywolidone, polyacrylic acid, co-polymers of acrylic acid and
malefic
acid, polyvinyl ak;ohol, xanthan, partly hydrolysed starches, alginates,
amylopectins,
22
CA 02317030 2000-09-08
starches or cellulo.;es carrying methylether, hydroxyethyl ether,
hydroxypropyl ether
and/or hydroxybutyl ether groups, phosphated starches such as starch
diphosphate but
also inorganic polymers such as layer silicates and their mixtures. Among the
polyvinyl pyrrolidones, those with a molecular weight of maximum 30000 are
preferred. Moleculiar weigr~t ranges between 3000 and 30000, e.g. around
10000, are
particularly preferred. The polymers which are preferably used include also
hydroxypropyl starch and starch diphosphate. The concentration of the polymers
in
the anhydrous liquids is preferably 5% by weight to 20% by weight, in
particular
approximately 6% by weight to 12% by weight.
Particularly advantageous embodiments of the above-mentioned invention contain
such swollen polymers as binders.
The content of binder or binders in the raw material compound described in the
above-mentioned application is preferably at least 2% by weight, but less than
20%
by weight, in particular less than 15% by weight, quantities in the region of
3% by
weight to 10% by weight being particularly preferred.
If desired, the raw material compounds may contain in minor quantities further
constituents which are solid at temperatures below 30°C (1 bars). In
this respect, it is
particularly desirable to choose, as further components, those which have
already
been mentioned above as teeing among the preferred raw materials and raw
material
classes. For example, bleach activator granules containing more than 60% by
weight
TAED could additionally .also contain anionic surfactant or anionic
surfactants, for
:?5 example alkyl sulphates and/or alkyl benzene sulphonates. Since it is
considered
advantageous within the fr~unework of the invention to make as high as
concentration
of merely one raw material. available in the compound, it is preferable for
the second
solid raw material to be present in the compounds in quantities of maximum 30%
by
weight. However, apart from the first and, if necessary, also the second solid
raw
:30 material, premanufactured compounds, for example surfactant compounds or
spray
dried powders, such as those commonly used in detergents, can also be used in
addition to the actual raw material. However, the proportions of such
compounds in
23
CA 02317030 2000-09-08
the compound according to the invention are preferably less than 25°C
and in
particular less than 20% by weight. In addition, further components such as
finely
particulate aluminosilicates,, for example zeolite A, X and/or P, amorphous or
crystalline silicates, carbonates, if necessary also sulphates in minor
quantities maybe
present, usually in quantitic;s not exceeding 5% by weight, based on the
compound
according to the invention. Finely particulate aluminosilicates, above all,
can be used
to powder the raw material compounds according to the invention.
Constituents which are liquid at temperatures below 30°C (1 bar) are
not contained in
the raw material compounds of the above-mentioned application - with the
exception
of the above-mentioned maximum 10% by weight of non-ionic surfactants and the
swollen polymers used as binders.
It is an essential characteristic of the above-mentioned application that the
raw
1 S material compounds according to the invention contain no free water, i.e.
no water
that is not bound to the solids in any chemical or physical form. This is
possible by
the essentially water-free production of the raw material compounds (compare
below)
as a result of which water is entrained only in quantities such as it is
contained as
"impurity", so to speak, in the solid raw materials used.
In a preferred embodiment of the above-mentioned application, a raw material
compound contains 55 to 85% by weight bleach activator, 0 to 25% by weight,
preferably 5 to 22~% by weight anionic surfactants such as alkyl benzene
sulphonates
and/or alkyl sulphates, if necessary in a pre-compounded form, 5 to 12% by
weight of
15 a non-aqueous binder, preferably polyethylene glycol with a molecular
weight above
3500, in particular around 4000, or of a swollen polymer.
In a further preff;rred embodiment of the above-mentioned application, the raw
material compound additionally contains 1 to 7.5% by weight, preferably 2 to
6% by
weight of a non-ionic surfactant which is liquid at temperatures below
35°C (1 bar),
for example a C12-C1g fatty alcohol with 3 to 7 EO.
24
CA 02317030 2000-09-08
In a further preferred embodiment of the above-mentioned application, the raw
material compound additionally also contains 0.5 to 5% by weight of a finely
particulate, in particular a non-water-soluble constituent such as an
aluminosilicate as
indicated above. Such components are generally used as powdering agents and
can
also subsequently be applied to the raw material compound, within the
framework of
this invention.
In a further preferred embodiment of the above-mentioned application, the raw
material compound contains 60 to 85% of one or more inorganic builders, 3 to
10%
by weight of a binder usef~ according to the invention and up to 20% by weight
of
anionic and/or non-ionic surfactants. In particular, builder compounds are
preferred
which contain 50 to 65% by weight of zeolite A, X, Y and/or P and 15 to 30% by
weight of an amorl>hous alkali silicate.
The use of anhydrous swollen polymers as slip agents and binders is also
described in
the earlier Internavtional Patent Application WO/PCT/EP97/05945. The process
disclosed in this application is also suitable for the execution of step a)
within the
framework of the present invention. Consequently processes are also preferred
within
the framework of the present invention in the case of which the production of
the
pourable and flowable high density granules in step a) is effected by joining
detergent
or cleaning agent compounds and/or detergent or cleaning agent raw materials
with
simultaneous or subsequent forming, a pre-mixture being initially produced
which
contains individual raw materials and compounds present as solids at room
temperature and a vpressure of 1 bar and this pre-mixture being subsequently
converted
into a grain by thf; application of compaction forces and, if necessary,
subsequently
being further treated or processed, with the proviso that the pre-mixture is
essentially
anhydrous and a forming aid is used which is liquid under the forming
conditions, in
particular also at room temperature and a pressure of 1 bar and has the form
of a
polymer swollen in a non-aqueous solution.
:30
The constituents used in the process described in this specification can
consist of
separately producc;d compounds but also of raw materials which have the form
of a
CA 02317030 2000-09-08
powder or (finely divided to coarse) particles and, in any case, are present
in the solid
form at room temperature and a pressure of 1 bar - with the exception of the
non-
ionic surfactants liquid at temperatures below 45°C and a pressure of 1
bar, which
may be present if r~ecessary~. The particulate particles used may, for
example, consist
of beads produced by spray drying or the agglomerates from a granulation
process etc.
The composition of the compounds as such is not important with respect to the
invention with the exception of the water content which must be such that the
pre-
mixture as defined above is essentially anhydrous and preferably contains not
more
than 10% by weight of water of hydration and/or constitutional water. In a
preferred
embodiment, super-dried compounds are used in the pre-mixture. Such compounds
can, for example, be obtained by spray drying, the temperature control being
such that
the tower discharge; temperatures are above 100°C, preferably
110°C or above. It is
also possible to use solid compounds in the pre-mixture which serve as
carriers for
liquid components,, for example liquid non-ionic surfactants or silicone oil
and/or
paraffins. These compounds can contain water to the level indicated above, the
compounds being flowable and preferably remaining flowable and/or at least
conveyable at higher temperatures of at least 45°C. In particular,
however, it is
preferable for compounds with maximum 12% by weight and particularly
preferably
with maximum 9°/<. by weight of water, based on the pre-mixture, to be
used in the
pre-mixture. Free water, i.e. water which not bound in any form to a solid and
is
consequently present "in the liquid form" should preferably not be contained
in the
pre-mixture since even very small quantities, for example around 0.2 or 0.5%
by
weight based on the; pre-mixture, are sufficient to partially dissolve the
forming agent
which is soluble as such. 7.'he consequence would be that the melting point or
the
softening point of the end product would be reduced and it would lose both
some of
its flowability and hulk density.
Joining of the detergent or cleaning agent compounds and/or detergent or
cleaning
agent raw materials with simultaneous or subsequent forming can be effected
according to the disclosure of the above-mentioned application by the usual
processes
in which compacting forces are applied such as granulation, compacting, for
example
roller compacting, or extruding and pelletising. It is in this connection
possible to use
26
CA 02317030 2000-09-08
also spray dried granules as premanufactured compounds in the pre-mixture;
however, the invention is in no way limited thereto. Instead, the process
according to
the invention provides for tile possibility of using no spray dried granules
since highly
finely particulate raw materials with dust-type fractions can be processed
according to
the invention without problems and without being previously precompounded,
e.g.
spray dried.
The essentially water-free execution of the process does not only make it
possible for
peroxy bleaching agents to be processed without loss of activity, it is
thereby also
made possible to process pe;roxy bleaching agents and bleach activators
jointly in one
particle without having to fear serious losses of activity.
In a preferred embodiment of the invention of the above-mentioned application,
compacting forming of the process is effected by means of an agglomeration
step, the
pre-mixture being ;>ubjected. to agglomerating granulation in a device
suitable for this
purpose, with the forming agent defined above assuming the role of binder. The
granulation process. can be carried out continuously or batchwise. In this
connection,
one proceeds in such a way that the solid components of the pre-mixture to be
compacted are introduced into a granulator for which a mixer can also be used,
if
necessary dusts which may be present being combined by the addition of a
liquid non-
ionic surfactants, the forming agent being introduced to the granulator. The
desired
average particle size of the granules can be adjusted by way of the type and
quantity
of forming agent and the machine and operating parameters such as the
rotational
speed and the residence time as well as the temperature. Suitable granulators
are, for
example, pelletisin~; pan mixers, revolving drums, ploughshare mixers with
choppers
made by Lodige~, high performance mixers with a rotating mixer vessel and
vortex
device, e.g. those made by Laeis Bucher~ or Eirich~, high-intensity mixers
with
shearing heads such as those made by LIPP Mischtechnik~ or Imcatec~, Drais~,
Fukae~ or Forberg;~ mixers as well as the so-called Rotorcoator~ made by
Glatt~
with a horizontal rotary disc; and those with a rotary disc inclined at up to
50°. Less
suitable are the following: Lodige~ CB mixers, zigzag mixers made by PK-Niro~,
27
CA 02317030 2000-09-08
the Ballestra~ chain mix and the Hosokawa~ or the Schugi~ mixer. A fluid bed
or a
horizontal mixer, e.g. a Nautamixer~ is also less suitable. Within the
framework of
this embodiment of the process according to the invention it is preferable to
operate at
room temperature or the temperature brought about by the energy input of the
mixer
or the granulator i.e. without a separate heating step, as described in
International
Patent Application WO 94/13779 and the state of the art detailed therein, for
example. In this connection it should be considered as an advantage of the
process
according to the invention that one dose not depend on a two-stage granulating
process such as that described in European Patent Application EP 0 367 339,
for
example, in which the granules are first compressed in a high speed mixer and
subsequently in a low speed mixer and granulator, it being possible to effect
the
compacting granulation in a single step using the anhydrous swollen polymer.
To sum up, the first step o f the process according to the invention is
carried out by
any usual process in which the constituents are plasticised and, by the
application of
shearing forces, compressed into a form. Preferred production processes are
granulation, extrusion, roller compaction or pelletising. Processes which are
particularly prefewed operate in step a) according to the theorem of the above-
mentioned earlier applications.
In process step b), further constituents to be optionally used are
agglomerated such
that they satisfy the; desired selection criteria with respect to the particle
size. In step
b), it is not necessary to p'.iasticise the mixture of the individual
constituents to be
agglomerated. Consequently, normal granulation processes are preferred for the
preparation of the agglomer;~tes in step b).
During the preparation of the agglomerates in step b) it is preferable for
this also to be
carried out essentially free from water, the term "essentially free from
water" being
3~D understood to refer to the state as defined above in which the content of
liquid water,
i.e. water not present in the form of water of hydration and/or constitutional
water, is
28
CA 02317030 2000-09-08
less than 5% by wc;ight, preferably less than 3% by weight and in particular
even less
than 0.5% by weight, based on the substances to be granulated in step b).
During the granulation of the constituents to be optionally used, auxiliary
agents can
be added which facilitate agglomerate formation. In particular, the addition
of the
plasticising and/or slip agents to be used in step a) is preferable also
during the
granulation in step b), the mixture to be agglomerated - in contrast to step
a) -
containing these substances not in order to be formed by compression via the
plastic
state but merely as a granulating aid.
Preferred granulating aids in step b) are the polyethylene glycols or
ethoxylated
alcohols. Particul~~rly preferably, the anhydrous swollen polymers described
above
are used as granulating aids..
In step b), it is also possible to use part of the granules obtained in step
a) as base
material and to "bond" further finely particulate constituents to these.
Obviously,
other coarser substances can be introduced as base material, more finely
particulate
substances being applied to them, the granulating aids having an increased
significance as adhesion-promoting component.
Apart from the above-mentioned process-specific auxiliary agents, it is
possible for
all constituents of dletergents and cleaning agents to be used as constituents
in steps a)
and b), no limits being set to the expert during formulation. It is possible,
without
causing any problems, to ;introduce individual constituents into the detergent
and
cleaning agent fornied bodic;s either exclusively via process step a) or
exclusively via
process step b). However, it is also conceivable and possible, without causing
problems, to use thc; constituents both in process a) and in process step b).
By separately incorporating certain constituents, positive effects can be
achieved. For
3'0 example, it is thus possible to add bleaching agents and bleach
activators) either in
process step a) or in process step b). By using bleaching agent or bleach
activator in
29
CA 02317030 2000-09-08
step a) and the other substance in step b) it is also possible to achieve a
separation of
the bleaching agent and the bleach activator, leading to advantageous
properties.
Whereas the separation of bleaching agent and bleach activator, i.e.
incorporation via
step a) or step b) is not preferred within the framework of the present
invention, other
process variants are preferred which lead to the enhanced stability of
sensitive
substances. In particular, it is thus preferred to add enzymes in the process
step in
which bleaching agent and/or bleach activators) are not added, in order to
thus
prevent a loss of activity of the enzymes. Since, moreover, enzymes are
temperature-
sensitive substances, it is recommended to introduce them into the process
according
to the invention vi.a process step b) so that it is preferable for at least
one of the
agglomerates prepaxed in step b) to contain enzymes.
In the following, th.e constituents of detergents and cleaning agents suitable
for use in
1 S both step a) and in ;step b) will be described in further detail.
In the detergent and cleaning agent formed bodies prepared according to the
process
of the invention, anionic, non-ionic, cationic and/or amphoteric surfactants
or
mixtures of these can be used. From the point of view of technical
application,
mixtures of anionic and non-ionic surfactants are preferred. The total
surfactant
content of the formed bodies produced according to the process of the
invention is 5
to 60% by weight, based on the weight of the formed body, surfactant contents
of
more than 15% by weight being preferred.
The anionic surfactants used are, for example, those of the sulphonate and
sulphate
type. Suitable surfactants of the sulphonate type, in this respect, are
preferably C9_~3
alkyl benzene sulphonates, olefin sulphonates, i.e. mixtures of alkene and
hydroxyalkane sulp~honates as well as disulphonates such as those obtained
from C12-
1g monoolefins with terminal or internal double bonds by sulphonation with
gaseous
sulphur trioxide and subsequent alkaline or acidic hydrolysis of the
sulphonation
products. Alkane sulphonates obtained from C12_1g alkanes, e.g. by
sulphochlorination
or sulphoxidation v~ith subsequent hydrolysis or neutralisation axe also
suitable. The
CA 02317030 2000-09-08
esters of alpha-sulphofatry acids (ester sulphonates), e.g. the alpha-
sulphonated
methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are
also
suitable.
Other suitable anionic surfactants are the sulphonated fatty acid glycerine
esters. The
term fatty acid glycerine esters should be understood to refer to the
monoesters,
diesters and triesters as well as the mixtures thereof such as those obtained
by
esterification of a rnonoglyc;erine with 1 to 3 mole fatty acids or by re-
esterification of
triglycerides with 0.3 to 2 mole glycerine. In this respect, preferred
sulphonated fatty
acid glycerine esters consist of the sulphonation products of saturated fatty
acids with
6 to 22 carbon atoms, for example caproic acid, caprylic acid, caprinic acid,
myristic
acid, lauric acid, palmitic acid, stearic acid or behenic acid.
The preferred alk(e,ne)yl sulphates are the alkali and in particular the
sodium salts of
the sulphuric acid half esters of the Cio-is fatty alcohols, e.g. of coconut
fatty alcohol,
tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the
CIZ_C20 ox0
alcohols and those half esters of secondary alcohols having this chain length.
Other
preferred alk(ene)yl sulphates with the above-mentioned chain length are those
which
contain a synthetic straight-chain alkyl radical produced by the petrochemical
route
which have an analogous decomposition behaviour to the adequate compounds
based
on fatty chemical raw materials. For wash technology reasons, the C12_C16
alkyl
sulphates and Cl2.Cis alkyl sulphates as well as the C14_Cis alkyl sulphates
are
preferred. 2.3-alkyl sulphates which are produced according to US patent
specifications 3,234;258 or 5,075,041, for example and can be obtained as
commercial products of Shell Oil Company under the tradename DAN~ are also
suitable anionic surfactants.
The sulphuric acid monoesters of the straight-chain or branched C~_21 alcohols
ethoxylated with 1 vto 6 mole; ethylene oxide, such as 2-methyl-branched C9_~
1 alcohols
with, on average, 3..5 mole ethylene oxide (EO) or C,z_ls fatty alcohols with
1 to 4 EO
are also suitable. Because of their strong foaming behaviour, they are used in
31
CA 02317030 2000-09-08
cleaning agents only in relatively small quantities, e.g. in quantities of 1
to 5% by
weight.
Further suitable anionic surfactants also consist of the salts of alkyl
sulphosuccinic
acid, also referred to as sulphosuccinates or as sulphosuccinic acid esters,
and the
monoesters and/or diesters of sulphosuccinic acid with alcohols, preferably
fatty
alcohols and in particular ethoxylated fatty alcohols. Preferred
sulphosuccinates
contain Cg_lg fatty .alcohol radicals or mixtures of these. Sulphosuccinates
which are
particularly preferred contain a fatty alcohol radical derived from
ethoxylated fatty
alcohols which, considered as such, represent non-ionic surfactants (for a
description
see below). In this respect: sulphosuccinates the fatty alcohol radicals of
which are
derived from ethoxylated fatty alcohols with a narrow homologue distribution,
are
particularly preferred. It is also possible to use alk(ene)yl succinic acid
with
preferably 8 to 18 carbon atoms in the alk(ene)yl chain or their salts.
Further suitable anionic surfactants are in particular soaps. Saturated fatty
acid soaps
such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid,
hydrogenated
erucic acid and be;henic acid as well as soap mixtures derived in particular
from
natural fatty acids e;.g. coconut, palm kernel or tallow fatty acids, are also
suitable.
The anionic surfaci:ants, including soaps, can be present in the form of their
sodium,
potassium or ammonium salts as well as in the form of soluble salts or organic
bases
such as mono, di or triethanol amine. Preferably, the anionic surfactants are
present
in the form of their sodium or potassium salts, in particular in the form of
the sodium
salts.
Preferably, alkoxylated, preferably ethoxylated, in particular primary
alcohols with
preferably 8 to 18 C atoms and an average of 1 to 12 mole ethylene oxide (EO)
per
mole alcohol are used as non-ionic surfactants in which the alcohol radical
can be
linear or preferably methyl-branched in position 2 or which may contain linear
or
methyl-branched radicals in the mixture in the same way as they are commonly
present in oxo alcohol radicals. In particular, however, alcohol ethoxylates
with
32
CA 02317030 2000-09-08
linear radicals of alcohols of native origin with 12 to 18 C atoms, e.g. of
coconut,
palm kernel, tallow fatty or oleyl alcohol and on average 2 to 8 EO per mole
alcohol
are preferred. The preferred ethoxylated alcohols include for example Clz-la
alcohols
with 3 EO or 4 EO~, C9_11 alcohols with 7 EO, Ci3-~s alcohols with 3 EO, 5 EO,
7 EO
or 8 EO, C~z_Ig alcohols with 3 EO, 5 EO or 7 EO and mixtures of these such as
mixtures of C~z_la alcohol with 3 EO and Clz-is alcohol with 5 EO. The degrees
of
ethoxylation indicated represent statistical mean values which may consist of
an
integer or a fraction for a particular product. Preferred alcohol ethoxylates
have a
narrow homologue distribution (narrow range ethoxylates, NRE). In addition to
these
non-ionic surfactants, fatty ,alcohols with more than 12 EO can be used.
Examples of
these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
In addition, alkyl glycosides with the general formula RO(G)X can be used as
further
non-ionic surfactmts, in which R represents a primary straight-chain or methyl-
1 S branched, in particular a position 2 methyl-branched, aliphatic radical
with 8 to 22,
preferably 12 to 18 C atoms; and G is the symbol which represents a glycose
unit with
5 or 6 C atoms, preferably glucose. The degree of oligomerisation x which
indicates
the distribution of monoglycosides and oligoglycosides is any number between 1
and
10; preferably x is l .2 to 1.4.
A further group o:f non-ionic surfactants, which axe preferably used and are
used
either as sole non-ionic surfactant or in combination with other non-ionic
surfactants,
are the alkoxylated, preferably ethoxylated or ethoxylated and~propoxylated
fatty acid
alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in
particular fatty
acid methyl esters such as those described in Japanese patent application JP
58/217598, for example, or which are preferably prepared according to the
process
described in International Patent Application WO-A-90/13533.
Non-ionic surfactaalts of the amine oxide type, for example N-coconut alkyl-
N,N-
dimethyl amine oxide and N-tallow alkyl-N,N-dihydroxyethyl amine oxide and of
the
fatty acid alkanol a~rnide type may also be suitable. The quantity of these
non-ionic
33
CA 02317030 2000-09-08
surfactants is preferably not more than that of the ethoxylated fatty
alcohols, in
particular not more than half of these.
Other suitable surfactants are the polyhydroxy fatty acid amides of formula
(I)
R~
R-CO-N-[Z] (I)
in which RCO represents an aliphatic acyl radical with 6 to 22 carbon atoms,
R'
:l0 represents hydrogen, an alkyl or hydroxy alkyl radical with 1 to 4 carbon
atoms and a
[Z] represents a linear or branched polyhydroxy alkyl radical with 3 to 10
carbon
atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amines are known
substances which can common be obtained by the reductive amination of a
reducing
sugar with ammonia, an alkyl amine or an alkanol amine and subsequent
acylation
with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
The group of polyhydroxy fatty acid amides includes also compounds of formula
(II),
R' -O-RZ
2.0
R-CO-N-[Z] (II)
in which R represents a linear or branched alkyl or alkenyl radical with 7 to
12 carbon
atoms, RI represenla a linear, branched or cyclic alkyl radical or an aryl
radical with 2
to 8 carbon atoms and RZ represents a linear, branched or cyclic alkyl radical
or an
aryl radical or an oxy alkyl radical with 1 to 8 carbon atoms, C»-alkyl or
phenyl
radicals being prefi~rred and [Z] represents a linear polyhydroxy alkyl
radical whose
alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated,
preferably
ethoxylated or propoxylated derivates of this radical.
[Z] is preferably obtained by the reductive amination of a reducing sugar,
e.g.
glucose, fructose, maltose, lactose, galactose, manose or xylose. The N-alkoxy
or N-
aryloxy-substituted compounds can then, for example, be converted into the
desired
34
CA 02317030 2000-09-08
polyhydroxy fatty acid ~unides according to the theorem of the international
application WO-A-95/073:31 by conversion with fatty acid methyl esters in the
presence of an alkoxide used as catalyst.
Within the framev~,rork of the present invention, it is preferable to
introduce anionic
and non-ionic surfactants) via the process into the detergent and cleaning
agent
formed bodies, the. advantages in terms of technical application being
obtained from
certain quantitative; ratios in which the individual surfactant classed can be
used.
Thus, detergent and cleaning agent formed bodies are, for example,
particularly
preferred in the case of which the ratio of anionic surfactants) to nio-ionic
surfactants) is between 10:1 and 1:10, preferably between 7.5:1 and 1:5 and in
particular between 5:1 and 1:2, it being possible to introduce the surfactants
in the
process according i:o the invention into the formed bodies again via steps a)
and/or b).
From the technical applications point of view, it may be advantageous if
certain
surfactant classes acre not present in some phases of the detergent and
cleaning agent
formed bodies or iin the overall formed bodies, i.e. in all phases. The term
phase
within the framework of the present invention should be understood to mean any
spatial separation, i.e. for example, the multiple phase state in multiple
layer or
ring/nucleus or jacketed tablets. In this connection, individual phases are
also formed
by the coarse particles from steps a) and b) of the process according to the
invention
being compressed, the particles from process step a) forming a phase whereas
the
other phase is formed by the particles from process step b). It is also quite
conceivable to produce detergent and cleaning agent formed bodies containing
four
different phases by preparing, mixing and tableting a granular product from
step a)
and three granular products from step b) or visa versa or to produce, mix and
tablet
two granular products from steps a) and b) each. This tableting process may
additionally lead to multiple layer formed bodies, if this is desired.
3 ~0
A further important embodiment of the present invention provides for at least
one
phase of the formed bodies to be free from non-ionic surfactants. This variant
can be
CA 02317030 2000-09-08
achieved particuhcrly easily by the process according to the invention if non-
ionic
surfactants from one of process steps a) or b) are completely omitted.
Conversely however, a positive effect can also be achieved by the content of
certain
surfactants in the individual phases or the total formed body, i.e. all
phases,. The
introduction of the alkyl polyglycosides described has proved advantageous in
this
connection so that detergent and cleaning agent formed bodies are preferred in
which
at least one phase ~of the formed body contains alkyl polyglycosides; this can
again be
achieved by introducing AI'G into process step a) and/or b).
:l 0
Similar to the case of non-ionic surfactants, it also possible, by omitting
anionic
surfactants from individual or all the phases, to obtain detergent and
cleaning agent
formed bodies which are better suited for certain fields of application.
Within the
framework of the :present invention, detergent and cleaning agent formed
bodies are
l.5 therefore also conceivable in which at least one phase of the formed body
is free from
anionic surfactants, this possible implementation being particularly easy to
realise by
the process according to the invention in a manner analogous to the above, if
anionic
surfactants from process step a) or b) are completely omitted.
2:0 Apart from surfactant substances, builders are the most important
constituents of
detergents and cleaning agents. By way of the process according to the
invention, any
builders commonly used in detergents and cleaning agents can be introduced
into the
detergent and cleaning agent formed bodies, in particular zeolites, silicates,
carbonates, organic; co-builders and - if no ecological prejudices exist
against their
25 use - also the phosphates.
Suitable crystalline, layer-type sodium silicates have the general formula
NaMSiX02x+1H24~ 1VI representing sodium or hydrogen, x being a number between
1.9
and 4 and y and number between 0 and 20, the preferred value for x being 2, 3
or 4.
30 Such crystalline layer silicates are described in European Patent
Application EP-A-0
164 514, for example. Preferred crystalline layer silicates of the formula
indicated
above are those in which M represents sodium and x assumes the values 2 or 3.
In
36
CA 02317030 2000-09-08
particular, both (3 and 8-sodium disilicates NazSi205yH20 are preferred, (3-
sodium
disilicate being, :for example, obtainable according to the process described
in
International Patent Application WO-A-91/08171.
Amorphous sodium silicates with a modulus of NazO : Si02 of 1:2 to 1:3.3,
preferably
1:2 to 1:2.8 and in particular 1:2 to 1:2.6 which have a delayed dissolution
and
secondary wash properties can also be used. The delayed dissolution compared
with
conventional amorphous sodium silicates may have been brought about in
different
ways, e.g. by surface treatment, compounding, compacting/compression or by
super-
l.0 drying. Within the framework of this invention, the term "amorphous" can
also be
understood to mean "X-ray amorphous". This means that in X-ray diffraction
experiments, the silicates provide no clear-cut X-ray reflexes such as those
typical of
crystalline substances but at most one or several peaks of scattered X-ray
radiation
having a width of several degree units of the diffraction angle. However, it
is
altogether possible: to obtain particularly good builder properties if the
silicate
particles provide indistinct or even clear diffraction peaks during electron
diffraction
experiments. This should be interpreted to mean that the products exhibit
microcrystalline areas of a size of 10 to some 100 nm, values of up to maximum
50
nm and in particular of up to maximum 20 nm being preferred. These so-called X-
ray
amorphous silicate, which also exhibit a delayed dissolution compared with the
conventional waterglass products, are described in German Patent Application
DE-A-
44 00 024, for example. C:ompressed/compacted amorphous silicates, compounded
amorphous silicates and ;super-dried X-ray amorphous silicates are
particularly
preferred.
The finely crystalline synthetic zeolite containing bound water consists
preferably of
zeolite A and/or P. The particularly preferred zeolite P is zeolite MAP~
(commercial
product from Crosfield). However, zeolite X and mixtures of A, X and/or P are
also
suitable. Commercially available and to be preferably used within the
framework of
the present invention is, for example, also a co-crystalisate of zeolite X and
zeolite A
(approximately 80°,~o by weight zeolite X) which is being marketed by
CONDEA
37
CA 02317030 2000-09-08
August S.p.A. under the tradename VEGOBOND AX~ and can be described by the
formula
nNa20 ' (1-r~)K20 ' A1203 ' (2 - 2.5)Si02 ' (3.5 - 5.5)H20
The zeolite can bc; used both as a builder in a granular compound and as a
type of
"powdering agent" on the total mixture to be compressed, usually both methods
of
incorporation of the zeolite into the pre-mixture being used. Suitable
zeolites have an
average particle size of less 10 ~m (volume distribution; method of
measurement:
110 Coulter Counter) and preferably contain 18 to 22% by weight, in particular
2o to 22%
by weight of combined water.
Obviously, using the generally known phosphates as builders is also possible,
provided such a use ought not to be avoided for ecological reasons. In
particular, the
sodium salts of the orthophosphates, pyrophosphates and in particular the
tripolyphosphates ~~re suitable.
Suitable organic builders are, for example, the polycarboxylic acids that can
be used
in the form of their sodium salts such as citric acid, adipic acid, succinic
acid, glutaric
acid, tartaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic
acid (NTA)
provided there is n~o objection to their use for ecological reasons, as well
as mixtures
thereof. Preferred salts consist of the salts of the polycarboxylic acids such
as citric
acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids
and mixtures
thereof.
In order to facilitate the breaking down of highly compacted formed bodies, it
is
possible to incoporate disintegration aids, the so-called tablet
disintegration
promoters into thc;m in order to shorten the time required for breaking down.
According to Rompp (editi.on 9, volume 6, page 4440) and Voigt "Lehrbuch der
3'0 pharmazeutischen Technolc>gie" (edition 6, 1987, page 182-184), the term
tablet
disintegration promoters or breaking down accelerators should be understood to
mean
38
CA 02317030 2000-09-08
auxiliary agents v~rhich ensure the rapid breaking down of tablets in water or
gastric
juice and the liberation of pharmaceuticals in a resorbable form.
These substances 'which, because of their effect, are also referred to as
"disintegrating
agents" increase their volume on access of water, their inherent volume being
increased on the one hand (swelling) and a pressure being possibly produced,
on the
other hand, by the liberation of gasses, which pressure causes the tablet to
break down
into smaller particles. Known disintegration aids are, for example the
(hydrogen-
)carbonate/citric acid systems, although other organic acids can be used. For
example, synthetic. polymers such as polyvinylpynrolidone (PVP) or natural
polymers
or modified natural substances such as cellulose and starch and their
derivatives,
alginates or casein derivatives, for example, are swelling disintegration
aids.
Preferred detergent and cleaning agents foamed bodies contain 0.5 to 10% by
weight,
l.5 preferably 1 to 8°/. by weight and in particular 2 to 6% by weight
of a disintegration
aid, based on the weight of the formed body.
As preferred disintegration aids within the framework of the present
invention,
disintegration aids based on cellulose are used so that preferred detergent
and cleaning
f.0 agent formed bodic;s contain such a cellulose-based disintegration aid in
quantities of
0.5 to 10% by weight, preferably 1 to 8% be weight and in particular 2 to 6%
by
weight. Pure cellulose has the formal gross composition (C6HloOs)" and,
formally
considered, represents a (3-1,4-polyacetal of cellobiose which, in turn, is
built of two
molecules of glucose. Suitable celluloses in this respect consist of
approximately 500
25 to 5000 glucose units and consequently have a molecular weight of 50000 to
500000.
Within the framework of the present invention, cellulose derivatives can also
be used
as cellulose-based disintegration aids which are obtainable from cellulose by
polymer-analogous reactions. Such chemically modified celluloses comprise
products from esterification or etherification reactions in which hydroxy
hydrogen
30 atoms were substituted. However, celluloses in which the hydroxy groups
were
replaced by functional groups not bound via an oxygen atom can be used as
cellulose
39
CA 02317030 2000-09-08
derivatives. For example, alkali celluloses, carboxymethyl cellulose (CMC),
cellulose
ester and ether as well as amino celluloses belong to the group of cellulose
derivates.
The above-mentioned cellulose derivates are preferably used as cellulose-based
disintegration aids not as such but in mixture with cellulose. The content of
cellulose
derivates in this mixture is. preferably below 50% by weight, particularly
preferably
below 20% by vveight, based on the cellulose disintegration aid. Particularly
preferably, pure cellulose free from cellulose derivates is used as cellulose-
based
disintegration aid.
Microcrystalline cellulose can be used as a further cellulose-based
disintegration aid
or as part of this component. This microcrystalline cellulose is obtained by
partial
hydrolysis of celluloses under conditions which attack and completely dissolve
only
the amorphous regions (approximately 30% of the total cellulose mass) but
leave the
L 5 crystalline areas (approximately 70%) undamaged. A subsequent
deaggregation of
the micro-fine cell.uloses firmed by hydrolysis provides microcrystalline
celluloses
which exhibit primary particle sizes of approximately 5 ~m and can be
compacted to
form granules with an average particle size of 200 pm.
Within the framework of the present invention, detergent and cleaning agent
formed
bodies are preferred which additionally contain a cellulose-based
disintegration aid in
the formed bodies.. Particularly preferred cellulose-based disintegration aids
are
agglomerated by compacting and water-free agglomeration processes and consist
in a
proportion of at least 90% b~y weight of particles with sizes above 400 Vim,
preferably
in a proportion of a.t least 6ti% by weight of particles with sizes above 800
p,m and in
particular in a proportion of at least 50% by weight of particles with sizes
above 1200
p.m.
Before the preparation of the pre-mixture (process step c)) the granules or
agglomerates from process steps a) and b) can be "powdered" with finely
particulate
surface treatment agents. 'This may be advantageous for the quality and
physical
CA 02317030 2000-09-08
properties of the pre-mixture (storage, compression) and that of the finished
detergent
and cleaning agent formed bodies. Finely divided powdering agents are well
known
in the state of the art, zeolites, silicates and other inorganic salts being
generally used.
Preferably, however, the pre-mixture is "powdered" with finely particulate
zeolite,
zeolite of the faujasite type being preferred.
Within the framework of the present invention it is preferable for at least
one of the
process end products from steps a) and b) to be subsequently powdered with
substances in powder form, the powdering agent being a zeolite of the
faujasite type
with particle sizes below 100 pm, preferably below 10 p,m and particularly
below 5
pm, at least 0.2% by weight, preferably at least 0.5% by weight and in
particular more
than 1% by weight being used. A precondition for powdering is that the
powdering
agent is applied onto the process end products from steps a) or b) without
detaching
itself, i.e. does not lead to undesirable fines present within the framework
of the
present invention.
Apart from the above-mentioned components, namely surfactant, builder and
disintegration aid, other constituents common in detergents and cleaning
agents
belonging to the group of bleaching agents, bleach activators, enzymes,
fragrances,
perfume earners, fluorescent agents, dyes, foam inhibitors, silicone oils,
anti-
redeposition agent;., optical brighteners, greying inhibitors, colour transfer
inhibitors
and corrosion inhitritors carp be introduced via the process according to the
invention
into the detergent and cleaning agent formed bodies.
Among the compounds used as bleaching agents and supplying H202 in water,
sodium perborate tetrahydrate and sodium perborate monohydrate have particular
significance. Other suitable; bleaching agents are, for example, sodium
percarbonate,
peroxpyrophosphates, citrate perhydrate-supplying and Hz02-supplying peracid
salts
or peracids such a:~ perbenzoates, peroxophthalates, diperazelaic acid,
phthaloimino
peracid or diperdodecane dioic acid.
41
CA 02317030 2000-09-08
To achieve an imI>roved bleaching effect during washing at temperatures of
60°C and
less, bleach activators can be incorporated as the only component or as a
constituent
of component b). Compounds providing aliphatic peroxycarboxylic acids with
preferably 1 to 10 C atoms" in particular 2 to 4 C atoms and/or if necessary
substituted
perbenzoic acids under pe:rhydrolysis conditions can be used as bleach
activators.
Suitable substances are those carrying the O and/or N acyl groups with the
above-
mentioned number of C atoms andlor, if necessary substituted, benzoyl groups.
Multiply acylated ;alkylene diamines, in particular tetaacetylethylenediamine
(TAED),
acylated triazine derivate;s, in particular 1,5-diacetyl-2,4-dioxohexahydro-
1,3,5-
l~ 0 triazine (DADHT), acylated glycolurils, in particular tetraacetyl
glycoluril (TAGL~,
N-acyl imides, in particular N-nonanoyl succinimide (NOSI), acylated phenol
sulphonates, in particular r~-nonanoyl or isononoanoyl oxybenzene sulphonate
(n or
iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated
polyhydric alcoho~ls, in particular triacetin, ethylene glycol diacetate and
2,5-
diacetoxy-2,5-dihydrofuran are preferred.
Apart from or instead of the conventional bleach activators, so-called bleach
catalysts
can also be incorporated into the formed bodies. These substances are
bleaching
effect enhancing transition metal salts or transition metal complexes such as,
for
example, Mn, Fe, <:o, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe,
Co,
Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligants and Co, Fe, Cu
and
Ru ammine complexes can also be used as bleach catalysts.
Suitable enzymes acre those from the class of proteases, lipases, amylases,
cellulases
or their mixtures. Particularly suitable are enzymatic active agents obtained
from
bacteria strains or fungi such as Bacillus subtilis, Bacillus licheniformis
and
Streptomyces griseus. Preferably, proteases of the subtilisin type and, in
particular,
proteases obtained from B<~cillus lentus are used. Enzyme mixtures, for
example
those of protease and amylase or protease and lipase or protease and cellulase
or
cellulase and lipase or of protease, amylase and lipase or protease, lipase
and
cellulase, in particular, however, cellulase-containing mixtures, are of
particular
interest. Peroxidasc;s and oxidases have proved suitable in some cases. The
enzymes
42
CA 02317030 2000-09-08
can be adsorbed to earner substances and/or embedded in coating substances in
order
to protect them .against premature decomposition. The proportion of enzymes,
enzyme mixtures or enzyme granules in the formed bodies according to the
invention
can, for example, be approximately 0.1 to 10% by weight, preferably 0.5 to
approximately 5% by weight.
In addition, the detergent and cleaning agent formed bodies can also contain
components which have a positive influence on the removal of oil and fats from
textiles by washing (so-called soil repellents). This effect becomes
particularly
l~ 0 obvious in cases where a textile is soiled which had previously been
repeatedly
washed with a detergent according to the invention containing this oil and fat
removing component. The preferred oil and fat removing components include, for
example, non-ionic cellulose ethers such as methyl cellulose and methyl
hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by
weight and of hydroxypropoxyl groups of 1 to 15% by weight, based on the non-
ionic
cellulose ether in each case, and the polymers, known from the state of the
art, of
phthalic acid and/or terephthalic acid or of their der~ivates, in particular
polymers of
ethylene terephthalates ancUor polyethylene glycol terephthalates or anionic
and/or
non-ionic modifiedL derivatives thereof. Among these, the sulphonated
derivatives of
2.0 the phthalic acid polymers amd terephthalic acid polymers are particularly
preferred.
The formed bodies. may contain derivatives of diamino stilbene disulphonic
acid or
their alkali metal salts as optical brighteners. Suitable salts are e.g. the
salts of 4,4'-
bis(s-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulphonic
acid or
similarly structured compounds which, instead of the morpholino group, carry a
diethanol amino group, a methyl amino group, an anilino group or a 2-
methoxyethyl
amino group. In addition, lbr~ighteners of the type of the substituted
diphenyl styryls
can be present, e.l;. the alkali salts of 4,4'bis(2-sulphostyryl)-diphenyl,
4,4'-bis(4-
chloro-3-sulphostyryl)-diphenyl or 4-(4-chlorostyryl)-4'-(2-sulphostyryl)-
diphenyl.
Mixtures of the above-mentioned brighteners can also be used.
43
CA 02317030 2000-09-08
Dyes and perfume-s are added to agents according to the invention in order to
improve
the aesthetic impression of the products and to provide the user not only with
softness
performance but also with a product that is "typical and non confusable" from
the
visual and sensory point o:P view. Suitable perfume oils or fragrances may
consist of
individual odorifi~rous compounds, e.g. synthetic products of the ester,
ether,
aldehyde, ketone, alcohol and hydrocarbon type. Odoriferous compounds of the
ester
type are, for example: benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl
cyclohexyl acetate, linalyl acetate, dimethyl benzylcarbinyl acetate,
phenylethyl
acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate,
allyl
l0 cyclohexyl propionate, styrallyl propinate and benzyl salicylate. The
ethers include,
for example, benzyl ethyl ether, the aldehydes include, for example, the
linear
alkanals with 8 -- 18 (: atoms, citral, citronellal, citronellyl
oxyacetaldehyde,
cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for
example, include ionones, a-isomethyl ionone and methyl-cedryl ketones, the
alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenyl
ethyl alcohols
and terpineol, the hydroca~:bons include mainly the terpenes such as limonene
and
pinene. Preferably, however, mixtures of different odoriferous substances are
used
which jointly produce an agreeable fragrance. Such perfume oils may also
contain
mixtures of natural odorii:erous substances such as those obtainable from
plant
sources, e.g. pine, .citrus, jasmine, patchouli, rose or ylang ylang oil.
Mace, sage oil,
camomile oil, clove oil; melissa oil, mint oil, cinnamon leaf oil, lime
blossom oil,
elderberry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as
well as
orange blossom oil" neroli oil, orange peel oil and sandalwood oil are also
suitable.
The fragrances can be incorporated directly into the agents according to the
invention;
however, it may allso be advantageous to apply the fragrances onto earners
which
enhance the adhesion of the; perfume to the clothes and ensure a lasting
fragrance of
the textiles by slow fragrance release. Cyclodextrines, for example, have
proved
suitable for use as such earner materials, it being possible to additionally
coat the
cyclodextrine perfume complexes with further auxiliary agents.
44
CA 02317030 2000-09-08
Within the frame;work of the present invention, it is particularly preferred
to
incorporate the fragrances via concentrated fragrance compounds, the so-called
"fragrance beads" into th.e detergent and cleaning agent foamed bodies. Such
concentrated fragrance compounds can be produced according to process steps a)
or
b), it being preferable for at least one of the agglomerates produced in
process step b)
to contain perfume.
The production of the "fragrance beads" preferably used in the process
according to
the invention is described in the earlier German Patent Application 197 46
780.6
(Henkel KGaA), for example. This application discloses a process for the
production
of fragrance formc;d bodies, in particular fragrance beads with bulk densities
above
700 g/1, in the case of which a solid and essentially anhydrous pre-mixture of
a) 65 to 95% bay weight carrier substances)
b) 0 to 10% be weight auxiliary agents) and
c) 5 to 25% by weight perfume
is subjected to granulation or compression agglomeration.
In this connection,, the preferred carrier substances are selected from the
group of
surfactants, surfactant compounds, di and polysaccharides, silicates,
zeolites,
2,0 carbonates, sulphal:es and citrates and are used in quantities of between
65 and 95%
by weight, preferably of between 70 and 90% by weight, based on the weight of
the
fragrance formed bodies produced.
Apart from the "jFragrance beads" that can be prepared by way of the process
described above, the incorporation of fragrance beads as described in the
earlier
German Patent Application 197 46 781.4 (Henkel KGaA) is preferred in the
process
in the present invention. In this specification, a process for the production
of
fragrance-enhanced detergents or cleaning agents or components for these with
bulk
densities above 601) g/1 is disclosed, in which a solid and essentially
anhydrous pre-
mixture of detergent or cleaning agent compounds and/or detergent or cleaning
agent
raw materials is produced which contains at least 0.1 % by weight perfume,
based on
the pre-mixture, and this pre-mixture is subjected to compression
agglomeration.
CA 02317030 2000-09-08
Such fragrance-enhanced detergents or cleaning agents or the above-mentioned
fragrance formed bodies can be used as the end products from a process step a)
or b)
also in the process according to the invention, provided they satisfy the
selection
criteria with respect to particle size.
In order to improve the aesthetic impression of the agents according to the
invention,
they ca be dyed with suitable dyes. Preferred dyes, the selection of which
causes no
problems whatsoever to the expert, have a high stability in storage and
insensitivity
vis-a-vis the other constituents of the agents and vis-a-vis light as well as
no
l~ 0 pronounced substantivity vis-a-vis textile fibres, so as not to discolour
the latter.
For aesthetic reasons it may be desirable to produce formed bodies in which
only
individual phases or layers are dyed. In the process according to the
invention, this is
possible without problems in the different variations. Thus - due to the
process steps
a) and b) - at least two phases are already present in the formed body only
one or
even both of which. can be dyed differently, thus obtaining "mottled" formed
bodies.
Dyeing of the process end products from intermediate steps a) or b) can be
effected in
the conventional way by the addition of dyes or dye solutions. However, the
use of
2,0 fully dyed powder agents is preferred which cover the surface of the
process end
products from the intermediate steps and thus optically suggest a fully dyed
grain. In
this way, dye is saved, on the one hand, and, on the other hand, problems due
to the
incorporation of excessive quantities of dye into the formed bodies and
consequently
into the wash liquor are avoided.
Process c) comprises combining the granules from steps a) and b) to form a
compressed pre-mixture. In the case of multiple layer tablets, several
differently
composed and/or dyed pre-:mixtures are provided. As already explained in terms
of
an approach, it is not necessary in this respect to homogeneously mix the
process end
products from intermediate steps a) and b), this procedure being preferred.
According
to the invention, it is also possible to produce double and multiple layer
tablets by
46
CA 02317030 2000-09-08
combining the granules from steps a) and b) only immediately before process
step d),
namely the comprc;ssing step.
However, since multiple layer or ring/nucleus or jacketed tablets require an
increased
process effort and reduce the rates of throughput (number of formed bodies per
unit of
time) in the tableting press, it is preferable within the framework of the
present
invention to mix the process end products from intermediate steps a) and b)
before
introduction into the matri:K. Mixing of the process end products from
intermediate
steps a) and b) can appropriately be effected in the mixer which was used for
the
1!.0 preparation of the agglomerates in step b). A batchwise process would be
such that
intermediate steps a) and b) would be corned out in parallel and the process
end
products from step a) transferred to the mixer used in step b) where they
would be
mixed with the process end products from step b). The pre-mixtures produced in
this
way could then undergo intermittent storage until processed further in step
d).
However, it is also possible to design a continuous process in the case of
which step
c) is carried out in a further mixer from which the pre-mixture to be
compressed is
then passed to a tableting press. This process variant is required in
particular in those
cases where, in step b) not just one granular product is formed but several
differently
2:0 composed granular products all of which are to be combined in step c).
When selecting suitable machines and process parameters, the expert is able to
fall
back on machines and equipment known in the literature and on technical
process
operations such as those described by W. Pietsch, in "Size Enlargement by
Agglomeration ", psublisher: Wiley, 1991 and the literature quoted therein.
The proportion of the individual process end products from steps a) and b) in
the pre-
mixture can vary within wide limits, depending on which type of formed body is
to be
produced. It is preferable during the production of the pre-mixture for the
portion of
the granules produced in step a) present in pre-mixture c) to amount to 40 to
95% by
weight, preferably .50 to 90'% by weight and in particular 60 to 85% by
weight, based
on the pre-mixture.
47
CA 02317030 2000-09-08
Process step dl:
Process step d) is executed by filling the pre-mixture produced in step c)
into the
appropriate matrices and forming it, in particular compressing it to tablets
or pellets, it
being possible to fall back: on conventional processes for the production of
formed
bodies. In the tableting press, the pre-mixtures are compacted in a so-called
matrix
between dies to form a firm compressed body. This process, referred to simply
as
tableting in the following, consists of four stages, metering, compaction
(elastic
deformation), plastic deformation and ejection.
to
Tableting takes place in commercially available tableting presses which,
basically,
may be equipped with single or double dies. In the latter case, the upper die
is not
only used for a pressure build up, the lower die moves during the compression
process
towards the upper die while the upper die presses downwards. For small
production
l.5 quantities, eccentric tableting presses are preferably used in the case of
which the die
or dies are fixed to an eccentric disc which in turn is mounted to a shaft
with a certain
rate of rotation. The movement of this compression die is comparable to the
method
of operation of a standard four-stroke engine. Compression can be effected
with any
upper and lower die; howewer, several dies can also be fixed to an eccentric
disc, the
~;0 number of matrix bores being correspondingly increased. The rates of
throughput of
the eccentric presses vary, depending on the type, between several hundred and
maximum 3000 tablets per hour.
For higher rates of throughput, rotary tableting presses are chosen in the
case of which
2;5 a larger number o:f matrices is arranged in a circular manner on a so-
called matrix
table. The number of matrices various between 6 and 55, depending on the
model,
larger matrices also being available on the market. An upper and a lower die
is
allocated to each matrix on the matrix table, it being again possible to build
up the
compression press~.ire actively only via the upper or the lower die but also
by both
30 dies. The matrix table and the dies move jointly around a vertical shaft,
the dies being
placed by means of rail-type curved paths during rotation into the positions
for filling,
compaction, plastic; deformation and ejection. At those points where a
particularly
48
CA 02317030 2000-09-08
pronounced lifting; or dropping of the dies is required (filling, compaction,
ejection),
these curved paths. are supported by additional low pressure pieces, low
traction rails
and ejection paths.. Filling of the matrices takes place via a rigidly
arranged input
device, the so-called filling shoe, which is connected to a storage container
for the
pre-mixtures. The compression pressure onto the pre-mixture concerned is
individually adjustable via the upper and lower die compression paths, the
pressure
build up being effected by rolling the die shaft heads past adjustable
pressure rollers.
To increase the rate of throughput, the rotary presses can also be equipped
with two or
several filling shoes. To produce double or multiple layer formed bodies,
several
~L 0 filler shoes are arranged behind each other without the slightly pressed
down first
layer being ejected before. further filling. By way of a suitable process
control,
jacketed and point type t;~.blets can be produced which have an onion skin
type
structure, the upper side of the nucleus or the nucleus layers not being
covered in the
case of the point type tablets, thus remaining visible. The rotary tableting
presses can
l~ 5 also be equipped with single or multiple tools so that, for example, an
outer circle
with 50 and an inner circle 'with 35 bores can be used simultaneously for
compressing.
The rates of throughput of modern rotary tableting presses are one million
formed
bodies per hour.
a!0 Tableting machines which are suitable within the framework of the present
invention
are, for example supplied by Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette
GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am
See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and
Courtoy N.V., Halle (BE,~LU). The hydraulic double pressure press HPF 630
25 manufactured by LAEIS, for example, is particularly suitable.
The formed bodies can be manufactured in a predetermined dimensional form and
predetermined size, it being; possible for them to consist of several phases,
i.e. layers,
inclusions or nuclei and rings. Suitable dimensional forms are, in practice,
all
?~0 manageable designs e.g. shaping them as a tablet, stick, rod or bar, cube,
rectangular
block and corresponding spatial elements with level lateral surfaces as well
as, in
particular, cylindrical designs with a circular or oval cross-section. This
latter design
49
CA 02317030 2000-09-08
includes the provision of forms ranging from the tablet to the compact
cylinder with a
ratio of height to diameter of more than 1.
The apportioned compacted bodies can, in each case, be shaped in the form of
separate individual elements which correspond to the predetermined dosage of
the
detergent and/or cleaning agent. It is also possible to form compressed bodies
combining a number of such mass units in one compressed body, the easy
reparability
of apportioned smaller units being provided in particular by predetermined
breaking
points. For the usc; of textile detergents in machines of the type common in
Europe
ll0 with horizontal mechanics., the formation of the apportioned compressed
bodies as
tablets, in cylinder or cube form may be appropriate, a ratio of diameter to
height in
the region of approximately 0.5 : 2 to 2 : 0.5 being preferable. Commercial
hydraulic
presses, eccentric lpresses or rotary presses, in particular, are suitable
devices for the
production of such compressed bodies.
1. 5
The dimensional form of aalother embodiment of the formed body has been
adjusted,
in terms of its dimensions, to the dispenser chamber of commercial domestic
washing
machines so that the formed body can be metered directly without metering aid
into
the dispenser charr~ber where it dissolves during the flushing-in process. As
a matter
~;0 of course, however, the use; of the detergent formed bodies via a metering
aid is also
possible without problems.
A further preferred formed body, which can be produced, has a plate or board-
type
structure with alternate thick and long and thin and short segments so that
individual
2.5 segments can be broken off from the "bar" at the rated breaking points
representing
the short thin segments anal introduced into the machine. This principle of
"bar-
shaped" formed body detergent can also be realised in the form of other
geometric
shapes, e.g. vertical upright triangles which are merely joined along one of
their sides
longitudinally. In this case, the possibility presents itself for optical
reasons to form
30 the triangular base which connects the individual segments as one phase
while the tip
of the triangle fo ms the second phase. Dyeing the two phases differently is
particularly attractive in the case of this embodiment.
CA 02317030 2000-09-08
Following compre;ssion, the detergent and cleaning agent formed bodies exhibit
a
high level of stability. The fracture strength of cylindrical formed bodies
can be
determined by way of the measured value of the diametral fracture stress. This
can be
determined according to thc~ following formula
2P
a= -
~Dt
in which a represents the diametral fracture stress, DFS, in Pa, P is the
force in N
which leads to the presswre exerted onto formed body causing the fracture of
the
formed body, D ins the formed body diameter in meters and t is the height of
the
formed body.
1'.5 According to the process of the invention it is possible and preferred to
adjust
compression pressures in process step d) which lead to formed bodies with
fracture
hardness of 20 to 150 N, preferably of 40 to 100 N and in particular of 50 to
80 N. If
multiple phase detergent and cleaning agent formed bodies are produced by the
process of the invention, it is again preferable for the fracture hardness of
the
individual phases to differ by maximum ~1 S%, preferably by maximum +10%.
By way of the quantity of pre-mixture compressed in process step d), the mass
of the
formed body can be accurately fixed. Within the framework of the present
invention,
processes are preferred which lead to detergent and cleaning agent formed
bodies with
2 5 a weight of between 10 and 150 g, preferably between 20 and 100 g and in
particular
between 35 and 75 g.
The process according to the invention is particularly suitable for the
production of
universal detergents in tablet form. However, colour care detergents can also
be
3'.0 produced by omitting the use of bleaching agents and bleach activators
and instead
introducing coarse-grained salts or organic oligocarboxylic acids, e.g. sodium
citrate
or citric acid into the formed bodies. Special detergents in the form of
compact
formed bodies can also be produced without problems by adding textile care
51
CA 02317030 2000-09-08
substances, for example, in one of the process steps a) of b) or matching
certain
constituents to the required profile for certain textiles. According to the
process of the
invention, it is thus also possible without problems to provide wool
detergents in
tablet form, for example. The expert is not restricted in his formulation
freedom by
the process of thc; invention and is now able to produce, by way of the
process
according to the invention, standard, universal and special detergents
familiar to him
also in the form o:f compac;ted formed bodies. Examples of formulations for a
wide
variety of detergents are given in W.H. de Groot, 1. Adamai, G.F. Moretti,
"The
Manufacture of ll~l~odern Detergent Powders ", published by W. Hermann de
Groot
li 0 Academic Publishers, 1995, for example.
The process according to the invention has a number of advantages compared
with
conventional production processes for detergent and cleaning agent formed
bodies.
On the one hand, tlhe particle size of the pre-mixture to be compressed is
substantially
greater than norm;~lly, on the other hand, the particle size distribution is
relatively
narrow. Without wanting to be restricted by the theory, the applicant starts
out from
the assumption that it is possible, as a result of the larger particles, to
exert a higher
compression pressure onto the mixture to be tableted without negatively
influencing
the solubility thereof. In the case of conventional more finely particulate
pre-
2;0 mixtures, compaction is brought about by the compression pressure in that
the fine
particles fill the gaps between the coarser particles leading, in extreme
cases, to a
compact though firmly bonded formed body throughout which is difficult to
dissolve.
By almost completely eliminating finely particulate substances from the pre-
mixture
and by way of a relatively narrow size distribution, formed bodies can be
produced by
the process according to l;he invention which exhibit a void between the
firmly
bonded "beads" anal are easily soluble in spite of their high density. This
effect is
enhanced by using large proportions of process end products from intermediate
step
a).
Due to the excellent reproducibility during the production of the process end
products
in intermediate step a), the pre-mixture has a highly homogeneous composition.
Each
(ideally "bead shaped") granule grain from intermediate step a) exhibits, due
to the
52
CA 02317030 2000-09-08
process, the same composition and always almost the same size as the other
grains.
As a result of the low water or completely water-free preparation, variations
in quality
due to different water contents of the pre-mixture are eliminated. In process
step d),
these characteristics of the process according to the invention provide the
advantage
that variations in t:he tablet hardness are reduced to a minimum. Whereas the
usual
pre-mixtures to be tableted provide formed bodies with a fixed compression
pressure
of the tableting press, which can vary in terms of their hardness by up to
30%, these
variation ranges are substantially less than 10% in the case of the process
according to
the invention.
The process seque-nce of the process according to the invention is optimised
since
subsequent admixing of further constituents is eliminated. Finely particulate
constituents which are to be used can "be bonded" to the large particles
providing
substantial advantages during dyeing of the particles, as detailed above. The
incorporation of fragrances or other liquid constituents via "fragrance beads"
or
"active substance beads" leads to the migration tendency of these substances
during
compression being; reduced to a minimum, this having a favourable effect on
the
properties of the formed bodies obtained.
Consequently, the detergent; and cleaning agent formed bodies produced
according to
the process of the invention are stable in storage even in the unpackaged
state, do not
become hard subsequently and require no air tight individual packaging.
Compared
with conventional formed bodies, they are characterised by a greater hardness
and
better solubility so that they can be metered into domestic washing machines
via the
dispensing chamber. Moreover, they are stable when subjected to sudden
stresses
such as being dropped, tending neither to break nor to exhibit edge breakage
phenomena.
Examples
E~~ample 1:
In a batch mixer (20 litres) equipped with a knife head comminuter (chopper)
further
components, includling a binder, were added to spray dried granules S 1 and S2
(for
53
CA 02317030 2000-09-08
details of the composition compare table 1). The addition of the possibly
present non-
ionic surfactants :liquid at temperatures below 45°C and a pressure of
1 bar was
effected in the mixer by atomising through nozzles into the powder stream. The
mixture was then homogenised for a further two minutes and subsequently passed
to a
double screw extruder whose granulation head had been preheated to
temperatures
between 50 and 65°C, preferably to 62°C. The pre-mixture was
plasticised under the
shearing effect of the exb,~-uder screw and subsequently extruded at a
pressure of
between 50 and 100 bar, preferably at around 78 bar through the perforated
extruder
head die to form fine strands of a diameter of 1.4 mm, which strands, after
discharge
from the die, were comminuted by means of a chopping knife to form
approximately
spherical granules (ratio of length to diameter approximately l, hot chop
effect). The
warm granules thus obtained were rounded off for one minute in a commercial
rounding device of the Mwumerizer4 type and, if necessary, coated with a
finely
particulate powder, The bulk density of the extrudates A1 and A2 thus produced
was
1 S 800 ~ 50 g/1, the particle sizes were entirely between 1200 and 1500 p,m.
The
composition of this process end product from intermediate step a) is detailed
in table
2.
Table 1: Composition of the spray dried granules (% by weight):
S1 S2
C9-C13 alkyl benzene sulphonate 26.3 12.07
Tallow fatty alcohol with an average1.1 -
of 5 EO
CIZ-C1g sodium fatty acid soap 1.4 3.0
Sodium hydroxide - 0.03
Sodium carbonate 9.4 4.15
Na-hydroxyethane-1,1-diphosphonate - p, g
Polyvinyl pyrrolidone - O,g
Copolymeric sodiu~.m salt of acrylic4.0 4.15
acid and
malefic acid
Zeolite A, based on anhydrous active39.5 57.75
substance
Amorphous sodium disilicate 2,g _
Water 13.6 16.65
Salts from solutions. Remainder ~ Remainder
54
CA 02317030 2000-09-08
Table 2: Composition of t:he process end products from intermediate step a) (%
by
weight)
Al A2
Spray dried granules ~ 61.0 (S 65.71 (S2)
1 )
C 1 Z-C 1 g fatty alkyl sulphate 6.0 11. 83
*
Copolymeric sodium salt of acrylic 3.0 2.96
acid and
malefic acid
Sodium perborate monohydrate 20.0 -
Polyethylene glycol (4000 ~,nno~ 6.0 3.59
CIZ-C1g fatty alcohol with m average4.0 8.92
of 7 EO
Trisodium citrate dihydrate - 6.99
* Composition of l:he fatty alkyl sulphate:
in Example A1: 9:2.00% by weight of active substance, 3.70% by weight of
sodium
sulphate, 2.80% by weight of other salts from raw materials and unsulphonated
fractions as well as 1.50% by weight of water.
in Examn a A2: T5% by weight C12-C,g alkyl sulphate, 17% by weight of sodium
sulphate, 3% by weight of sodium carbonate, 1% by weight of water, remainder
salts
from solutions.
For the production of the process end products from intermediate step b), a
soil
release polymer, enzymes, defoamer and bleach activator were introduced into a
Lodige ploughshare; mixer and sprayed with perfume oil and an anhydrous
swollen
1.5 polymer while the mixing tool was operating. After an agglomeration time
of 30
seconds, a powdering agent was added. After 30 seconds, the agglomerates were
coated with the powdering .agent. The addition of the cellulose-based
disintegration
aid took place last without an intense wetting with agglomeration liquid
occurring.
The agglomerates obtained had particle sizes of between 1000 and 1600 p,m;
their
composition is detaiiled in Table 3.
CA 02317030 2000-09-08
Table 3: Composition of the process end product from intermediate step b) (%
by
weight)
Terephthalic acid ethylene ;glycol 4.8
PEG ester
Enzyme mixture (protease, lipolase, 11.3
cellulase,
amylase)
Paraffin silicone defoamer, 15% on 18.2
soda -
Tetreaacetylethylenediamine 33.4
Perfume oil 1.9
Hydroxypropyl starch, 5%, swollen in 1.9
glycerine
Zeolite A (powdering agent) 1.9
Cellulose disintegrating agesnt ~ 26.6
In process step c), 79.33% by weight of extrudates A1 was mixed with 20.67% by
weight of granules B and subsequently compressed in process step d) on an
eccentric
press to form the formed bodies E1 according to the invention. The tablets had
a
diameter of 44 mm, a height of 17 mm and a weight of 36g.
The hardness of thc; tablets was measured by forming the tablets up to
breaking point,
the force being applied to the lateral surfaces of the tablet, determining the
maximum
force which the tablet withstood.
To determine the 'tablet disintegration, the tablets were placed into a glass
beaker
1 S containing water 0600 ml water, temperature: 30°C) and the time
which passed up to
complete tablet disintegration was measured.
To determine the residual behaviour and/or the solubility behaviour
(solubility test),
one tablet was introduced into one litre water in a 2 litre glass beaker with
stirring
(800 rpm, with laboratory stirrer/propeller stirrer head, centred at a
distance of 1.5 cm
from the glass beaker bottom) and stirred for 1.5 minutes at 30°C. The
test was
carried out with water of 16° German hardness. Subsequently, the wash
liquor was
56
CA 02317030 2000-09-08
poured through a sieve (80 pm). The glass beaker was rinsed with very little
cold
water over the sieve. A double determination was carned out. The sieves were
dried
in the drying cabinet at 40°C + 2°C until a constant weight was
reached and the
detergent residue vvas weighed. The residue is indicated as the mean value of
the two
S individual determinations, in %. In the case of deviations between the
individual
results by more than 20%, further experiments are usually carned out; however,
this
was not necessary in the case of the present investigations.
The physical properties of the detergent tablets are detailed in Table 4.
Table 4: Detergent tables (physical data)
E1
Fracture hardness (l~ 50
Disintegration times) 12
Dissolution test (residue) 1 g
(% by
weight)
Drop test from a height Stable, no edge disintegration
of 1 m
1:5 By mixing the individual components in a Lodige ploughshare mixer (process
step
c)), two pre-mixtures were produced which were subsequently compressed into
two
layer tablets E2 by sequential filling of the matrices of an eccentric press.
The
proportion of blue phase of the tablet was 25%, the proportion of white phase
75%.
The extrudates A1 described above were used as end product from partial step
a), the
process end product: from partial step b) is obtained from the details in
table 5 in that
all constituents, with the exception of extrudates A1, were agglomerated in a
mixer
granulator. The particle size of these agglomerates was between 1200 and 1400
pm.
The composition of the individual phases is indicated in Table 5.
2 'i
57
CA 02317030 2000-09-08
Table 5: Composition of i;he double layer tablets (broken down according to
layers)
(% by weight)
Blue phase White phase
~
Terephthalic acid ethylene; - ~ 1.32
glycol PEG
ester
Enzyme mixture (protease, lipolase,9.35 -
cellulase, amylase)
Paraffin silicone defoamer, 3.75 3.75
15% on soda
Tetreaacetylethylenediamine - 9.21
-
Fragrance beads * 4.00 4.00
Hydroxypropyl st~crch, 5/~, 0.40 0.40
swollen in
glycerine
Extrudate A1 76.60 75.24
Zeolite A (powdering agent) - 0.40
Zeolite A (powdering agent), 0.40 -
dyed blue
Cellulose disintegrating agent- ~ 5.50
Cellulose disintegrating agent,5.50 -
dyed blue
.5 * Fragrance beads produced according to the theorem of the earlier German
patent
application 197 46 '780.6, containing 10% perfume.
Process step d) wa.s earned out by introducing first the pre-mixture for the
white
phase and subjecting it to light preliminary compression followed by the pre-
mixture
11) for the blue phase and fully compressing the formed body.
The physical properties of the double layer detergent tablets are shown in
Table 6.
58
CA 02317030 2000-09-08
Table 6: Detergent tablets (physical data)
E2
Fracture hardness (I~ 60
Disintegration time:(s) 6
Dissolution test (residue;) 1 g
(% by
weight)
Drop test from a height Stable, no edge disintegration
of 1 m
Example 3:
In an analogous m;~nner as for example 2, double layer detergent and cleaning
agent
formed bodies were produced, the extrudates A2 described above being used as
the
end product from process step a). The composition of the process end product
from
step b) was also different in this case and is in turn shown in the following
table, in
which all components, with the exception of A2, were granulated to form
particles
with particle sizes of between 1200 and 1400 pm.
In contrast to example 2, the bleaching agent is introduced into the process
in this
example not via the product of step a) but via step b). The composition of the
1:5 individual phases is shown in Table 7.
25
59
CA 02317030 2000-09-08
Table 7: Composition of the double layer tables (broken down according to
layers)
(% by weight)
Blue phase White phase
Terephthalic acid ethylene glycol1.00 ~ 1.00
PEG ester
Enzyme mixture; (protease, lipolase,2.35 2.35
cellulase, amylase)
Paraffin silicone de:foamer, 3.75 3.75
15% on soda
Tetreaacetylethylenediamine, 21.00 -
dyed blue
Sodium percarbonate - 21.00
Fragrance beads * 4.00 4.00
Hydroxypropyl starch, S'%, swollen0.60 0.60
in
glycerine
Extrudate A2 61.50 61.50
Zeolite A (powdering agent) - 0.30
Zeolite A (powdering agent), 0.30 -
dyed blue
Cellulose disintegrating agent - 5.50
-
Cellulose disintegrating agent,5.50 -
dyed blue ~
:5 * Fragrance beads produced according to the theorem of the earlier German
patent
application 197 46 '780.6, containing 10% perfume.
Process step d) was. earned out in an analogous manner to example 2 by
introducing
first the pre-mixture for the white phase and subjecting it to light
preliminary
11) compression followed by the; pre-mixture for the blue phase and fully
compressing the
formed body E3.
The physical properties of the double layer detergent tablets are shown in
Table 8.
1-'i
CA 02317030 2000-09-08
Table 8: Detergent tablets (physical data)
E3
Fracture hardness ( I~ 50
Disintegration times) 10
Dissolution test (residue) 16
(% by
weight)
Drop test from a height Stable, no edge disintegration
of 1 m ~
61
