Note: Descriptions are shown in the official language in which they were submitted.
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METHOD FC~R THE PRODUCTION OF STABLE AND RAPIDLY
DISINTEGRATING SHAPED DETERGENT UNITS
The present invention relates to the production of shaped detergent and
cleaning
composition units. The invention relates, in particular, to a method for the
production
of detergent and cleaning-active shaped units that can be produced through com-
pression shaping of p<3rticulate detergent and cleaning compositions and stand
out
for great solidify and, at the same time, favourable disintegration and
dissolution
characteristics.
Detergent and Leaning-active shaped units are produced by applying pressure to
a
compound to be compressed that is located in the hollow space of a press. In
the
simplest case of shaped unit production - hereinafter, for reasons of
simplicity, re-
ferred to as tablet prcasing - the compound to be shaped into tablets is
directly
compressed, i.e. withcaut previous granulation. The advantages Qf this so-
called di-
rect tablet pressing consist in its simple and cost-efficient application
resulting from
the fact that no further process steps and, hence, no further machines are
required.
These advantages, however, are accompanied by disadvantages. A powdery com-
pound to be subjected to direct tablet pressing must, for instance, be
characterised
by sufficient plastic ductility and good flow properties; additionally,
absolute absence
of demixing tendenciE~s during storage, transport and charging of the mould is
re-
quired. These three preconditions are extremely difficult to control in many
sub-
stance compounds so that direct tablet pressing is, especially in the context
of the
production of detergent and cleaning composition tablets, applied very rarely.
The common method to produce detergent and cleaning composition tablets uses
powdery components ("primary particles") as a starting material which is then
ag-
glomerated or granul~~ted, respectively, into secondary particles with a
greater parti-
cle diameter by application of appropriate methods. These granulates or
mixtures
of different granulate:: are then mixed with individual additive substances
and sub-
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jacked to tablet pressing. In this respect, the characteristics of the
granulates are of
decisive importance for the physical characteristics of the shaped units:
particle size,
content of moisture and other parameters that can be controlled in the
granulates
contribute decisively t~~ the characteristics of the resulting shaped units.
In this re-
spect, two physical clharacteiistics of shaped units are of decisive
importance in
connection with shaped detergent and cleaning composition units: hardness and
speed of disintegraticm_ In the course of tablet production, application of
corre-
spondingly high pressure allows the production of shaped units of any desired
sta-
bility, but the time required for disintegration of the resulting shaped unit
rapidly
grows with the pressure applied. As a consequence of the fact that the desired
charackeristics of a hard tablet characterised by stability during transport
and han-
dling that will nevertheless disintegrate rapidly are opposed to each other,
the pro-
duction of detergent .and cleaning composition tablets generally is faced with
the
problem of overcoming, to the greatest possible extent, the dichotomy between
hardness and disintegration.
As far as the production of granulates is concerned, prior art comprises an
almost
endless amount of v~~ritten nnaterial ranging from patent documents to
complete
monographs of granulating technology.
EP-B-642 576 (Henkel) discloses a method for the continuous production of
granu-
lates wherein the: product flows horizontally through a first, low-speed
mixer/granulator (circumferential speed of the mixing tools 2 - 7 m/s) where
it is pre-
granulated and then vertically through a second, high-speed mixer/granulator
where
it is fully granulated (circumferential speed of the mixing tools ~ 8 m/s).
The combination of stow and fast mixers with different sojourn times of the
products
in the mixing granula~tors is also extensively described in prior art_ The
European
patent application EP-A-264 ~D49 (BAYER AG), for example, describes a method
for
the production of granulates where the powder to be granulated is granulated,
add-
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3
ing a granulating liquid, i=trst ins a fast and then in a slow mixing
granulator and sub-
sequently dried in a fluidised bed. The product stays in the fast mixer (speed
800 -
3000 r_p_m.) for a period of 0.5 to 60 seconds and in the slow mixer (speed 60
to
250 r.p.m.) far another period of 60 to 300 seconds_
The adaptation of the: above-mentioned procedure for the production of
detergent
granulates is described in EEC A-367 339 (Unilever). This document discloses
the
production of detergent granulates with bulk densities exceeding 650 g/I
through
treatment of a powdery starting material in a high-speed mixer (speed 100-2500
r_p.m_, sojourn time :r30 s), subsequent mixing in a slow mixer (speed 40-160
r.p.m., sojourn time 6C1-600 s) and final drying.
EP-A-390 251 (Unilever) expands the latter method by adding 0_1 to 40 percent
in
weight of a powder between the fast and the slow mixer. This measure is
intended to
minimise formation of particle:a with excessively large particle diameters_
Shaped detergent and cleaning composition units are produced by compressing
particulate detergent and deaaning compositions that consist, at least in
part, of
granulates. Shaped detergeni: and cleaning composition units as well as
methods for
their production are also ext~:nsively described in prior art. EP-A-0 522 766
(Unile-
ver), for example, disnloses shaped units consisting of a compacted,
particulate de-
tergent composition that contains tensides, builders and substances enhancing
dis-
integration (e_g_ cellulose-based), wherein at last part of the particles is
coated with
the disintegration enhancing substance which, during dissolution of the shaped
units
in water, displays both binding and disintegrating effects_ The same document
points
out the general problem of producing shaped units of adequate stability that
are, at
the same time, easily soluble. The particle-size of the compound to be
compressed
should exceed 200 Nm, and i:he upper and the lower limits for the individual
particle
sizes should not be more than 700 Nm apart_ The shaped units are produced by
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4
mixing a detergent and cleaning composition granulate produced in one of the
known ways with powdery upgrading agents and subsequent compression shaping.
Additional documents relating to the production of shaped detergent units are
EP A-
0 716 14.4 (Unilever), which describes shaped units with an external coating
of wa-
ter-soluble material, and EP-A-0 711 827 (Unilever), which specifies a citrate
of de-
fined solubility as an ingredient.
The application of binding agents which exert a disintegrating effect, if any,
(espe-
cially polyethylene ghrcol) is disclosed in EP-A-0 711 828 (Unilever), which
de-
scribes shaped deten~ent unfits that are produced by compressing a particulate
detergent composition at temperatures between 28°C and the melting
point of the
binding material, the pressing always taking place below the melting
temperature_
Examples mentioned in this dfocument indicate that shaped units manufactured
ac-
cording to the disclosed method display a higher resistance to breaking where
the
pressing process was performed at a higher temperature_
Detergent tablets where individual ingredients are arranged in discrete
regions
separate from the rest are also described in EP-A-0 481 793 (Uniiever). The
deter
gent tablets disclosed in this document contain sodium percarbonate arranged
in a
discrete region separ<~te from all other components that might exert an
influence on
its stability.
The production methods for c[etergent and cleaning-active shaped units
indicated in
poor art consist of compressing shaping the respective substances, which
partly
takes place at difFerernt temperatures. As further influencing parameters,
prior art
only mentions physical characteristics of the compound compressed such as the
particle size, the spafiial distribution of the individual components of
physical char-
acteristics of individu<~I components.
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Prior art, however, do~as not describe how purposeful preparation of the
particulate
detergent and cleaning composition to be compressed can exert a positive
influence
on the physical charac~eristic~; of the resulting shaped detergent and
cleaning com-
position units_
The objective of the present invention consists in providing, in addition to
the seleo-
tion of individual components, another influencing factor that can be used to
improve
the physical characteristics of shaped detergent and cleaning composition
units. The
present invention, in F~articular, focussed on the task of providing a method
to sup-
ply, through purposeW I preliminary treatment of the compound to be
compressed,
detergent and cleannng composition tablets that are hard and yet disintegrate
quickly.
It has been found that: compliance with certain mixing times is essential,
when mix-
ing the granular components with the powdery mixing components in the course
of
the production of the particulate detergent and cleaning composition to be com-
pressed, in order to produce tablets characterised by great hardness and
favourable
disintegration charade:rlstics at the same time_
The object of the prersent invention is, therefore, a method for the
production of
shaped detergent andl cleaning composition units by mixing a detergent and
clean-
ing composition granulate maanufactured in one of the known ways with powdery
upgrading components and subsequent compression shaping, wherein the mixing of
the granulate with the; powdery upgrading components takes place in a mixer
and
the mixture is, after audition of the final component and for a sojourn time
between
one and 300 seconds" subjecl:ed to .at least four mixer revolutions.
The detergent and cleaning composition granulate used in the context of the
process
disclosed hereunder can be rnanufactured in different ways and can contain
varying
amounts of the common ingrE>dients of detergents and cleaning agents_ The
granu-
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6
lar particles can be differently shaped depending on the production method,
nearly
spherical granulates often being referred to as pellets_
The range of possible granulation methods comprises, for example, wet
granulation,
dry granulation or grainulation on the basis of melt cooling, of which wet
granulation
represents the most a~mmon granulation method as it is subject to fewest
limitations
and with the greatest probability yields granulates with favourable
properties_ In the
context of this granulaition method, we distinguish between granulation
involving the
use of glue and granulation involving crust formation, and between granulation
by
building up and granulation by breaking down of substances. In the first case,
the
distinction depends vn wheither the powdery compounds to be granulated are
granulated with soluti~~ns of binding agents or glues on the one hand or with
pure
solvents or solvent mi;~ctures on the other. In the second case, the
distinction is made
between processes ~rrhere finer particles are combined into larger aggregates
or
larger units are comminuted into fine granulates.
Granulation can be p~srforme~d with different devices such as fluid bed
granulators,
fast and slow mixing ~aranulal:ors, roller type compactors, ring matrix
presses, pellet
presses and many others_ Extrusion, which can be used in the form of both wet
and
dry granulation, can also be applied for the production of the granulates used
in the
context of the method disclosed hereunder_
The granulates can bE: subjec:ted tv the known types of aftertreatment. A
drying step
may, in particular, be required after wet granulation, or the granular
partiGes can be
treated with a view to improving their surface characteristics, e.g_ by
applying a layer
of a finely pulverised ~;ubstanc:e to prevent granular partiGes from sticking
together.
The granulates can consist oil all ingredients commonly contained in
detergents and
cleaning composition:;_ This iincludes, in particular, builders and tensides,
but also
bleaching agents and bleach activators, enzymes, co-builders, foam inhibitors,
opti-
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7
cal brightening agents, phosphonates, polymers as well as colorants and
scents. In
the framework of the invention disclosed hereunder, a process is preferred
where
detergent and cleaning composition granulates manufactured in one of the known
ways contain tenside~(s), builders) as well as optional other ingredients
commonly
used in detergents and cleansing compositions.
The expert will encounter no~ difficulty at all in including individual
detergent and
cleaning composition ingredients in the course of granulate produckion or
during
mixing of the granulates with powdery upgrading components_ Depending on the
desired characteristics of the shaped units, it is therefore possible to
integrate the
detergent and cleaning composition ingredients into the shaped unit either via
the
granulate or via the powdery upgrading components. In this connection, it is
pre-
ferred to integrate deitergent ~2~nd cleaning composition ingredienfis that
could suffer
deterioration during the granulation process into the shaped unit via the
powdery
upgrading components.
In a preferred process. for the production of shaped detergent and cleaning
composi-
tion units, one or several substances from the group of tensides, tenside com-
pounds, builders, bleaching agents, bleach activators, enrymes, foam
inhibitors,
colorants and scents as well as binding agents and substances enhancing
disinte-
gration are added to the granulate in the form of a powdery upgrading
component.
Significant variations ~~re also possible as far as the quantities of
granulate and pow-
dery upgrading components are concerned. In the framework of the invention dis-
dosed hereunder, a process is preferred where 30 - 80, or preferably 40 - 75,
or
optimally 50 - 70 percent in weight of granulate and 20 - 70, or preferably 25
- 60, or
optimally 30 - 50 percent in v~reight of powdery components (all percentages
relating
to the quantity of the resuftin<,~ mixture to be subjected to tablet pressing)
are mixed
with each other and the mixture is, after addition of the final component and
during a
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g
sojourn time of 1 -30~D, or preferably 10 - 180, or optimally 20 - 120
seconds, ex-
posed to at least four mixer revolutions.
In order to make better use of existing granulation facilities or to use
existing types of
granulates, the detergent and cleaning composition granulate manufactured in
one
of the known ways aan also be composed of two or more separately manufactured
individual granulates. It is, for example, possible to combine a niotenside
zeolite
granulate with an anionic tens;ide silicate granulate and the powdery
upgrading com-
ponents without noting any reduction in quality whatsoever in comparison with
one
single granulate consiisting of all four components_ In the framework of the
present
invention, a process is preferred where the detergent and cleaning composition
granulate manufactunrd in one of the known ways consists of two or several
sepa-
rately manufactured granulates.
In order to achieve an even distribution of granulates) and powdery upgrading
com-
ponents, the mixture to be sulbjected to tablet pressing must be subjected to
at least
four mixer revolutions. The tinne required for these revolutions is
irrelevant. Both fast
high-intensity mixers and slower mixers can be used. The sojourn time of the
granulates must, irrespective of the type of mixer used, be less than 300
seconds.
The upper time limit beyond which a negative impact on the characteristics of
the
tablets will occur is ~~00 seconds even though granulates are subjected to
sign~-
cantly more revolutions in a fast than in a slow mixer. For economic reasons,
how-
' ever, it can be desirat~le to adlapt the sojourn times of the mixture to be
subjected to
tablet pressing in the mixer to the rotational speed of the device_ When using
slow
mixers with speeds between 10 and 250 r_p_m_, sojourn times of 1-300 seconds,
or
preferably 20 - 180 seconds, or optimally 30 - 150 seconds should be
preferred. In
the case of fast mixera with speeds between 250 and 3000 r.p.m., sojourn times
of 1
- 300 seconds, or preferably 2 - 180 seconds, or optimally 3 - 90 seconds are
reo-
ommended.
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In order to achieve an even distribution of components, the mixture of
granulates)
and powdery components must be thoroughly blended. For this purpose, at least
four mixer revolution; are required, though a higher number of revolutions can
be
useful from a process-engineering point of view_ In the framework of the
present ap-
plication, the terms "revolve" and "revolutions" refer to the minimum number
of re~
quired revolutions of the mixer shaft which, depending on the rotational speed
of the
device, creates more or less turbulence and carries along mere or less of the
prod-
uct. At a mixer spe~d of 40 r.p_m_, for instance, a minimum of four mixer
revolutions
means that the produ~;.t to be compressed must stay in the mixer for a minimum
pe-
riod of f seconds.
In the framework of the present invention, a process is preferred wherein the
mixture
of granulates) and powdery .components is subjected to at least four, or
preferably
at feast eight, or optimally at least ten mixer revolutions_
The actual production of the shaped units subject of the present invention
begins
with dry mixing of the granulate and the powdery components, followed by
shaping,
in particular tablet pressing, which can be performed by applying conventional
meth-
ods_ For the production of the shaped units covered by the present invention,
the
preliminary mixture i:: compressed, resulting in a solid compressed unit, in a
so-
called female mould located (between two dies. This process, hereinafter
simply re-
ferred to as tablet prEasing, consists of four stages: charging, compression
(elastic
deformation), plastic cteformaltion and ejection_
The first step consist'c of charging the mould with the preliminary mixture,
the quan-
tity of product filled irnto the mould and, thus, the weight of the resulting
shaped unit
being determined by t:he posit:ion of the lower die and the shape of the
pressing tool.
Constant charging even at high throughput rates is preferably achieved by
volumet-
ric apportioning of thc~ preliminary mixture. tn the further course of tablet
pressing,
the upper die touches the preliminary mixture and continues to move in the
direction
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of the lower die. During this compression process, the distances between the
indi-
vidual particles of the: preliminary mixture are reduced, the total volume of
hollow
space within the matE~rial between the two dies continuously decreasing.
Plastic de-
formation, in the course of wlhich the particles flow together and the shaped
unit is
created, occurs from a certain position of the upper die (and thus from a
certain
pressure exerted on -the preliminary mixture) onwards_ Depending on the
physical
characteristics of the preliminary mixture, part of the particles of the
preliminary
mixture is crushed and sintering of the preliminary mixture occurs as the
pressure
continues to increase. As the pressing speed increases, i.e. at high
throughput rates,
the elastic deformaticm phase is increasingly shortened, which means that the
re-
sulting shaped units can contaain smaller or larger hollow spaces. In the
course of the
last step of tablet pressing, the finished shaped unit is pushed out of the
mould by
the lower die and removed by subsequent conveying equipment_ At this moment,
only the weight of the shaped unit is finally determined, as the pressed units
can still
change their shape amd size as a consequence of physical processes (elastic re-
laxation, crystallographic effects, cooling, etc.).
Tablet pressing is performed in commercial tablets presses which can basically
be
equipped with single or double dies. In the latter case, pressure is exerted
not only
by the upper die, but the lower die also moves in the direction of the upper
die dur
ing the compression process while the upper die exerts pressure from above. Ec-
centric tablets presses where the dies) is/are mounted on an eccentric disc
that is
mounted on an axle with a cxrtain rotational speed should be preferred for
small
production volumes. 'the movement of these press dies can be compared with the
working method of a common four-stroke engine. Compression can be performed
with one upper and one lower die each, but is also possible to have several
dies
mounted on one eccentric disk, the number of die recesses in this case being
corre-
spondingly increased. Depending on the type of machine, the throughput rates
of
eccentric presses vary between several hundred to a maximum of 3000 tablets
per
hour.
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1~
Rotary tablet presses where as larger number of moulds is arranged in a circle
on a
press plate are used for larger throughput numbers. Depending on the type of
ma-
chine, the number of moulds; varies between 6 and 55, larger moulds also being
commercially available. An upper die and a lower die are allocated to each of
the
moulds on the press plate, active pressure being exerted by either the upper
or the
lower die alone or both dies at the same time. The press plate and the dies
move
around a common vertical axiis, rail-like curved guides serving to move the
dies into
the positions for filling, compacting, plastic deformation and ejection in the
course of
the . rotation_ Addition,~l holding-down pieces, lowering rails and lifting
guides are
used to support said .curved guides in places where particularly significant
lifting or
lowering of the dies is required (filling, compacting, ejectiony_ Filling of
the moulds is
performed by means of an immovable charging device, the so-called filling
shoe,
which is connected with a storage tank containing the preliminary mixture. The
pres-
sure exerted on the preliminary mixture can be individually adjusted by
modifying the
stroke lengths of the upper and lower dies, pressure being built up as the die
shaft
heads pass adjustable pressure rollers.
Rotary presses can be equipped with two filling shoes in order to increase
their
throughput rates, which means that. manufacturing of one tablet n~quires the
mould
to perform only half a rotation. For the production of shaped units consisting
of two
or more layers, several filling shoes are arranged one after the other in such
a way
that the first layer, being only slightly compacted, is not ejected prior to
further filling_
In this way, tablets with an outer enclosure or spherical insert that consist
of several
concentric layers can be produced by selecting a corresponding process design,
the
upper side of the corn= or core-layers remaining uncovered and, thus, visible
in the
case of tablets with a spherical insert. Rotary tablet presses can also be
equipped
with single or multiples tools :>o that it is, for example, possible to
simultaneously
compact material contained in an external circle of 54 and an internal circle
of 35
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recesses_ The throughput rate, of modern rotary tablet presses amount to more
than
one million of shaped units peer hour.
Tablet pressing machines suitable for application in the framework of the
present
invention are, for example, oflPered by the following companies_ Firmen
Apparatebau
Holzwarth GbR, Aspe,rg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil,
KILIAN, Cologne, KOI~AAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag
Maschinenbau AG, Bern (GH) and Courtoy N.V., Halle (BFJLU)_ A particularly
suit-
able machine is, for example, the hydraulic double press "Hydraulische Doppel-
druckpresse HPF $30" offered by the company l,AEIS, D_
The shaped units can be produced in a predetermined three-dimensional shape
and
a pre-determined sizE:_ The three-dimensional shape can be practically any
shape
with reasonable handling characteristics, which means that units can be shaped
as
stabs, sticks or bars, cubes, cuboids yr similar three-dimensional structures
with
plane lateral surfaces or, in p<~rticular, in the form of cylinder-shaped
elements with a
circular or oval cross sectian_ This latter design comprises all shapes
ranging from
tablets to compact cylinders wherein the ratio that the height bears to the
diameter
exceeds 1, particularly homogeneous distribution of density in the shaped
units be-
ing achieved where the ratio that the diameter bears to the height is
approximately
4.
The apportioned pressed unii;s can be designed as separate individual elements
of
which each contains i:he predletermined dose of the detergent and/or cleaning
com-
position_ However, it is also possible to produce pressed units that contain
several
times said dose, in which ca:>e the units should, in particular, be provided
with pre-
determined breaking lines allowing splitting of the unit into smaller units
each con-
taining a predeterminE:d dose of the product. For application of laundry
detergents in
washing machines of the type commonly used in Europe, i_e_ washing machines
equipped with a horizontally arranged mechanism, shaping of the apportioned
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pressed unifis in the form of tiablets, cylinders or cuboids can be
recommendable for
functional reasons, the diameter/height ratio preferably being in the range of
ap-
prox. 0.5 : 2 to 2 : 0.,5. Usual commercial hydraulic presses, eccentric
presses or
rotary presses are appropriate devices, in particular for the producfion of
such
pressed units.
The three~imensiona,l shape of a different type of shaped units is adapted, in
terms
of its dimensions, to the soap dispenser of usual commercial household washing
machines, thus allowing direct placing of the shaped units, without a dosing
device,
in the soap dispenser where they dissolve as water flows through the dispenser
into
the machine. It is, of course, also easily possible to use shaped detergent
units in
combination with a dosing device.
Another preferred type of shaped unit that can be manufactured is
characterised by
a slab or plate-like structure containing an alternating series of long thick
and short
thin segments, thus allowing individual segments to be broken off this "bar',
at the
predetermined breakang lines represented by the short thin segments, and put
into
the machine. The principle underlying the "bar-type" shaped detergent unit can
also
be translated into practice in the form of other geometric shapes such as
vertically
aligned triangles that ~~re only longitudinally connected at one of their
sides.
However, it is also possible to manufacture shaped units where the different
compo-
nents are not compacted into a homogeneous tablet but which are characterised
by
several layers, i.e. which comprise a minimum of iwo layers. In this
connection, it is
also possible to manufacture different layers that dissolve at different
speeds. This
can yield advantageous characteristics of the shaped units in terms of their
practical
application. If the sh;~ped units, for example, contain components that
negatively
influence each other, it is possible to integrate one of the components
concerned
into a layer that dissolfves faslter and the other into another layer that
dissolves more
slowly so that the fir:,t component has already exerted its effect when the
second
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14
begins to dissolve. The layers of the shaped units can be stacked, which means
that
dissolution of the internal laye~r(s) begins at the sides of the shaped unit
before com-
plete dissolution of the outer layers. Alternatively, it is also possible to
fully enGose
the inner layers) by the respective outer layer(s), which prevents premature
disso-
lution of components ~.ontaine~d in the inner layer(s).
In another preferred version of the invention, the shaped unit consists of at
least
three layers, i.e. two outer and at least one inner layer, whereof at least
one of the
inner layers contains ~~ peroxy bleaching agent while the top and bottom layer
of the
stack Type shaped unit and the outermost layers of the enclosure-type shaped
unit
are free from peroxy bleaching agent. Furthermore, it is also possible to
spatially
separate peroxy bleaching agents and bleach activators and/or enzymes, if any,
within a shaped unit_ Such multi-layered shaped units are characterised by the
fa-
vourable feature that they can not only be applied via a soap dispenser or a
dosing
device put amidst thE~ laundr~~. Instead, it is in such cases also possible to
put the
shaped unit into the Hrashing machine in direct contact with the laundry
without risk-
ing staining of fabrics by bleal:hing agents or similar damage.
Similar efFects can al;~o be achieved by coating individual components of the
deter
gent and cleaning composition to be compressed or the entire shaped unit,
respeo-
tively. For this purpose, the elements to be coated can, for example, be
sprayed with
aqueous .solutions or emulsions or be subjected to melt film coating.
After compression, the shaped detergent and cleaning composition units are
char
acterised by great stability. T'he resistance to breaking of cylindrical
shaped units
can be expressed by using the diametral fracture stress value. This value is
calcu-
lated using the following formula=
2P
ai -
nDr
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1s
In this formula, a stands for t;he diametral fracture stress (DFS) indicated
in Pa_ P
stands for the force N resuliting in the pressure exerted on the shaped unit
that
causes breaking of the shapE:d unit. D is the diameter of the shaped units
indicated
in meters, and t the height of the shaped units.
In preferred variation:; of the: process disclosed hereunder, the mixture of
granu-
lates) and powdery upgrading components to be compacted is subjected to com-
paction at a pressure of 10 ~- 150 N/cm2, or preferably 15 - 100 N/cm2~ or
optimally
20 - 100 N/cm~~ and .a temperature of 10 - 80°C, or preferably 15 -
70°C, or opti-
orally 20 - 60°C_
The following section ~:ontains; a brief description of the most important
ingredients of
shaped detergent and cleaning composition units which can, in the context of
the
process disclosed hereunder, be contained in the granulates or in the powdery
up-
grading componenfis_ The granular components of the mixture tv be compacted
are
manufactured in one ~of the familiar ways and one of the familiar
compositions, the
selection of ingredients always depending on the desired purpose of the shaped
units.
For the shaped detergent and leaning composition units disclosed hereunder, it
is
possible to use anionic; non-ionic, cationic and/or amphoteric tensides_ From
an ap-
plicativn-related point of view, mixtures of anionic and non-ionic tensides
where the
share of anionic tensides should exceed the share of non-ionic tensides are
prefer
able. The total tensidn content of the shaped units amounts to 5 - 60 percent
in
weight in relation to the weight of the shaped unit, tensile contents
exceeding 15
percent in weight being preferred.
Examples for possible anionic tensides are sulphonate-type or the sulphate-
type
tensides_ Preferable :;ulphonate-type tensides are C~.,a-alkylbenzene
sulphonate,
olefin sulphonates, i.e:. mixtures of alkene sulphonates and hydroxyalkene
sulpho-
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16
pates as well as disul~~honates of the type produced from C~2_~e-monoolefins
with a
terminal or internal double bond by sulphonation with gaseous sulphur trioxide
and
subsequent alkaline or acid hydrolysis of the sulphonation products_ Further
suitable
substances are alkane sulphonates produced from Ct2-~a-alkanes, for examples,
through sulphochlorination or sulphoxidation with subsequent hydrolysis or
neutrali-
sation, respectively_ E=stars of a-sulphonic fatty acids (ester sulphonates)
such as
a-sulphvnated methyl esters of hydrated coconut, palm kernel or tallow fatty
acids_
Further suitable anionic tensides are represented by sulphurised fatty acid
glycerine
esters. Fatty acid glycerine esters are monoesters, diesters and triesters as
well as
compounds then~f of the type produced through esterification of one
monoglycerine
with 1 to '3 mol of father acid or transesterification of triglycerides with
0.3 to 2 mol of
glycerine. Preferred :~ulphurised fatty acid glycerine esters are the
sulphurisation
products of saturated fatty acids with 6 - 22 carbon atoms such as caproic
acid, cap-
rylic acid, capric acid, myristic: acid, lauric acid, palrnitic acid, stearic
acid or behenic
acid _
Among the alk(en)yl sulphates, preference is given to alkali and, in
particular, so-
dium salts of sulphuric acid semi-esters of C,z-C~8-fatty alcohols, e.g. of
coconut
fatty alcohol, tallow fatty alGOhol, (auryl alcohol, myristy) alcohol, cetyl
alcohol or
stearyl alcohol, or of n~o-C2o~oxo-alcohvls and semi-esters of secondary
aloohols of
the same chain lengtlhs_ Additional preferred substances are alk(en)yl
sulphates of
the chain lengths indicated above which contain a synthetic straight-chain
alkyl rest
manufactured on a petrochemical basis and are characterised by similar
degradation
behaviour as the adequate compounds on the basis of fat-chemical raw
materials.
From the point of viev~r of washing, preference is given to C~rC~s-alkyl
sulphates and
C~Z-C,5-alkyl sulphates as well as C~6-C~5-alkyl sulphates. 2,3-alkyl
sulphates that
can be manufactured, for example, according to the US patents 3,234,258 or
5,075,04.1 and are supplied bay the Shell Oil Company under the name DAN~ also
represent suitable anionic tensides.
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Sulphuric acid monoe~sters of straight-chained or branched-chain C~_z,-
2tlcohols eth-
oxylated with 1 - 6 mil of ethylene oxide such as 2-methyl-branched C~~~-
alcohols
with an average of 3..5 mol of ethylene oxide (EO) or C~Z.~e-fatty alcohols
with 1 - 4
EO are suitable_ Because they give rise to signficant foam development, they
are
only used in relatively small amounts in cleaning compositions, e.g. in
quantities of 1
- 5 percent in weight.
Further suitable anionic tensides are represented by the salts of alkyl
suiphonic suc-
cinic acid which are rilso called sulphonic succinates or sulphonic succinic
acid es-
ters and are monoesters andJar diesters of sulphonic succinic acid with
aleohols, or
preferably fatty alcohols, or optimally, ethoxylated fatty alcohols_ The
preferred sut-
phonic succinates contain a C~~8-fatty alcohol rests or mixtures of the
latter. The
particularly preferred sulphonic succinates contain a fatty alcohol rest
derived from
ethoxylated fatty alcohols which by themselves represent non-ionic tensides
(see
description below). In this connection, particular preference is given to
sulphonic
succinates with fatty alcohol rests derived from ethoxylated fatty alcohols
with a nor
rowed distribution of homolocaues_ It is also possible to use alk(en)yl
succinic acid
with preferably 8 --18 carbon atoms in the alk(en)yl chain or its salts.
Further suitable anionic tensides are, in particular, soaps. Suitable soaps
are satu-
rated fatty acid soaps such as the salts of lauric acid, myristic acid,
palmitic acid and
stearic acid, hydratedl erucic acid and behenic acid as well as mixtures of
different
soaps derived from natural faitty acids, e_g_ coconut, palm kernel or tallow
fatty acids.
Anionic tensides including soaps can be used in the farm of their sodium,
potassium
or ammonium salts a:~ well as in the form of soluble salts of organic bases
such as
mono-, di- or triethanolamine. Anionic tensides should preferably be used in
the farm
of their sodium or pot~3ssium salts or, optimally, in the form of their sodium
salts_
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1s
Where preliminary mixtures ~~ontaining fatty alcohol sulphates as anionic
tensides
are manufactured in the framework of the process disclosed hereunder, fatty
alcohol
sulphates should prelPerably be integrated into the preliminary mixture to be
com-
pressed via the povvdery upgrading components. Preference is, in this respect,
given to the use of faitty alcohol sulphate compounds with an active substance
con-
tent of at least 30 percent in weight. The process disclosed hereunder yields
par-
ticularly favourable si- aped units when the powdery component containing the
fatty
alcohol sulphate is added to i:he product in the mixer as the very last
ingredient and
when mixing times below 3 minutes ace observed after addition of the fatty
alcohol
sulphate compound.
A preferred process is, therefore, one where the last powdery upgrading
component
added during the mixing process is a tensile compound containing at least 30
per-
cent in weight (in rel~~tiori to the tensile compound) of fatty alcohol
sulphate and
where the mixture is" after addition of the fatty alcohol sulphate compound,
sub-
jected to at feast four mixer rE:volutions during a sojourn time in the mixer
of 1 - 180
seconds, or preferable: 10 - 1.50 seconds, or optimally 20 - 120 seconds.
Furthermore, it is also possible to integrate finely pulverised components
into the
process disclosed hereunder which stick to the surface of the granulates) and
the
other powdery upgrading components and serve to envelope these in a fine coat
of
powder. The advantage of adding this "coating powder" consists in the fact
that it
minimises or totally prevents ithe material to be compressed from sticking to
the dies
during the subsequent compression process. The substances suitable to be used
as
such finely pulverised coating powders include, for example, the builders
described
below, zeolites and, erspecially the zeolite X described in detail below being
particu-
larly suitable. In a further preferred process, a tensile compound containing
at least
30 percent in weight (in relation to the tensile compound) of fatty alcohol
sulphate
as well as zeolite X are added as powdery upgrading components. In this case,
zeo-
tits X should preferably be added as the very last component, and the mixture
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19
should, after addition of zeolite X, be subjected to at least four mixer
rotations dur-
ing a sojourn time in the mixer of 1 - 180 seconds, or preferably 10 - 150
seconds,
or optimally 20 -120 aeconds..
The quantify of anionic tensile integrated into the shaped units via the
preliminary
mixture amounfis, for example, to between 5 and 60 percent in weight. The
anionic
tensides should, however, preferably not be used alone but mixed with non-
ionic
tensides, the total content of anionic tensides in the shaped units in this
case
amounting to between 5 and ~f0 or, preferably, between 5 and 30 percent in
weight.
In the framework of another preferred process, a fatty alcohol sulphate
compound is
added in the form of a powdery upgrading component in such a quanfrty that the
compound to be Gompressed~ contains at least 2 percent in weight, or
preferably at
least 4 percent in wei~~ht, or optimally more than 5 percent in weight of
fatty alcohol
sulphate.
The non-ionic tensides preferably used are alkoxylated, or preferably
ethoxylated, or
optimally primary alco~hols with preferably 8 to 18 carbon atoms and an
average of 1
to 12 mot of ethylene oxide (I=O) per mot of alcohol in which the alcohol rest
can be
linear or, preferably, methyll-branched in the 2-position or can contain
methyl-
branched rests in the mixturE: of the kind commonly contained in oxo-alcohol
rests.
Particular preference, however, is given to alcohol ethoxylates with linear
rests from
alcohols of native origin with 12 to 18 carbon atoms, e.g. from coconut, palm
or tal-
low fatty alcohol or ol',eyl alcohol, and an average of 2 to 8 EO per mot of
alcohol
The preferred ethoxylated alc:ohols comprise, for example, C~2_~4-alcohols
with 3 EO
or 4 EO, C~»-alcohol with 7 E-O, C~3~5-alcohols with 3 EO, 5 EO, 7 EO or 8 EO,
C~2_
,$-alcohols with 3 EO" 5 EO or 7 EO and mixtures thereof, such as mixtures of
C~2_
~a-alcohol with 3 EO ~~nd C,2..~8-alcohol with 5 EO. The indicated
ethoxylation levels
represent statistical average values that can be a whole or a fractional
number for a
specifc product. The preferrerd alcohol ethoxylates are characterised by a
narrowed
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ao
distribution of homologues (narrow range ethoxylates, NRE)_ In addition to
these
non--ionic tensides, it is also possible to use fatty alcohols with more than
12 EO, for
example tallow fatty allcohol with 14 EO, 25 EO, 30 EO or 40 EO_
Additionally, alkyl glycosides of the general formula RO(G)x can be used as
further
non-ionic tensides, R s,taoding for a primary aliphatic rest with $ to 22 or,
preferably,
12 to 18 carbon atoms that is straight-chained or methyl-branched or, in
particular,
methyl-branched in the 2-posiition, while G is the symbol representing a
glycose unit
with 5 or 6 carbon atoms, pre=ferably glucose. The level of oligomerisation x,
which
indicates the distribution of rnonoglycosides and oligoglycosides, is any
desirable
number between 1 arnd 10, preferably in the range between 1 _2 and 4.
Another class of preferably used non-ionic tensides, which are applied either
as the
sole non-ionic tenside~ or in combination with ether non-ionic tensides;
consists of
alkoxylated or, preferably, ethoxylated or ethoxylated and propoxylated fatty
acid
alkyl esters, preferably with 1 - 4 carbon atoms in the alkyl chain, in
particular fatty
acid methyl esters of the type described, for example, in the Japanese patent
appli-
cation JP 58/217598 ~~r preferably manufactured applying the process described
in
the international patent application WO-A-90/13533.
Non-ionic tensides of the aminoxide type such as N-coconut-alkyl-N,N-
dimethylaminoxide and N-tallow-alkyl-N,N~iihydroxyethylaminoxide, and of the
fatty
acid 2~Ikanolamide type can ailso, be adequate. The quantity of these non-
ionic ten-
sides should preferably amount to not more than the quantity of ethoxylated
fatty
aicohols or, optimally, to not more than half thereof_
Additional suitable tensides are polyhydroxy fatty acid amides composed
according
to fom~u[a (1),
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R1
R-CO-N-[ZJ (I)
where RCO represents an aliphatic acyl rest with 6 to 22 carbon atoms, R1
hydro-
gen, an alkyl or hydn~xyafkyl rest with 1 to 4 carbon atoms and a [Z] a linear
or
branched polyhydroxyalkyl resst with 3 to 10 carbon atoms and 3 to 10 hydroxyl
groups. Polyhydroxy fatty aciid amides are known substances that can normally
be
produced through reductive amination of a reducing sugar with ammonia, an
alkyl
amine or an alkanolamine and subsequend acylation with a fatty acid, a fatty
acid
alkyl ester or a fatty acid chlvride_
The group of the polyhodroxy fatty acid amides also comprises substances com-
posed according to formula (II),
R ~-O-R2
R-CO-N-[Z] (I I)
where R represents a linear or branched alkyl or alkenyl rest with 7 td 12
carbon at-
oms, R~ a linear, branched or cyclical alkyl rest or an aryl rest with 2 to 8
carbon at-
oms and RZ a linear, branched or cyclical alkyl rest or an aryl rest or an oxy-
alkyl
rest with 1 to $ carbon atoms., preference being given to C~.~-alkyl or phenyl
rests,
and [Z] stands for a linear polyhydroxy alkyl rest with an alkyl chain
substituted
with at least two hydrnxyl groups or alkoxylated or, preferably, ethoxylated
and pro-
poxylated derivatives of said rest_
[ZJ is preferably produced through reductive amination of a reducing sugar
such as
glucose, fructose, malltose, lactose, galadose, mannose or xylose_ The N-
alkoxy or
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22
N-aryloxy-sustituted compounds can then, for example, be converted into the de-
sired polyhydroxy fathy acid amides through reaction with fatty acid methyl
esters in
the presence of an alkoxide functioning as a catalyst according to the
international
application WO-A-95/07331.
Among the substances eligible as builders, which can be contained in the
shaped
detergent and cleaning composition units covered by the invention, silicates,
alu-
minium silicates (in p~articulair zeolites), carbonates, salts or organic
dicarbon and
polycarbon acids as vvell as rnixtures of the mentioned substances deserve
particu-
lar mention.
Appropriate crystalline:, strat~ed sodium silicates are defined by the general
formula
NaMSixO~~~H20, wherein M :>tands for sodium or hydrogen, x for a number
between
1 _9 and 4 and y for a number between 0 and 20, x values of 2, 3 or 4 being
prefer-
able Crystalline stratified silicates of this type are, for example, described
in the
European patent application EP-A-0 164 514. Preference is given to crystalline
stratfied silicates of the indicated formula where M stands for sodium and x
for a
value of 2 or 3_ Particular preference is given to both t3- and s-sodium
disilicates
Na2Si205yH20, whereof f~so~dium disilicate can, fvr example, be produced
through
application of the process described in the international patent application
WO-A-
91108171.
It is also possible to use amorphous sodium silicates with a modul Na20 : SiOz
be-
tween 1.2 and 1:3_3, or preferably between 1:2 and 1:2.8, or optimally between
1:2
and 1:2.6, that are characterised by delayed dissolution and secondary washing
properties. Delayed dissolution in comparison with conventional amorphous
sodium
silicates can be a result of different procedures such as surface treatment,
com-
pounding, compactincl/compressing or drying. In the framewortc of the present
inven-
tion, the term "amorphous" also signifies "X-ray-crystallographically
amorphous".
This means that silicates subjected to X-ray diffraction experiments do not
yield
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23
sharply defined X-ray reflexes. of the type typical of crystalline substances
but, if any,
one or several maximums of the diffracted X-rays with a width of several
degree
units of the diffraction angle. (However, it is definitely possible to achieve
particularly
good builder properties where silicate partiGes yield blurred or even sharply
defined
diffraction maximums in the context of X-ray diffraction experiments. This
must be
interpreted in the sen:~e that i;he products contain micro-crystalline areas
measuring
between 10 and several hundred nm, preference being given to values of up to
50
nm and, in particular, of up to 20 nm. Such so-called "X-ray-
crystallographically
amorphous" silicates, which .are also characterised by delayed dissolution in
com-
parison with normal mater glass, are, for example, described in the German
patent
application DE-A- 44 00 024_ Preference is, in particular, given to com-
pacted/compressed amorphous silicates, compounded amorphous silicates and
dried X-ray-crystallographically amorphous silicates.
The fine--crystalline, synthetic zeolite containing bound water that is
applied should
preferably be zeolite i~ and/or P. The particularly preferred zeolite P is
Zeolith MAP~
(commercial product ~>upplied by the company Crosfield). However, it is also
possi-
ble to use zeolite X a:: well a~~ mixtures of A, X and/or P_ A co-
crystallisate of zeolite
X and zeolite A (contauning approximately 80 percent in weight of zeolite X),
which is
distributed by the ca~mpany CONDEA Augusta S.p.A under the trade name
VEGOBOND AXE' and defined by the formula below, is also commercially available
and applicable in the framework of the process covered by the present
invention.
nNa20 ~ (1-n)K~~O ' AIZ03 - (2 - 2,5)Si02 ~ (3,5 - 5,5) Ha0
Zeolite can be used as a spray-dried powder or in the form of an undried,
stabilised
suspension that still ~~ntain:: the humidity gained during the production
process.
Where zeolite is usedl in the Form of the suspension, it is possible that the
suspen-
sion contains small arnounts of non-ionic tensides as stabilisers, e_g_
between 1 and
3 percent in weight (nn relation to the zeolite) of ethoxylated C1z-C,$ fatty
alcohols
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24
with 2 to 5 ethylene oxide groups, C~Z-C~4-fatty alcohols with 4 to 5 ethylene
oxide
groups or ethyloxated isotridecyl alcohols_ Appropriate zeolites have an
average
particle size below i C~ ~m (volume distribution; measuring method: Coulter
Counter)
and contain preferably betwecsn 18 and 22, or optimally between 20 and 22
percent
in weight of bound water.
Of course it is also possible to use the generally familiar phosphates as
builders
unless the application of this substance type should preferably be avoided for
eco-
logical reasons. Partinularly appropriate are the sodium salts of
orthophosphates,
pyrophosphates and, tin particular, tripolyphosphates_
Appropriate organic guilders are, for example, polycarf~on acids such dtric
acid,
adipic acid, succinic ~~cid, glutaric acid, tartaric acid, saccharic acids,
amino carbon
acids or nitrilotriacetic acid (IOTA) that can be used in the form of their
sodium salts
unless such applicati~an is objected to for ecological reasons as well as
mixtures
thereof. Preferred salts are thie salts of polycarbon acids such as citric
acid, adipic
acid, succinic acid, gt~utaric acid, tartaric acid, saccharie acids and
mixtures thereof.
These salts are used due to their builder characteristics and must not be
considered
as part of the gas de~relopme~nt system as the salts are not able to release,
for ex-
ample, carbon dioxides out of hydrocarbonates.
Among the compounds serving as bleaching agents that yield H202 when dissolved
in water, particular importance is attached to sodium perbor-ate tetrahydrate
and so-
diem perborate monohydrate. Additional substances that can be used as
bleaching
agents are, for examble, sodium percarbonate, peroxypyrophosphate, citrate
perhy-
drate as well as peracidic salts or peracids yielding H202 such as
perbenzoate, per
oxophthalate, diperaz~elaic aciid, pthaloiminoperic acid or diperdodecan
diacid.
In order to achieve an improved bleaching effect at washing temperatures of 60
°C
and below, it is possible to integrate bleach activators into the shaped
detergent and
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leaning composition unrts_ Substances that can be used as bleach activators
are
compounds that, in perhydrolytic conditions, yield peroxocarbon acids with
pref
erably 1 to 10 carbon atoms or, in particular, 2 to 4 carbon atoms and/or
substituted
perbenzoic acid, if apF~licable. Suitable substances bear O and/or N-acyl
groups with
the number of carbon atoms indicated above and/or substituted benzoyl groups,
if
applicable. Preference: is given to multiply acylated alkylene diamines such
as, in
particular, tetraaceiyl ~ethylenE: diamene (TAED), acylated tnazine
derivatives such
as, in particular, 1,5~diacetyl~-2,4-dioxvhexahydro-1,3,5 triazine (DADHT),
acylated
glykouriles such as, in particular, tetraacetylglykolurile (TAGU),
N..acylimides such
as, in particular, N-nc~nanoyls~uccinimide (NOSI), acylated phenolsulphonates
such
as, in particular, n-nonanoyl- or isononanoyloxybenzolsulphonate (n- or iso-
NOBS,
respectively), carbon acid anhydrides such as, in particular, phthalic acid
anhydride,
acylated polyhydric alc:ohols such as, in particular, triacetine,
ethylenglykoldiacetate
and 2,5-diacetoxy-2,5-~dihydro~furane.
In addition to the conventional) bleach activators or instead of such, it is
also possible
to integrate so-called bleach catalysts into the shaped units_ These are
bleach-
enhancing transitional metal salts or transitional metal complexes,
respectively, such
as Mn, Fe, Co, Ru or Mo salene complexes or carbonyl complexes. Mn, Fe, Co,
Ru,
Mo, Ti, V and Cu complexes ~nrith nitrogen~containing tripod ligands as well
as a Co,
Fe, Cu and Ru amine complexes can also be used as bleach catalysts.
Possible foam inhibitors, which can be part of component b) or altogether make
up
component b), are, for example, soaps of natural or synthetic origin with a
high con-
tent of C~8_zd-fatty acids. Appropriate non-tensidic foam inhibitors are, for
example,
organopolysilvxanes and mixtures thereof with microfine, possibly silanated
silicic
acid or bistearylethylene diamide. Advantages are also offered by mixtures of
differ-
ent foam inhibitors, e.g_ mixtures of silicones, paraffines or waxes. Foam
inhibitors
should preferably be hound to a granular, water soluble or in water
dispersible car
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26
rier substance. Preference in this respect is given to mixtures of parafFnes
and
bistearylethylene dian-iides_
In addition, shaped deetergent and cleaning composition units can also contain
com-
ponents that facilitate the removal of oil and grease from textile materials
(so-called
soil repellents). This effect becomes especially apparent when a textile
material pre-
viously washed several times. with a detergent of the type covered by the
present
invention that contain: this oil and grease solving component is soiled. The
preferred
oil and grease-solving components comprise, for example, non-ionic cellulose
ethers
such as methyl cellulose methylhydroxy-propylcellulose with a share of
methoxyl
groups amounting to 15 to 3.0 percent in weight and a share of hydroxypropoxyl
groups amounting to 7 to 15 percent in weight (both in relation to the non-
ionic cel-
lulose ether) as well a,s the polymers of phthalic acid and/or terephthalic
acid or de-
rivatives thereof described in prior art, in particular polymers of ethylene
terephtha-
lates and/or polyethylene glyc:olterephthalates or anionic and/or non-ionic
modified
derivatives thereof. Particular preference in this respect is given to
sulphonated de-
rivatives of phthalic arid and i:erephthalic acid polymers.
The range of enzyme: that can be used contains enrymes from the class of
prote'
ases, lipases, amylasE~s, cellulases or mixtures thereof. Enzymatic agents
produced
from bacteria strains or fungi such as Bacillus subtilis, Bacillus
licheniformis and
Streptomyces griseus are pari:icularly suited. Preference is given to
proteases of the
subtilisine-type and, in particular, to proteases produced from Bacillus
lentus. Of
particular interest in this respect are mixtures of enzymes such as mixtures
of prote-
ase and amylase or protease and lipase or protease and cellufase or cellulase
and
lipase or protease, amylase and lipase or protease, lipase and cellulase, but
in par-
ticular cellulose-containing mixtures_ Peroxidases and oxidases also proved
appro-
priate in several casca_ The enzymes can be adsorbed onto carrier substances
and/or be embedded in enclosing substances in order to protect them against
pre-
mature disintegration. The share of enzymes, mixtures of enzymes or enzyme
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27
granulates in the shaped unih> produced according to the present invention
can, for
example, amount to about 0.1 to 5 or, preferably, to 0_1 to about 2 percent in
weight.
As optical brightening agents, it is possible to integrate into the shaped
units deriva-
tives of diaminostilbendisulphonic acid or the alkali metal salts thereof.
Suitable sub-
stanees in this respect are, 'for example, salts of 4,4'-bis(2-anitino-~-
morphofino-
1,3,rtriazinyl-6-amine)stilben~-2,2'-disulphonic acid or similarly composed
com-
pounds which bear a <~iethanol amino group, a methyl amino group, an anilino
group
or a 2-methoxy ethlyamino group instead of the. morpholino group.
Additionally,
brightening agents frcrm the :>ubstituted Biphenyl styryle type can be present
such
as, for example, the allkali salts of 4,4'-bis(2-sulphostyryl~diphenyl, 4,4'-
bis(4-chlor-3-
sulphostyryl)~iphenyl, or 4-(4-chlorine styryl)-4.'-(2-sulphostyryl)-Biphenyl.
Further-
more, it is also possiblle to use' mixtures of the above-mentioned brightening
agents..
Colorants and scents are added to the products covered by the present
invention in
order to improve the aesthetic: impression created by the products and to
provide the
buyer with a product that performs not only a washing and cleaning function
but is
also "typical and unmistakable" in terms of its optical and sensory
characteristics.
The perfume oils or scents, respectively, can consist of various compounds of
odor-
iferous substances such as, ifor example, synthetic products of the ester,
ether, al-
dehyde, ketone, alcohol or hydrocarbon type. Ester-type compounds of
odoriferous
substances ace, for example benzyl acetate, phenoxyethyl isobutyrate, p tert_-
butylcyclohexyl acetate, linahyl acetat, dimethylbenzylcarbinyl acetate,
phenylethyl
acetate, linalyl benzoate, benzyl formiate, ethylmethylphenyl glycinate,
allylcyclo-
hexyl propionate, styiallyl propionate and benzyl salicylate_ The ether group
com-
prises, for example, benZylethyl ether and the aldehyd group linear alkanales
with 8
to 18 carbon atoms c:itral, citronellal, citronellyloxyacetaldehyde,
cyclamenaldehyde,
hydroxycitronellal, lili2il and b~ourgeonal_ The ketone group comprises, for
example,
jonones, ~-isomethyl ionone and methylcedryl ketone, the alcohol group
anethol,
citronellol, eugenol, g~er-aniol, linalool, phenylethyl alcohol and terpineol,
and the hy-
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drocarbon group mainly the te:rpenes such as limonen and pinen. Preference,
how-
ever, is given to mixtuires of different odoriferous substances which together
result in
an attractive scent. Such perfi.ime oils can, of course, contain mixtures of
odoriferous
substances of the type' produced from plants such as, for example, pine,
citrus, jas-
mine, patchouli, rose or ylang~~ylang oil_ Further possible substances are
muscatefler
oil, salvia oil, camomile oil, cloves oil, melissa oil, mint oil, cinnamon
leaf oil, tilia oil,
juniper berry oil, vetivE:r oil, olibanum oil, galbanum oil and labdanum oil
as well as
orange blossom oil, n~~roli oil, .orange peel oil and sandalwood oil_
The content of colorants contained in the shaped units covered by the present
in-
vention is normally 0_01 in weight while scents can amount to up to 2 percent
in
weight of the entire formula.
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Example:
In order to produce dletergen~t tablets, a detergent granulate (composition as
indi-
cated in table 1) was filled ini;o different types of mixers, sprayed with
perfume and
subsequently mixed with the upgrading components indicated in table 2. Prior
to
tablet pressing, 4 percent in weight of cellulose (disintegration enhancing
agent) and
1 percent in weight of zeolil:e (coating powder component) were mixed with the
preparation (all percE:ntages indicated in relation to the weight of the
resulting
shaped unit). The compound was mixed for respective total mixing times of 30
seG
onds and 3 minutes in each of three different mixer types- The results
summarised in
table 3 show that detergent tablets manufactured from the preliminary mixture
that
was mixed longer took significantly longer to disintegrate in spite of much
"softer'
compression.
Table 1: Composition of the tenside granulate [percent in weight]:
C,3alkylb~enzol sulphonate - 22_0
C,z_,$-fatty alcohol with 7 EO 6_2
Soap 1.6
Zeolite A 31.3
Sodium carbonate 18.8
Sodium silicate 5.5
Acrylic acid - malefic acid copolymer5.5
Optical brilahteninc,~ agent 0_3
Salts / water Rest
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Table 2: Composition of the ~~haped detergent and cleaning composition units
[per-
cent in weight]:
Tenside grianulate 65.2
Pertume 0.5
Sodium peeborate 16.0
Tetraacetylethylene diamine (TAED)7.3
Foam inhibitor 3.5
Enzymes 2.5
Cellulose 4.0
Zeolite A or zeolite X 1 _0
Salts/water Rest
The hardness of the tablets was measured through deformation of the tablet
until
breaking, the force at;ting on the lateral surfaces of the tablet as well as
the maxi-
mum force sustained by the tablet being determined.
For the determination of tablet disintegration, the tablet was placed in a
beaker glass
of water (600 ml water, temperature 30°C) and the time until complete
disintegration
pf the tablet without mechanic, intervention was measured.
Table 3 contains a summary of the corresponding experimental data.
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Table 3: Detergent tatrlets [physical specifications]
Tablet Example Example Example Example Example Example
1 1 2 2 3 3
Mixing time 30 sec 6 min 30 sec 6 min 30 sec 6 min
Tablet hardness30 N 20 N 30 N 20 N 30 N 20 N
Tablet disintegra-< 30 > 60 < 30 > 60 < 30 > 60
tion sec sec sec sec sec sec
Example 1: Lodige FM 130 C1, Gebruder Lbdige Maschinenbau, D (blade mixer)
Example 2- Bolz Surnmiz ML 003, Fa_ Helpman Verfahrenstechnik, Wangen, D
(conical :>piral mixer)
Example 3: Pegasus PG 120, Fa. Dinnissen, Sevenum, NL (paddle mixer)
In the course of several further series of experiments, detergent tablets
containing
fatty alcohol sulphate were produced, fatty alcohol sulphate (FAS) in some of
the
experiments being added at tlhe very end in the form of a powdery upgrading
com-
ponent while zeolite X was in other cases added to the compound in the mixer
as a
coating powder after addition of powdery FAS. In another experiment. FAS was
added in the form of a granulate.
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Table 4: Composition of the shaped detergent and cleaning composition units
(ex-
ample 4) [percent in weight]=
Tenside gr<;nulate 60_5
Perfume 0_5
Sodium perborate 16.0
Tetraacetylethylene diamine (TAED)7.3
Foam inhibitor 3_5
Enaymes 2_5
Cellulose 4.0
Zeolite A or zeolite X 1.0
C~Z_~$-fatty alcohol sulphate, 4_7
96%~
Salts / watesr Rest
': Fatty alcohol sulphate compound with 96% active substance,
2°l° sodium carbon-
ate and 2% water
In this example, the fatty alcohol sulphate compound was added as the last com-
ponent and the product was mixed in a Lodige FM 130 D mixer. The mixing times
after addition of the FAS wE:re measured, and the physical specifications of
the
shaped detergent and cleaning composition units after compression were deter-
mined. The experimental data is summarised in table 6.
In a further example, 1 percent in weight of zeolite X was added as a coating
pow-
der after addition of 3.8 percent in weight of the FAS compound used in
example 4,
and the mixing was pe:rformedl in a L~dige FM 130 D mixer. The mixing times
after
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addition of zeolite X were measured, and the physical specifications of the
shaped
detergent and cleaning composition units after compression were determined.
The
experimental data is summari,~ed in table C_
FAS can, in the framework of the present invention, also be used in the farm
of a
tenside granulate. For this purpose, the tenside granulate used in example 6
was
modified as follows. Instead of 6.2 percent in weight of C~2_~~-fatty alcohol
with 7
EO, a quantity of 3.2 percent in weight of 96% FAS compound and 3_0 percent in
weight of C~2_~$-fatty alcohol with 7 EO were used. This granulate was mixed
with
the other components in a L~~dige FM 130 D mixer, the mixing time after
addition of
zeolite X (last component, coating powder) being measured_ The composition of
the
shaped detergent and cleaning composition units is indicated in table 5, the
physical
specifications of the shaped detergent and cleaning composition units of
examples
4, 5 and 6 are summarised in table 6_
Table 5: Composition of the :>haped detergent and cleaning composition units
(ex-
ample 6) [percent in w~aight]:
Tenside granulate= 64..5
Perfume 0_45
Sodium perborate 16.0
Tetr-yaacetyl~ethyfenE: diamine 7.3
(TAED)
Foam inhibitor 3.5
Enzymes 2.5
Cellulose 4.0
Zeolite X 2_0
Salts I water Rest
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As indicated in table 1 containing 3.2 percent in weight of 9C% FAS compound
and 3.0 percent in weight of (~~z_~$-fatty alcohol with 7 EO instead of 62
percent in
weight of C~2.~$-fatty allcohol with 7 EO_
Table 6: Detergent tat~lets [physical specifications]
Tablet (ExampleExample Example Example Example Example
4 4 5 5 6 G
Mixing time 5 sec 360 sec 120 sec 450 sec 180 sec 480 sec
Tablet hardness33 N 31 N 34 N 33 N 35 N 34 N
Tablet disintegra-25 sec ~ 60 15 sec > 60 20 set > 60
tion sec sec sec
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