CA2305563A1 - Method for the production of stable and rapidly disintegrating shaped detergent units - Google Patents

Abstract

The present invention relates to a process for the production of shaped detergent and cleaning composition units through compression of a particulate detergent and cleaning composition that can be produced through mixing of a detergent and cleaning composition granulate manufactured in one of the known ways with powdery upgrading components. Particularly stable shaped units that stand out for short disintegration times can be produced by mixing the granulate with the powdery upgrading components in a mixer and subjecting the mixture, after addition of the last component, to at least four mixer rotations during a sojourn time in the mixer of 1-300 seconds.

Description

MAY-12-A0 1B:11 FROM=SWABEY OGILVY RENAULT ID: PAGE 8/44 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-05/12/00 FRI 17:07 (TX/RX NO 8990] 0 008 MAY-12-00 1B=11 FROM=SWABEY OGILVY RENAULT ID= PAGE 9/44 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-05/12/00 FRI 17:07 ITX/RX NO 8990] f~009 MAY-12-00 1B=12 FROM:SWABEY OGILVY RENAULT ID: PAGE 10/44 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 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 05/12/00 FRI 17:07 ITX/RX NO 8990] f~010 MAY-12-00 1A:12 FROM:~WABEY OGILVY RENAULT ID: PAGE 11/44 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.
05/12/00 FRI 17:07 [TX/RX NO 8990] [X011 MAY-12-00 18:13 FROM:SWABEY OGILVY RENAULT Ice: PAGE 12/44 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-05/12/00 FRI 17:07 ITX/RX NO 8990] f~]012 MAY-12-00 1B=13 FROM-SWABEY OGILVY RENAULT ID: PAGE 13/44 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-05/12/00 FRI 17:07 [TX/RX NO 8990] f~013 MAY-12-00 1A:14 FROM:SWABEY OGILVY RENAULT ID: PAGE 14/44 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 05/12/00 FRI 17:07 [TX/RX NO 8990] 0]014 MAY-12-00 1A:14 FROM:SWABEY OGILVY RENAULT ID. PAGE 15/44 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.
05/12/00 FRI 17:07 [TX/RX NO 8990] 1~J015 MAY-12-00 18:15 FROM:SWABEY OGILVY RENAULT ID: PAGE 16/44 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 05/12/00 FRI 17:07 [TX/RX NO 8990] ~ 016 MAY-12--00 1A:15 FROM:SWABEY OGILVY RENAULT ID: PAGE 17/44 Id 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.
05/12/00 FRI 17:07 [TX/RX NO 8990] f~]017 MAY-12-~00 1B:16 FROM:SWABEY OGILVY RENAULT ID: PAGE 1B/44 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 05/12/00 FRI 17:07 [TX/RX NO 8990] 0 018 MAY-12-00 18.16 FROM:SWABEY OGILVY RENAULT ID: PAGE 19/44 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 05/12/00 FRI 17:07 [TX/RX NO 8990] l~]019 MAY-12-~00 18:16 FROM:SWABEY OGILVY RENAULT ID: PAGE 20/44 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 05/12/00 FRI 17:07 [TX/RX NO 8990] 0 020 MAY-12-00 18:17 FROM:SWABEY OGILVY RENAULT ID. PAGE 21/44 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=

ai -nDr 05/12/00 FRI 17:07 ITX/RX NO 8990] (~J021 MAY-12--00 1B:17 FROM:SWABEY OGILVY RENAULT ID. PAGE 22/44 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-05/12/00 FRI 17:07 [TX/RX NO 8990] C~]022 MAY-12-00 18:18 FRDM:SWABEY OGILVY RENAULT ID: PAGE 23/44 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.
05/12/00 FRI 17:07 [TX/RX NO 8990] f~023 MAY-12-00 lA:lB FROM:SWABEY OGILVY RENAULT ID: PAGE 24/44 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_ 05/12/00 FRI 17:07 ITX/RX NO 8990] f~024 MAY-12-00 1A:19 FROM:sWABEY OGILVY RENAULT ID: PAGE 25/44 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 05/12/00 FRI 17:07 [TX/RX NO 8990] 1~J025 MAY-12-00 18:20 FROM:5WABEY OGIL~7Y RENAULT ID: PAGE 26/44 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 05/12/00 FRI 17:07 ITX/RX NO 8990] f~026 MAY-12-00 1B:20 FROM:SWABEY OGIL~IY RENAULT ID: PAGE 27/44 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), 05/12/00 FRI 17;07 [TX/RX NO 8990] 0 027 MAY-12-00 lA=21 FROM=SWASEY OGILVY RENAULT ID= PAGE 28/44 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 05/12/00 FRI 17:07 [TX/RX NO 8990] 0]028 MAY-12-00 18:21 FROM:SWABEY OGILVY RENAULT ID: PAGE 29/44 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 05/12/00 FRI 17:07 ITX/RX NO 8990] C~J029 MAY-12-00 18:21 FROM:SWABEY OGI1_VY RENAULT ID. PAGE 30/44 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 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 05/12/00 FRI 17:07 ITX/RX NO 8990] (~J030 MAY-12-00 1B-22 FROM-SWABEY OGILC~Y RENHULT ID. PAGE 31/44 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 05/12/00 FRI 17:07 [TX/RX NO 8990] [~J031 MAY-12-00 IA:23 FROM=$WABEY OGILVY RENAULT ID: PAGE 32/44 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 05/12/00 FRI 17:07 [TX/RX NO 8990] ~ 032 MAY-12-00 IB=23 FROM:SWABEY OGILGY RENAULT ID= PAGE 33/44 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 05/12/00 FRI 17:07 lTX/RX ND 8990] f~033 MAY-12-00 1A:24 FROM=SWABEY OGILVY RENAULT ID: PAGE 34/44 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-05/12/00 FRI 17:07 [TX/RX NO 8990] 1034 MAY-12-00 IA:24 FROM:SWABEY DGILVY RENAULT ID: PAGE 35/44 2$
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.
05/12/00 FRI 17:07 [TX/RX NO 8990] 1~J035 MAY-12-00 IA:24 FROM:SWABEY DGILVY (RENAULT Ice: PAGE 36/44 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 05/12/00 FRI 17:07 lTX/RX NO 8990] ~ 036 MAY-12-00 1B-25 FROM-SWABEY ~DGILVY RENAULT ID: PAGE 37/44 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.
05/12/00 FRI 17:07 (TX/RX NO 8990] 0 037 MAY-12-00 1B=25 FROM:SWABEY ~7GILVY RENAULT ID: PAGE 38/44 Table 3: Detergent tatrlets [physical specifications]
Tablet Example Example Example Example Example Example 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.
05/12/00 FRI 17:07 ITX/RX NO 8990] 0 038 MAY-12-00 1A:25 FROM:SWABEY OGILVY RENAULT ID: PAGE 39/44 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 05/12/00 FRI 17:07 lTX/RX NO 8990] 0 039 MAY-12-00 IA-26 FROM=SWABEY OGILCIY RENAULT ID= PAGE 40/44 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_~$-fatty alcohol with 7 EO were used. This granulate was mixed with the other components in a L~~dige FM 130 D mixer, the mixing time after addition of zeolite X (last component, coating powder) being measured_ The composition of the shaped detergent and cleaning composition units is indicated in table 5, the physical specifications of the shaped detergent and cleaning composition units of examples 4, 5 and 6 are summarised in table 6_ Table 5: Composition of the :>haped detergent and cleaning composition units (ex-ample 6) [percent in w~aight]:
Tenside granulate= 64..5 Perfume 0_45 Sodium perborate 16.0 Tetr-yaacetyl~ethyfenE: diamine 7.3 (TAED) Foam inhibitor 3.5 Enzymes 2.5 Cellulose 4.0 Zeolite X 2_0 Salts I water Rest 05/12/00 FRI 17:07 ITX/RX NO 8990] f~040 MAY-12-00 18:26 FROM=SWABEY DGILVY RENAULT ID: PAGE 41/44 As indicated in table 1 containing 3.2 percent in weight of 9C% FAS compound and 3.0 percent in weight of (~~z_~$-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 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 05/12/00 FRI 17;07 [TX/RX NO 8990] I~ 041

Claims (12)

1. Process for the production of shaped detergent and cleaning composition units through mixing of a detergent and cleaning composition granulate manufactured in one of the known ways with powdery upgrading components and subsequent compression shaping, characterised in that mixing of the granulate with the powdery upgrading components takes place in a mixer and the mixture is, after addition of the last compound, subjected to at feast four mixer rotations during a sojourn time in the mixer of 1 - 300 seconds.

2. Process according to Claim 1, characterised in that the detergent and cleaning composition granulate manufactured in one of the known ways contains tenside(s), builder(s) as well as optional additional ingredients commonly contained in detergent and cleaning compositions.

3. Process accord ing to one of Claims 1 or 2, characterised in that one or several substances from the group of tensides, tenside compounds, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, colorants and scents as well as binding agents and disintegration enhancing agents are added as powdery upgrading components during the mixing process.

4. Process according to one of Claims 1 to 3, characterised in that 30 - 80 percent in weight, or preferably 40 - 75 percent in weight, or optimally 50 -percent in weight of granulate and 20 - 70 percent in weight, or preferably 25 - 60 percent in weight, or optimally 30 - 50 percent in weight of powdery components (all percentages indicated in relation to the quantity of the resulting mixture to be compressed) are mixed with each other in the course of the mixing process and that the mixture is, after addition of the last component, subjected to at feast four mixer rotations during a sojourn time in the mixer of 1 - 300 seconds, or preferably 10 - 180 seconds, or optimally 20 - 120 seconds.

5. Process according to one of Claims 1 to 4, characterised in that the detergent and cleaning composition granulate manufactured in one of the known ways consists of two or more separately produced individual granulates.

6. Process according to one of Claims 1 to 5, characterised in that the mixing of the granulate with the powdery components takes place in a slowly moving mixer at a speed between 10 and 250 r.p.m. and during a sojourn time in the mixer of 1 - 300 seconds, or preferably 20 - 180 seconds, or optimally 30 - 150 seconds.

7. Process according to one. of Claims 1 to 5, characterised in that the mixing of the granulate with the powdery components takes place in a fast moving mixer at a speed between 250 and 3000 r.p.m. and during a sojourn time in the mixer of 1 - 300 seconds, or preferably 2 - 180 seconds, or optimally 3 - 90 seconds.

8. Process according to one of Claims 1 to 7, characterised in that the mixture of granulate(s) and powdery components is subjected to at least four, or preferably at least eight, or optimally at least 10 mixer rotations.

9. Process according to one of Claims 1 to 8, characterised in that a tenside compound containing at least 30 percent in weight (in relation to the tenside compound) of fatty alcohol sulphate is added as the last powdery upgrading component in the course of the mixing process and that the mixture is, after addition of the fatty alcohol sulphate compound, subjected to at least four mixer rotations during a sojourn time in the mixer of 1 - 180 seconds, or preferably 10 - 150 seconds, or optimally 20 - 120 seconds.

10. Process according to gone of Claims 7 to 8, characterised in that a tenside compound containing apt least 30 percent in weight (in relation to the tenside compound) of fatty alcohol sulphate as well as zeolite X are added as powdery upgrading components in the course of the mixing process, with zeolite X preferably being added as the last upgrading component, and that the mixture is, after addition of the fatty alcohol sulphate compound and zeolite X, subjected to at least four mixer rotations during a sojourn time in the mixer of 1 - 180 seconds, or preferably 10 - 150 seconds, or optimally 20 - 120 seconds.

11. Process according to one of Claims 9 or 10, characterised in that the fatty alcohol sulphate compound is added as a powdery upgrading component in such a quantity that the mixture to be compressed contains at least 2 percent in weight, or preferably at least 4 percent in weight, or optimally more than percent in weight of fatty alcohol sulphate.

12. Process according to one of Claims 1 to 11, characterised in that compression shaping of the mixture takes place at a pressure of 10 - 150 N/cm2, or preferably 15 - 100 N/cm2 or optimally 20 - 100 N/cm2 and a temperature of - 80°C, or preferably 15 - 70 °C, and optimally 20 -60°C.