CA2289305A1 - Detergent shaped body with enhanced dissolving properties - Google Patents

Abstract

An effervescent shaped detergent body of compacted particulate is presented which disintegrates rapidly in wash liquor without leaving residues on fabrics. They shaped detergent includes 1 to 10 percent by weight of one or more swellable, water-insoluble disintegration aids selected from the group consisting of polyvinyl pyrrolidone, polyvinyl alcohol, and natural and chemically modified biopolymers and 3 to 60 percent by weight of a gas-generating effervescent system.

Description

Detergent Shaped Body with Enhanced Dissolving Properties Field of the Invention This invention relates generally to compact shaped bodies having detersive properties. More particularly, the invention relates to detergent shaped bodies such as, for example, detergent tablets, dishwasher tablets, stain remover tablets or water softening tablets for use in the home, more particularly for use in machines.
Background of the Invention Detergent shaped bodies are widely described in the prior-art literature and are enjoying increasing popularity among consumers because they are easy to dose. Tabletted detergents have a number of advantages over powder-form detergents: they are easier to dose and handle and, by virtue of their compact structure, have advantages in regard to storage and transportation. As a result, detergent shaped bodies are also comprehensively described in the patent literature. One problem which repeatedly arises in the use of detergent shaped bodies is the inadequate disintegrating and dissolving rate of the shaped bodies under in-use conditions. Since sufficiently stable, i.e. dimensionally stable and fracture-resistant, shapedl bodies can only be produced by applying relatively high pressures, the ingredients of the shaped body are heavily compacted so that: disintegration of the shaped body in the wash liquor is delayed which results in excessively slow release of the active substances in the washing pro~;,ess.
The problem of tlhe overly long disintegration times of highly compacted shaped bodies is known in particular from the pharmaceutical industry where certain disintegration aids, so-called tablet disintegrators, have been used for some time in order to shorten the disintegration times.
According to Roimpp (9th Edition, Vol. 6, page 4440) and Voight "Lehrbuch der ~rharmazeutischen Technologie" (6th Edition, 1987, pages 182-184), tablet disintegrators or disintegration accelerators are auxiliaries which provide for the rapid disintegration of tablets in water or gastric juices and' for the release of the pharmaceutical principles in an absorbable form.
"Hagers Handbuch der pharmazeutischen Praxis" (5th Edition, 1991, page 942) classifies the disintegration accelerators or disintegrators according to their action mechanism, the most important action mechan-isms being the swelling mechanism, the deformation mechanism, the wicking mechanism, the repulsion mechanism and the evolution of gas bubbles on contact with water (effervescent tablets). In the case of the swelling mechanism, the particles swell on contact with water and undergo an increase in volume. This produces local stresses which spread throughout the tablet and thus lead to disintegration of the compacted structure. The deformation mechanism differs from the swelling mechanism in the fact that the swelling particles were previously compressed during the tabletting process and now return to their original size on contact wiith water'. In the case of the wicking mechanism, water is drawn into the intE~rior of the shaped body by the disintegration accelerator and loosens the binding forces between the particles which also results in disintegration of the shaped body. The repulsion mechanism differs additionally in the fact that the particles released by the water drawn into the pores repel ~~ne another under the effect of the electrical forces generated. A totally different mechanism forms the basis of "effervescent tablets" which contain active substances or active-substance systems which, on contact with water, release gases that cause the shaped body to burst. In addition, it is known to use hydrophilicizing agents which provide for better wetting of the compressed particles in water and hence for faster disintegration.
Whereas substances which act by the last two of the above-mentioned mechanisms can easily be distinguished from other disintegration me~chanisrns, the effects on which the swelling and deformation mechanisms and the wicking and repulsion mechanisms are based cannot always be clearly distinguished from one another, so that classification into hydrophilicizing agents, gas-releasing systems and swelling disintegrators is nnore appropriate for practical reasons.
The use of these various disintegrators either on their own or in combination with oneanother is well known from pharmaceutical applications. Thus, EP-k3-0 396 335 (Beecham Group PLC) discloses chewing tablets which, in addition to 1 to 30% by weight of an effervescent system of 0.5 to 20% by weight of citric, tartaric, adipic, fumaric or malefic acid and 0.5 to 30% by weight of Na, K or Ca (hydrogen) carbonate or Na glycine carbonate, also contain 5 to 30% by weight of a disintegrating agent, such as (modified) cellulose, polyvinyl pyrrolidone or starch glycolate. According to the document in question, the advantage of these chewing tablets liens in a more pleasant application for the patient and in a more pleasant feeling during ingestion.
Combinations of effervescent granules and swelling disintegrators are also known from JP 06 024 959 (BAYER YAKUHIN KK, Derwent Abstract). This document describes pharmaceutical compositions in tablet form, the active principles being mixed with a disintegrator (methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone) and partly coated with disintegrators containing a swelling gel-forming polymer (sodium alginate, carrageenan, polyethylene oxide) and a C02-generating effervescent system. Despite the use of two disintegration systems, these tablets arE~ claimed to be delayed-release active-principle carriers.
The proposed solutions mentioned above produce the required result in the tabletting of pharmaceutical products. Although, in the field of detergents, they contribute; towards improving the disintegration properties of detergent tablets, the improvement achieved is inadequate in many cases. This applies in particular when the percentage content of tacky organic substances in the tablets, for example anionic and/or nonionic surfactants, increases. In addition, the use of the disintegration aids in detergent tablets c;an lead to specific problems which are entirely unknown in the case of pharmaceutical products.
For example, the use of an effervescent system in detergent tablets does not produce the rapid disintegration required, instead the effervescing and disintegrating effect known from conventional effervescent tablets does occur to begin with, but stops after only a short time so that, thereafter, the tablet does not undergo any further disintegration. It would appear that a water-impermeable layer is formed after a short time from the detergent ingredients mentioned, thus preventing the water from entering the tablet and, hence, the tablet from disintegrating.
Accordingly, European patent application EP-A-0 466 484 (Uni lever), for examplE~, describes tablets of compacted particulate detergent which, besides :~urfactant(s) and builder(s), optionally contain other detergent ingredients, including binders/disintegrators among which swelling types are preferred.
Effervescent detergent tablets are described in DE 35 35 516 (Bucher). These i:ablets contain 2 to 6% by weight of a surfactant, 40 to 60% by weight of hydrogen carbonate, 33 to 53% by weight of a solid organic acid (more particularly a 2:3 mixture of citric and tartaric acid), 1.5 to 2.5% by weight of polyvinyl pyrrolidone and, in addition, colloidal silicon dioxide. However, thesE~ tablets are not laundry detergents, but are preferably used in the screen washer system of motor vehicles and for floor care.
Where conventional swelling disintegrators, such as starch and cellulose or derivatives thereof and polymers, such as polyvinyl pyrrolidone or polyvinyl alcohol, are used in laundry detergents, the tablets obtained disintegrate more or less quickly in water. However, disintegrators of the type mentioned cause residue problems on the treated laundry when used in the quantities required for rapid disintegration.
Summary of the Invention Accordingly, the problem addressed by the present invention was to 5 provide effervescent detergent shaped bodies which, on the one hand, would disintegrate rapidly in the wash liquor but which, on the other hand, would not leave any residues on fabrics.
It has now been found that the disintegration problems of an effervescent detergent shaped body can be overcome by introducing a swellable water-in.~oluble .disintegration aid - in addition to the effervescent system - into the shaped body.
In a first ernbodimE~nt, therefore, the present invention relates to a detergent shaped body of compacted particulate detergent containing surfactant(s), builders and optionally other detergent ingredients, the shaped body additionally containing a) to 10% byy weight of one or more swellable water-insoluble disintegration aids and b) 3 to 60% by weight of a gas-generating effervescent system.
More particularly, the present invention provides a shaped detergent body of compacted particulate detergent comprising:
a) 1 to 10 percent by weight of one or more swellable, water-insoluble disintegration aids selected from the group consisting of polyvinyl pyrrolidone, polyvinyl alcohol, and natural and chemically modified biopolymer~;;
b) 3 to 60 percent by weight of a gas-generating effervescent system;
c) at least one ;~urfacta~nt; and d) at least one builder.
In another aspect, the invention provides a process for the production of shaped detergent bodies comprising compressing a particulate detergent comprising:

a) 1 to 10 percent by weight of one or more swellable, water-insoluble disintegration aids selected from the group consisting of polyvinyl pyrrolidone, polyvinyl alcohol, and natural and chemically modified biopolymer.~;
b) 3 to 60 percent by weight of a gas-generating effervescent system;
c) at least one surfactant; and d) at least one builder.
In the context of the present invention, the contents of a) and b) in the detergent are hereinafter referred to in short as "component a)" and "component b)". The term "component" in this context is purely a linguistic construction. More particularly, the effervescent system b) may consist of several chemical compounds which do not have to be present in the form of a single compound. O~n the contrary, the total content of the chemical compounds in question, which may also be present in totally different individual raw materials or compounds, is calculated and referred to as "component b)". :>imilarly, the swellable water-insoluble disintegration aids do not have to be present in the form of a single compound. In their case, too, several disintegration aids of the type mentioned may optionally be present in the various individual raw materials and/or compounds which are calculated together as "component a)".
Detailed Description of the Invention The swellalble water-insoluble disintegration aids {component a)}
used include, above all, polymeric substances having molecular weights of a few ten thousand to a few hundred thousand gmol-'. Besides synthetic polymers such as, for example, polyvinyl pyrrolidone and polyvinyl alcohol, natural and chemically modified biopolymers selected, for example, from the group of alginates, starches and cellulose are particularly suitable for use as component a). Component a) is preferably selected from natural and synthetic polysaccharides and derivatives thereof.
These groups include, for example, the pure polysaccharides, starch and cellulose, bui: also esterification and etherification products in which hydroxy hydrogen atoms have been substituted. However, celluloses and starches in which the hy~droxy groups have been replaced by functional groups not attached via an oxygen atom may also be used as polysaccharide derivative:.. The group of cellulose derivatives includes, for example, alkali mE~tal celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers .and aminocelluloses while the group of starch derivatives includes, for example, carboxymethyl starch (CMS).
Microcrystalline cellulose may of course also be used as a swellable water-soluble disintegration aid. This cellulose has primary particle sizes of ca. 5 Nm and can be compacted, for example, to granules with an average particle size of 200 Nm. The resulting compactates are stable and can be mixed with other' substances without disintegrating into the primary particles.
Not only can the swellable water-soluble disintegration aids be used in the form of fine-particle powders, they can also be converted into coarser particles by spray drying, granulation, agglomeration, compacting, pelleting or extrusion. These "granulated" disintegration aids include not only granular disintegrators, Ibut also, for example, disintegrators in co-granulated or otheirwise compacted form.
In preferred detergent shaped bodies, 1 to 10% by weight, prefer-ably 2 to 7% by weight and more preferably 3 to 5% by weight, based on the shaped body as a whole, of a cellulose or cellulose derivative is used as component a).
The gas-gE~nerating effervescent system {component b)} may consist of a single substance which releases a gas on contact with water.
Among these compounds, the magnesium peroxide already referred to in the foregoing, which releases oxygen on contact with water, is mentioned in particular. However, the gas-generating effervescent system normally consists of at lea;~t two components which react together to form gas.

Whereas a numk>er of systems which, for example, release nitrogen, oxygen or hydrogE~n may be used for this purpose, the effervescent system used in the detergent ahaped bodies according to the invention is preferably selected according to both economic and ecological criteria.
Preferred components b) consist of alkali metal carbonate and/or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
Among the alkali nnetal carbonates and hydrogen carbonates, the sodium and potassium salts are clearly preferred to the other salts for reasons of cost. It is not of course necessary to use the corresponding pure alkali metal carbonates or hydrogen carbonates. Instead, mixtures of different carbonate's and hydrogen carbonates may be preferred from the point of view of they washing process.
In preferred detergent shaped bodies, 2 to 20% by weight, preferably 3 to 15'% by wE~ight and more preferably 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15% by weight, preferably 2 to 12'% by weight and more preferably 3 to 10% by weight of an acidifying agent, based on the shaped body as a whole, are used as component b).
Suitable aciidifying agents, which release carbon dioxide from the alkali metal salts in aqueous solution, include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids in particular may also be used. Within this group, tartaric acid, succinic acid, malonic acid, adipic acid, malefic acid, fumaric acid, oxalic acid and polyacnylic acid are preferred. Organic: sulfoni~:, acids, such as amidosulfonic acid, may also be used. An acidifying agent which is commercially available and which may also be used with advantage for the purposes of the present invention is Sokalan~ DCS (a trademark of BASF), a mixture of succinic acid (max.
31% by weight,) glutaric acid (max. 50% by weight) and adipic acid (max.
33% by weight).
According i:o the invention, preferred detergent shaped bodies are those in which ~~ substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof is used as acidifying agent in component b).
The detergent shaped bodies according to the invention preferably contain other typical detergent ingredients from the group of surfactants, builders, bleaching agents,, bleach activators, enzymes, optical brighteners, foam inhibitors, perfumes and dyes. These ingredients are described in more detail in the following.
Anionic, nonionic, cationic and/or amphoteric surfactants may be used in the detergent shaped bodies according to the invention. From the performance poinl: of vievu, it is preferred to use mixtures of anionic and nonionic surfactants in which the percentage content of anionic surfactants should be greater 'than that of the nonionic surfactants. The total surfactant content of the shaped bodies is between 5 and 60% by weight, based on the weight of the shaped body, surfactant contents of more than 15% by weight being preferred.
Suitable aniionic surfactants are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C9_~3 alkyl benzenE~sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C~Z_~$ monoolefins with an internal or terminal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Other suitable surfactants of the sulfonate type are the alkane sulfonate:~ obtained from C~2_~$ alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of a-sulfofatty acids (ester sulfonates), for example the a-sullfonated methyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids, are also suitable.
Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters in the context of the present invention are 5 the monoesters, diesters, and triesters and mixtures thereof which are obtained where production is carried out by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol esters are the sul~fonation products of saturated fatty acids containing 6 to 10 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauri~c acid, palmitic acid, stearic acid or behenic acid.
Preferred ;alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid semiesters of C~2_~$ fatty alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C~o_2o oxoalcohols and the corresponding semiesters of secondary alcohols with the same chain length. Other preferred alk(en)yl sulfates are those with the chain length mentioned which contain a synthetic, linear alkyl chain based on a petrochemical and which are similar in their degradation behavior to the corresponding compounds based on olE:ochemical raw materials. C~2_~s alkyl sulfates, C~2-~5 alkyl sulfates and G~a-~5 alkyl sulfates are preferred from the point of view of washing l:echnology. Other suitable anionic surfactants are 2,3-alkyl sulfates which may k>e produced, for example, in accordance with US
3,234,258 or US 5,075,041 and which are commerially obtainable as products of the Shell Oil Company under the name of DAN~.
The sulfuric: acid rnonoesters of linear or branched C~_2~ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9_~~ alcohols containing .on average 3.5 moles of ethylene oxide (EO) or C~2_~$ fatty alcohols containing 1 to 4 EO, are also suitable. In view of their high foaming capacity, they are only used in relatively small quantities, for example in quantities of 1 to 5% by weight, in detergents.
Other preferred anionic surfactants are the salts of alkyl sulfosuccinic acid which are also known as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and, more particularly, ethoxylated fatty alcohols. Preferred sulfosuccinates contain C$_~8 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a~ fatty alcohol residue derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants (for a description, see below). Of these sulfosuccinates, those of which the fatty alcohol residues are derived from narrow-range ethoxylated fatty alcohols are particularly preferred. Alk(en)yl succinic acid preferably containing 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof may also be used.
Other suitable anionic surfactants are, in particular, soaps. Suitable soaps are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and soap mixtures derived in particular from natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acids.
The anionic: surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts and, more preferably, in the form of their sodium salts.
Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, more especially primary alcohols preferably containing 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the form of the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates containing linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut oil, palm oil, tallow fatty or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol acre particularly preferred. Preferred ethoxylated alcohols include, for exam~~le, C~2_~4 alcohols containing 3 EO or 4 EO, C9_» alcohol containing 7 EO, C~3-~5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C~2_~$ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C~2_~4 alcohol containing 3 EO and C~2_~$ alcohol containing 5 EO. The degrees of ethoxylation mentioned represent statistical mean values which, for a specual product, can be a whole number or a broken number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used, examples including tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
In addition, alkyl glycosides corresponding the general formula RO(G)X where R is a primary, linear or methyl-branched, more particularly 2-methyl-branchecl, aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G stands for a glycose unit containing 5 or 6 carbon atoms, preferably glucose, may also be used as further nonionic surfactants. Thf~ degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is between 1 and 10 and preferably befiNeen 1.2 and 4.
Another claws of preferred nonionic surfactants which may be used either as sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylatE~d, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl ~;,hain, more especially the fatty acid methyl esters which are described, for example, in Japanese patent application JP 581217598 or which are preferably produced by the process described in International patent application IJVO-A-90113533.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl-amine oxide, and the fatty acid alkanolamide type are also suitable. The quantity in which these nonionic surfactants are used is preferably no more than the quantity in which the ethoxylated fatty alcohols are used and, more preferably, no more 'than half that quantity.
Other suitable surfactants are polyhydroxyfatty acid amides corresponding to f~~rmula (I):
R' R-CO-N-[Z] (I) in which RCO is am aliphatic acyl group containing 6 to 22 carbon atoms, R' is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms and [Z] is a~ linear or branched polyhydroxyalkyl group containing 3 to 10 carbon atom: and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are known substances which may normally be obtained by reductive amination of a rE~ducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds corresponding to formula (II):
R'-O-R2 R-C O-N-[Z] ( I I ) in which R is a linear or branched alkyl or alkenyl group containing 7 to 12 carbon atoms, R' is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl group or an aryl grnup or an oxyalkyl group containing 1 to 8 carbon atoms, C~~ alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxy-alkyl group, of which the ;~Ikyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of that group.
[Z] is preferably obi;ained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alhoxy- or N-aryloxy-substituted compounds may then be converted into the required polyhydroxyfatty acid amides by reaction with fatty acid methyl esters iin the presence of an alkoxide as catalyst, for example in accordance with the teaching of International patent application WO-A-95/07331.
Silicates, aluminium silicates (especially zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are mentioned in particular as builders which may be present in the detergent shaped bodies according to the invention.
Suitable cr,~stalline layer-form sodium silicates correspond to the general formula N~~2MSiXO2X+~~ y H20, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layer silicates such as these are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both [3- and 8-sodium disilicates Na2Si2O5~ y H;>Oare particularly preferred, [i-sodium disilicate being obtainable, for example, by the process described in International patent application 'WO-A- !91108171.
Other useful builders are amorphous sodium silicates with a modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodiunn silicates can have been obtained in various ways, for example by surface treatnnent, compounding, compacting or by overdrying.
In the context of the invention, the term ~amorphous0 is also understood to encompass ~X-ray amorphous0. In other words, the silicates do not produce any of the sharp X-ray reflexes typical of crystalline substances in 5 X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. However, particularly good builder properties may even be achieved where the silicate particles produce crooked or even sharp diffraction maxima in electron diffraction experiments. This may be 10 interpreted to mean that the products have microcrystalline regions between 10 and a~ few hundred nm in size, values of up to at most 50 nm and, more particu'~larly, up to at most 20 nm being preferred. So-called X-ray amorphous sillicates such as these, which also dissolve with delay in relation to conventional waterglasses, are described for example in 15 German patent application DE-A-44 00 024. Compacted amorphous silicates, compounded amorphous silicates and overdried X-ray-amorphous silicatE~s are particularly preferred.
The finely crystalline, synthetic zeolite containing combined water used in accordance with the invention is preferably zeolite A and/or zeolite P. Zeolite MAP° (Crosfileld) is a particularly preferred P-type zeolite.
However, zeolite :K and mixtures of A, X and/or P are also suitable. The zeolite may be used as a spray-dried powder or even as an undried suspension still moist from its producrtion. If the zeolite is used in the form of a suspension, vthe suspension may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C~2..~$ fatty alcohols containing 2 to 5 ethylene oxide groups, C12-14 fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have a mean particle size of less than 10 ~m (volume distribution, as measured by the Coulter Counter Method) and contain preferably 18 to 22% by weight and more preferably 20 to 22% by weight of combined water.
The generally known phosphates may of course also be used as builders providing their use should not be avoided on ecological grounds.
The sodium salt: of the orthophosphates, the pyrophosphates and, in particular, the tripolyphos~>hates are particularly suitable.
Useful organic builders are, for example, the polycarboxylic acids usable, for examyle, in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, amino-carboxylic acids, nitrilotriiacetic acid (NTA), providing their use is not ecologically unsafe, and mixtures thereof. Preferred salts are the salts of the polycarboxylic: acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. These salts are used for their (building properties and should not be regarded as part of the effervescent ;system, especially since the salts are not suitable for releasing carbon clioxide, for example from hydrogen carbonates.
Among they compounds yielding HZOZ in water which serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, sodium perc;arbonate, peroxypyrophosphates, citrate perhy-drates and HZO2-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecane dioic acid.
In order to obtain an improved bleaching effect where washing is carried out at temperatures of 60°C or lower, bleach activators may be incorporated as a component as such or as an ingredient of component b).
The bleach actiivators may be compounds which form aliphatic peroxocarboxylic .acids containing preferably 1 to 10 carbon atoms and more preferably 2 to 41 carbon atoms and/or optionally substituted perbenzoic acid under perhydrolysis conditions. Substances bearing O-and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable. Preferred bleach activators are pol~~acylate~d alkylenediamines, more particularly tetraacetyl ethylenediamine I;TAED), acylated triazine derivatives, more particularly 1,5-diacetyl-2,4-di~oxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, more particul<~rly tetraacetyl glycoluril (TAGU), N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzene-sulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, more particularly triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
In addition to or instead of the conventional bleach activators mentioned above, so-called bleach catalysts may also be incorporated in the shaped bodies, according to the invention. Bleach catalysts are bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands dud cobalt-, iron-, copper- and ruthenium-ammine complexes may al:~o be used as bleach catalysts.
Suitable foam inhibitors - which may form part of component b) or may be used on their own as component b) - are, for example, soaps of natural or synthetic origin which have a high percentage content of C~8_24 fatty acids. Suitalble non-surface-active foam inhibitors are, for example, organopolysiloxan~~s and mixtures thereof with microfine, optionally silanized, silica or bis-stearyl ethylenediamide. Mixtures of different foam inhibitors, for example mixtures of silicones, paraffins and waxes, may also be used with advantage. The foam inhibitors are preferably fixed to a granular water-soluble or water-dispersible support. Mixtures of paraffins and bis-stearyl ethylenediamides are particularly preferred.
In addition, the detergent shaped bodies according to the invention may also contain components with a positive effect on the removability of oil and fats from fiextiles by washing (so-called soil repellents). This effect becomes particularly clear when a textile which has already been repeatedly washed with a detergent according to the invention containing this oil- and fat-dlissolving component is soiled. Preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers, such as methyl cellulose <~nd methyl hydroxypropyl cellulose containing 15 to 30% by weight of methoxyl groups and 1 to 15% by weight of hydroxy-propoxyl groups, based on the nonionic cellulose ether, and the polymers of phthalic acid and/or terephthalic acid known from the prior art or derivatives thereof, more particularly polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus, are: particularly suitable. Proteases of the subtilisin type are preferred, proteases obtained from Bacillus lentus being particularly preferred. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or of protease, lipase and cellulase, but especially cellulase-containing mixtures, are of particular interest. Peroxidases or oxidases have also proved to be suitable in some cases. The enzymes may be adsorbed to supports and/or encapsulated in shell-forming substances t;o protect them against premature decomposition.
The percentage content of the enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention may be, for example, from about 0.1 to 10% by weight and is preferably from 0.5 to about 5% by weight.

The shaped bodies may contain derivatives of diamino-stilbenzenedisulfonic acid or alkali metal salts thereof as optical brighteners. Suitable optical brighteners are, for example, salts of 4,4'-bis-(2-anilino-4-morph~olino-1,3,5-triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or compounds of similar composition which contain a diethanolamino group, a methylarnino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted Biphenyl styryl type, for example alkali metal salts of 4,4'-bis-(2-sulfostyryl)-diphenyl, 4,4'-bis-(4-chloro-3-sulfostyryl)-Biphenyl or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-Biphenyl, may also be present. Mixtures of the brighteners mentioned above may also be used.
In another ~embodirnent, the present invention relates to a process for producing the detergent shaped bodies according to the invention by compressing a particulate detergent containing surfactant(s), builders and optionally other detergent ingredients, the detergent to be compressed additionally containing a) 1 to 10% by weight of one or more swellable water-insoluble disinte-gration aids and b) 3 to 60% by weight of a gas-generating effervescent system, based on the sha~~ed body formed, components a) and b) optionally being compounded with other ingredients of the detergent or being separately incorporated.
The particulate compound (premix) to be compressed may be present as a pure powder mixture containing components a) and b), although individual raw materials are preferably introduced into the compound in pretreated and, more particularly, precompacted form. In one particular embodirnent, the disintegration aids are preferably introduced into the compound in the form of granules, pellets, compactates or extrudates. The Name alao applies to certain other ingredients, such as surfactants, which may be introduced into the compound in the form of advantageously builder-containing particles obtainable by spray drying, granulation, pelleting, compacting or extrusion.
In preferred embodiments of the process according to the invention, 5 the particulate detergent composition is compressed at temperatures below 30°C and under pressure below 15 N/cmz. The actual production of the shaped bodies according to the invention is carried out by initially dry-mixing the ingredients, which may be completely or partly pregranulated, and then convE~rting the resulting mixture, more particularly by 10 compression, into tablets using conventional methods (for example as described in the conventional patent literature on tabletting, above all in the field of detergents, more particularly as described in the above-mentioned patent applications and the Article entitled "Tablettierung: Stand der Technik", SOFW-Journal, Vol. 122, pp 1016-1021 (1996)).
15 The shaped bodies can be made in predetermined three-dimensional forms. and predetermined sizes. Suitable three-dimensional forms are virtually any easy-to-handle forms including, for example, slabs or bars, cubes, squares and corresponding three-dimensional elements with flat sides and, more particularly, cylindrical forms with a circular or oval 20 cross-section. This particular three-dimensional form encompasses tablets and compact cylinders with a height-to-diameter ratio of more than 1.
The portion shaped bodies may be formed as separate individual elements which correspond to a predetermined dose of the detergent.
However, it is also possible to form shaped bodies which combine several such units in a single shaped body, individual portioned units being easy to break off in particular through the provision of predetermined weak spots.
For the use of laundry detergents in machines of the standard European type with horizons:ally arranged mechanics, it can be of advantage to produce the portioned shaped bodies as cylindrical or square tablets, preferably with a diameter-to-height ratio of about 0.5:2 to 2:0.5.

Commercially available hydraulic presses, eccentric presses and rotary presses are particularly suitable for the production of shaped bodies such these.
The three-dimensional form of another embodiment of the shaped bodies according to the invention is adapted in its dimensions to the dispensing compartment of commercially available domestic washing machines, so that the shaped bodies can be introduced directly, i.e. without a dosing aid, into the dispensing compartment where they dissolve on contact with water. However, it is of course readily possible - and preferred in accordance with the present invention - to use the detergent shaped bodies in conjunctlion with a dosing aid.
Another preferred shaped body which can be produced has a plate-like or slab-like structure with alternately thick long segments and thin short segments, so that individual segments can be broken off from this "bar" at the predetermined) weak :,pots, which the short thin segments represent, and introduced into the machine. This "bar" principle can also be embodied in other geomE~tric forms, for example vertical triangles which only joined to one another at one of their longitudinal sides.
In another possible embodiment, however, the various components are not compressed to form a single tablet, instead the shaped bodies obtained comprise several layers, i.e. at least two layers. These various layers may have different dissolving rates. This can provide the shaped bodies with favorable performance properties. If, for example, the shaped bodies contain components which adversely affect one another, one component may bE~ integrated in the more quickly dissolving layer while the other component rnay be incorporated in a more slowly dissolving layer so that the first comlponent can already have reacted off by the time the second component dissolves. The various layers of the shaped bodies can be arranged in the form of a stack, in which case the inner layers) dissolve at the edges of the shaped body before the other layers have completely dissolved. Alternatively, however, the inner layers) may also be completely surrounded by the layers lying further to the outside which prevents constituents of the inner layers) from dissolving prematurely.
In another preferred embodiment of the invention, a shaped body consists of at least three layers, i.e. two outer layers and at least one inner layer, a peroxy bleaching agent being present in at least one of the inner layers whereas, in the case of the stack-like tablet, the two cover layers and, in the case of the envelope-like tablet, the outermost layers are free from peroxy bleaching agent. In another possible embodiment, peroxy bleaching agent ;end any bleach activators or bleach catalysts present and/or enzymes nnay be ;spatially separated from one another in one and the same shaped body. llAultilayer shaped bodies such as these have the advantage that thE:y can be used not only via a dispensing compartment or via a dosing unit which is added to the wash liquor, instead it is also possible in cases such as these to introduce the shaped body into the machine in direct contact with the fabrics without any danger of spotting by bleaching agent on the likes.
Similar efl~ects can also be obtained by coating individual constituents of the: detergent composition to be compressed or the shaped body as a whole. To this end, the shaped bodies to be coated may be sprayed, for example, with aqueous solutions or emulsions or a coating may be obtained by the process known as melt coating.
The shaped bodies according to the invention, more particularly the hitherto poorly di:~integrai:ing and poorly soluble detergent and bleaching tablets, have excellent disintegration properties through the presence of water-insoluble, :>wellable disintegration aid and effervescent system components a) and b)}. This can be tested, for example, under critical conditions in a standard domestic washing machine (direct introduction into the wash liquor by a conventional dosing unit, delicates program or coloreds program, washing temperature max. 40°C).

In another embodirnent, therefore, the present invention relates to a washing process in which the shaped body is introduced into the wash liquor from the di;>pensing compartment of a domestic washing machine.
The dissolving times of the shaped bodies in the washing machine are preferably less than 8 minutes and more preferably less than 5 minutes. In another embodimE:nt, the invention relates to a washing process in which the shaped body is placed directly - optionally using a dosing aid - on the laundry loaded into the drum of a domestic washing machine. In this case, the shaped body may advantageously be added to the washing directly, i.e.
without an additional dosing aid. However, known dosing aids, such as bags, sachets, plastic containers and the like, may also readily be used.
Examples Detergent :>haped bodies 1 and 2 according to the invention and comparison shaped bodies 3 and 4 which have the composition shown in Table 1 were produced by compressing a particulate detergent composition.
The comparison shaped bodies contained either no component a) (Example 3) or no component b) (Example 4), small quantities of Na2C03 being used as buil~~er.

Table 1 Detergent shaped bodies [% by weight]
Detergent shaped body 1 2 3 4 C9_,3 Alkyl benzene:~ulfonate 11.4 10.0 10.6 10.0 C,2_,S Fatty alcohol ;>ulfate - 6.6 2.4 6.8 C,z_,8 Fatty alcohol ~ 7E0 5.8 - 4.8 6.2 Soap 0.7 2.1 1.6 1.8 Sodium tripolyphosphate - 23.5 - -Zeolite 4A (based on water-free18.5 3.5 20.0 20.0 substance) Sodium perborate 18.2 - 18.6 18.6 Sodium percarbonaile - 23.0 - -Tetraacetyl ethylenediamine 6.4 3.4 5.8 5.8 (TAED) Cellulose {component a)} 3.4 4.0 - 6.0 Citric acid {constituent of 3.2 3.5 3.5 -cornponent b)}*

Na2C03 {constituent: of component8.6 - 8.1 6.3 b)}*

NaHC03 {constituent of component6.4 7.0 6.8 -b)}*

Amorphous sodium silicate 3.3 2.1 3.0 3.4 Acrylic acid/maleic acid copolymer2.7 2.5 2.5 2.6 Enzymes 2.3 4.0 2.7 2.7 Brightener 0.2 0.2 0.2 0.2 Polyethylene glycol (molecular - 0.5 - -weight ca.
4000 g/mol) Salts/water BalanceBalanceBalanceBalance ") separately incorporated The hardness of the tablets was measured by deforming the tablets until they broke, the force being applied to the sides of the tablets and the maximum force the: tablets, withstood being determined.
To determine tablet disintegration, a tablet was placed in a glass beaker filled with water (600 ml of water, temperature 30°C) and the time which the tablet took to disintegrate completely was measured.
For the dis~pensincl test, three 40 g tablets were placed in the dispensing compartment of the washing machine used. After the dispensing phase, the residue in the compartment was dried and weighed.
The experirnental data are shown in Table 2.
Table 2 Detergent tablets [physical data]
Tablet Example Example Example Example Tablet hardness 33 N 24 N 30-35 30-35 N
N

Tablet disintegration5-10 secs.5-10 secs.> 5 mins.3 mins.

Residue - - 34 g 12 g

Claims (22)

1. A shaped detergent body of compacted particulate detergent comprising:
a) 1 to 10 percent by weight of one or more swellable, water-insoluble disintegration aids selected from the group consisting of polyvinyl pyrrolidone, polyvinyl alcohol, and natural and chemically modified biopolymers;
b) 3 to 60 percent by weight of a gas-generating effervescent system;
c) at least one surfactant; and d) at least one builder.

2. The shaped detergent body of claim 1 wherein component a) comprises coarse particles formed by spray drying, granulation, agglomeration, compacting, pelleting or extrusion.

3. The shaped detergent body of claim 1 wherein component a) comprises one or more natural or synthetic polysaccharides, derivatives thereof, or mixtures thereof.

4. The shaped detergent body of claim 3 comprising 1 to 10 percent by weight of a cellulose or cellulose derivative.

5. The shaped detergent body of claim 4 comprising 2 to 7 percent by weight of a cellulose or cellulose derivative.

6. The shaped detergent body of claim 5 comprising 3 to 5 percent by weight of a cellulose or cellulose derivative.

7. The shaped detergent body of claim 1 wherein component b) comprises an alkali metal carbonate, hydrogen carbonate, or mixtures thereof, and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

8. The shaped detergent body of claim 7 comprising 2 to 20 percent by weight of said alkali metal carbonate, hydrogen carbonate, or mixtures thereof, and 1 to 15 percent by weight of said acidifying agent.

9. The shaped detergent body of claim 8 comprising 3 to 15 percent by weight of said alkali metal carbonate, hydrogen carbonate, or mixtures thereof, and 2 to 12 percent by weight of said acidifying agent.

10. The shaped detergent body of claim 9 comprising 5 to 10 percent by weight of said alkali metal carbonate, hydrogen carbonate, or mixtures thereof, and 3 to 10 percent by weight of said acidifying agent.

11. The shaped detergent body of claim 7 comprising an organic acidifying agent.

12. The shaped detergent body of claim 11 comprising citric acid as the acidifying agent.

13. The shaped detergent body of claim 11 comprising organic di-, tri- and oligocarboxylic acids or mixtures thereof as the acidifying agent.

14. The shaped detergent body of claim 1 further comprising from 5 to 60 percent by weight of one or more surfactants.

15. The shaped detergent body of claim 14 comprising at least 15 percent by weight of one or more surfactants.

16. A process for the production of shaped detergent bodies comprising compressing a particulate detergent comprising:
a) 1 to 10 percent by weight of one or more swellable, water-insoluble disintegration aids selected from the group consisting of polyvinyl pyrrolidone, polyvinyl alcohol, and natural and chemically modified biopolymers;
b) 3 to 60 percent by weight of a gas-generating effervescent system;
c) at least one surfactant; and d) at least one builder.

17. The process of claim 16 wherein the disintegration aids are in the form of granules, pellets, compactates or extrudates.

18. The process of claim 16 comprising compressing the particulate detergent at a temperature below 30°C and under a pressure below 15 N/cm2.

19. The process of claim 15 further comprising dry mixing all components of the particulate detergent prior to compression.

20. The shaped detergent body of claim 1 in a form adapted to the dispensing compartment of commercially available washing machines.

21. The shaped detergent body of claim 11 in a form of a plate-like or slab-like structures with alternately thick long segments and thin short segments to enable breaking individual segments from the shaped detergent.

22. The shaper detergent body of claim 1 comprising three layers, wherein the inner layer comprises a peroxy bleaching agent and the two outer layers are free of any peroxy bleaching agent.