CA2318000A1 - Detergent component with finely divided solids - Google Patents

Abstract

Mixtures (dispersions/emulsions) having long-term stability, possessing little tendency to separate, and providing effective and stable detergent components comprise from 10 to 89.9% by weight of surfactant(s), from 10 to 89.9% by weight of meltable substance(s) having a melting point above 30°C and a water solubility of less than 20 g/l at 20°C, from 0.1 to 15%
by weight of one or more solids at least 90% by weight of whose particles have sizes below 300 µm, and also, optionally, from 0 to 15% by weight of further active substances and/or auxiliaries.

Description

DETERGENT COMPONENT WITH FINELY DIVIDED SOLIDS
Field of the Invention The present invention is situated in the field of machine dishwashing compositions for customary domestic dishwashing machines. It relates to detergent components for use in machine dishwashing compositions (MDWCs) and also to detergent compositions and detergent tablets which comprise such components.
Background of the Invention The machine cleaning of kitchen- and tableware in domestic dishwashing machines normally involves a prewash cycle, a main wash cycle and a rinse cycle, interrupted by intermediate wash cycles. With the majority of machines, the prewash cycle may be selected for highly soiled ware, but is selected by the user only in exceptional cases, so that in the majority of machines a main wash cycle, an intermediate wash cycle with clean water, and a rinse cycle are conducted. The temperature of the main wash cycle varies, according to machine type and program step choice, between 40 and 65°C. In the rinse cycle, rinse aids are added from a dosing tank within the machine, these rinse aids normally comprising nonionic surfactants as their principal constituent.
Rinse aids of this kind are in liquid form and have been widely described in the prior art. Their primary object is to prevent lime spots and deposits on the cleaned ware. Besides water and low-foaming nonionic surfactants, these rinse aids often also include hydrotropes, pH
modifiers such as citric acid, or scale-inhibiting polymers.
The reservoir tank within the dishwashing machine has to be filled up at regular intervals with rinse aid, one fill being sufficient for from 10 to 50 cycles, depending on machine type. If the user forgets to fill up the tank, then glasses, in particular, acquire unsightly lime spots and deposits. In the prior art, therefore, there exist a number of proposals for integrating a rinse aid into the machine dishwashing detergent.
For instance, European Patent Application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets whose first layer comprises peroxy bleach, builder and enzyme while the second layer comprises acidifiers, a continuous medium having a melting point of between 55 and 70°C and scale inhibitors. It is intended that the high-melting continuous medium will effect retarded release of the acids) and scale inhibitors) to produce a rinse aid effect. This document makes no mention of powder-form machine dishwashing compositions or rinse aid systems comprising surfactant.
The prior German Patent Application DE 198 51 426.3 (Henkel KGaA) describes a process for producing multiphase detergent tablets which comprises compressing a particulate premix into tablets which have a depression, which is subsequently filled with a separately prepared melt comprising a meltable substance and one or more active substances suspended or dispersed therein. The teaching of this document is also tied to the tablet commercial form.
The melt suspensions or melt emulsions disclosed in the last-mentioned document, however, especially when surfactants are incorporated as an active substance, have a long-term stability which is in need of improvement.
After the emulsion has cooled, the meltable substances are supposed to enclose the active substance and protect it against premature release. If the emulsion is not sufficiently stable, it undergoes partial separation in the melted state prior to dosing, leading to dosing inaccuracies. Slightly more stable emulsions can be dosed but undergo partial separation prior to solidification, so that the active substance is released early on in the cleaning operation. Proposing a solution, this document discloses the use of diverse auxiliaries/stabilizers.
where solids are mentioned, however, nothing is said about their physical properties.
Sux~nary of the Invention It is an object of the present invention to further develop the teaching of prior German Patent Application DE 198 51 426.3 and to provide mixtures which possess long-term stability, which have no propensity to separate in the course of dosing and cooling and which, accordingly, give effective and stable detergent components. These long-term-stable mixtures and the detergent components prepared from them ought to make it possible to utilize all known advantages of the controlled release of ingredients, especially a clear-rinse effect, both for powder-form detergents and for detergent tablets.
It has now been found that separation-stable melts may be prepared from meltable hydrophobic substances having melting points above 30°C, surfactants) and, optionally, further ingredients such as dyes and fragrances, etc., if these mixtures contain at least 0.1% by weight of finely divided solid (s) .
The melting point of such mixtures may be tailored to the desired value by the nature and amount of the individual ingredients, in particular by way of the melting points and amounts of meltable substances) and surfactant(s).
Above the melting point, the mixtures are stable toward separation; below the melting point there exist solidified mixtures in any desired shape, which in the context of the present specification are referred to as detergent components.
The present invention provides a detergent component comprising a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substances) having a melting point above 30°C
and a water solubility of less than 20 g/1 at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries, with the proviso that at least 90% by weight of the particles c) have sizes below 300 ~,m.
Detailed Description of the Invention In the context of the present application, the term "detergent component" denotes solidified mixtures of the ingredients a) to d), irrespective of their shape.
"Detergent components" in the sense of the present application therefore include, for example, flakes, prills, pellets, tablet regions, tablets per se, etc. In order to obtain an extremely fine distribution of the ingredient a) in a matrix of the ingredient b) , both the ingredients are melted, separately or mixed with one another, combined if appropriate, and stirred together with the addition of c) and the optional addition of d) .
The melt suspension. or melt emulsion prepared in this way, sometimes referred to below simply as "mixture", may then be converted to the desired form.
Preferred detergent components comprise as ingredient a) from 15 to 80, preferably from 20 to 70, with particular preference from 25 to 60, and in particular from 30 to 50% by weight of surfactant(s). All surfactants from the groups of the anionic, nonionic, cationic, and amphoteric surfactants may be used, preferred detergent components comprising as ingredient a) anionic and/or nonionic surfactant(s), preferably nonionic surfactant(s).
Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C9_13 alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkenesulfonates and hydroxyalkanesulfonates, and also disulfonates, as are obtained, for example, from Cla-is monoolefins having a terminal or internal double bond by sulfonating with gaseous sulfur trioxide followed by alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are obtained from Clz-is alkanes, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, respectively.
Likewise suitable, in addition, are the esters of a-sulfo fatty acids (ester sulfonates), e.g., the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
Further suitable anionic surfactants are sulfated fatty acid glycerol esters . Fatty acid glycerol esters are the monoesters, diesters and triesters, and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with from 1 to 3 mol of fatty acid or in the transesterification of triglycerides with from 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfation products of saturated fatty acids having 6 to 22 carbon atoms, examples being those of caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid, or behenic acid.

Preferred alk(en)yl sulfates are the alkali metal salts, and especially the sodium salts, of the sulfuric monoesters of Clz-Cls fatty alcohols, examples being those of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of Clo-Czo oxo alcohols, and those monoesters of secondary alcohols of these chain lengths. Preference is also given to alk(en)yl sulfates of said chain length which contain a synthetic straight-chain alkyl radical prepared on a petrochemical basis, these sulfates possessing degradation properties similar to those of the corresponding compounds based on fatty-chemical raw materials. From a detergents standpoint, the Clz-Cls alkyl sulfates and Clz-Cls alkyl sulfates, and also C14-Cls alkyl sulfates, are preferred. In addition, 2,3-alkyl sulfates, which may be obtained as commercial products from Shell Oil Company under the name DAN~, are suitable anionic surfactants.
Also suitable are the sulfuric monoesters of the straight-chain or branched C~_zl alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9_11 alcohols containing on average 3.5 mol of ethylene oxide (EO) or Clz-le fatty alcohols containing from 1 to 4 EO. Because of their high foaming behavior they are used in detergents only in relatively small amounts, for example, in amounts of from 1 to 5% by weight.
Further suitable anionic surfactants include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which constitute monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates comprise Cs_lg fatty alcohol radicals or mixtures thereof. Especially preferred sulfosuccinates contain a fatty alcohol radical derived from ethoxylated fatty alcohols which themselves represent nonionic surfactants (for description, see below). Particular preference is given in turn to sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols having a narrowed homolog distribution.
Similarly, it is also possible to use alk(en)ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk(en)yl chain, or salts thereof.
Further suitable anionic surfactants are, in particular, soaps. Suitable soaps include saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and, in particular, mixtures of soaps derived from natural fatty acids, e.g., coconut, palm kernel or tallow fatty acids.
The anionic surfactants, including the soaps, may be present in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, the anionic surfactants are in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
Nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary, alcohols having preferably 8 to 18 carbon atoms and on average from 1 to 12 mol of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, methyl-branched in position 2 and/or may comprise linear and methyl-branched radicals in a mixture, as are commonly present in oxo alcohol radicals.
In particular, however, preference is given to alcohol ethoxylates containing linear radicals from alcohols of natural origin having 12 to 18 carbon atoms, e.g., from coconut, palm, tallow fatty or oleyl alcohol and on average from 2 to 8 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, Clz-14 alcohols containing 3 EO or 4 EO, C9_11 alcohol containing 7 EO, C13-is alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Clz-is alcohols containing 3 EO, 5 EO or 7 EO, and mixtures thereof, such as mixtures of Clz-i4 alcohol containing 3 EO
and Clz-la alcohol containing 5 EO. The stated degrees of ethoxylation represent statistical mean values, which for a specific product may be an integer or a fraction.
Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NREs). In addition to these nonionic surfactants it is also possible to use fatty alcohols containing more than 12 EO. Examples thereof are tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
As further nonionic surfactants, furthermore, use may also be made of alkyl glycosides of the general formula RO(G)X, where R is a primary straight-chain or methyl-branched aliphatic radical, especially an aliphatic radical methyl-branched in position 2, containing 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol representing a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization, x, which indicates the distribution of monoglycosides and oligoglycosides, is any desired number between 1 and 10;
preferably, x is from 1.2 to 1.4.
A further class of nonionic surfactants used with preference, which are used either as sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated, or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
Nonionic surfactants of the amine oxide type, examples being N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamide type, may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethaxylated fatty alcohols, in particular not more than half thereof.
Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I) Rl R-CO-N-[Z] (I) where RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R1 is hydrogen or an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and from 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which are customarily obtainable by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine, and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
The group of the polyhydroxy fatty acid amides also includes compounds of the formula (II) R 1-Q _R?
R-CO-N-[Z] (II) where R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and RZ is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C1_4 alkyl radicals or phenyl radicals, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of said radical.
[Z] is preferably obtained by reductive amination of a reduced sugar, e.g., glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may be converted to the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
Preferred surfactants used are low-foaming nonionic surfactants. With particular preference, the detergent components of the invention for machine dishwashing comprise nonionic surfactants, especially nonionic surfactants from the group of the alkoxylated alcohols.
Nonionic surfactants used are preferably alkoxylated, advantageously ethpxylated, especially primary, alcohols having preferably 8 to 18 carbon atoms and on average from 1 to 12 mol of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or, preferably, methyl-branched in position 2 and/or may comprise linear and methyl-branched radicals in a mixture, as are commonly present in oxo alcohol radicals.
In particular, however, preference is given to alcohol ethoxylates containing linear radicals from alcohols of natural origin having 12 to 18 carbon atoms, e.g., from coconut, palm, tallow fatty or oleyl alcohol and on average from 2 to 8 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, Cia-i4 alcohols containing 3 EO or 4 EO, C9_11 alcohol containing 7 EO, Ci3-is alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C12_le alcohols containing 3 EO, 5 EO or 7 EO, and mixtures thereof, such as mixtures of Clz-14 alcohol containing 3 EO
and Clz-is alcohol containing 5 EO. The stated degrees of ethoxylation represent statistical mean values, which for a specific product may be an integer or a fraction.
Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NREs). In addition to these nonionic surfactants it is also possible to use fatty alcohols containing more than 12 EO. Examples thereof are tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
Especially preferred detergent components of the invention are those that comprise a nonionic surfactant having a melting point above room temperature.
Accordingly, preferred detergent components comprise as ingredient a) nonionic surfactants) having a melting point above 20°C, preferably above 25°C, with particular preference between 25 and 60°C, and in particular between 26.6 and 43.3°C.
Suitable nonionic surfactants having melting or softening points within the stated temperature range are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, then it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas, and in particular above 40 Pas. Also preferred are nonionic surfactants which possess a waxlike consistency at room temperature.
Preferred nonionic surfactants for use that are solid at room temperature originate from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols, and mixtures of these surfactants with surfactants of more complex construction such as polyoxypropylene/polyoxyethylene/ polyoxypropylene (PO/EO/PO) surfactants. Such (PO/EO/PO) nonionic surfactants are notable, furthermore, for good foam control.
In one preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant originating from the reaction of a monohydroxy alkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, with particular preference at least 15 mol, in particular at least 20 mol, of ethylene oxide per mole of alcohol or alkylphenol, respectively.
A particularly preferred nonionic surfactant for use that is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (Cls-ao alcohol), preferably a C18 alcohol, and at least 12 mol, preferably at least 15 mol, and in particular at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.
Accordingly, particularly preferred detergent components of the invention comprise as ingredient a) ethoxylated nonionic surfactant (s) obtained from Cs-20 monohydroxyalkanols or C6_2o alkylphenols or Cls-ao fatty alcohols and more than 12 mol, preferably more than 15 mol, and in particular more than 20 mol, of ethylene oxide per mole of alcohol.
The nonionic surfactant which is solid at room temperature preferably further possesses propylene oxide units in the molecule. Preferably, such PO units account for up to 25% by weight, with particular preference up to 20% by weight, and in particular up to 15% by weight, of the overall molecular mass of the nonionic surfactant.
Particularly preferred nonionic surfactants are ethoxylated monohydroxy alkanols or alkylphenols, which additionally comprise polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol moiety of such nonionic surfactant molecules in this case makes up preferably more than 30% by weight, with particular preference more than 50% by weight, and in particular more than 70% by weight, of the overall molar mass of such nonionic surfactants. Preferred detergent components comprise as ingredient a) ethoxylated and propoxylated nonionic surfactants wherein the propylene oxide units in the molecule account for up to 25% by weight, preferably up to 20% by weight, and in particular up to 15% by weight, of the overall molecular mass of the nonionic surfactant.
Further nonionic surfactants whose use is particularly preferred, with melting points above room temperature, contain from 40 to 70% of a polyoxypropylene/
polyoxyethylene/polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene containing 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 mol of ethylene oxide and 99 mol of propylene oxide per mole of trimethylolpropane.
Nonionic surfactants which may be used with particular preference are, for example, obtainable under the name Poly Tergent~ SLF-18 from the company Olin Chemicals.
Further preferred detergent components of the invention comprise as ingredient a) nonionic surfactants of the formula R10 [CH2CH (CH3) O] x [CHzCH20] Y [CHzCH (OH) R2]
in which R1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms, or mixtures thereof, RZ is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms, or mixtures thereof, and x is between 0.5 and 1.5, and y is at least 15.
Further nonionic surfactants which may be used with preference are the endgroup-capped poly(oxyalkylated) nonionic surfactants of the formula R10 [CHZCH (R3) O] X [CH2] kCH (OH) [CH2] ~ORz in which R1 and RZ are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 3 0 carbon atoms , R3 is H or a methyl , ethyl , n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5. Where x >_ 2, each R3 in the above formula may be different. R1 and RZ are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R3, H, -CH3 or -CHzCH3 are particularly preferred. Particularly preferred values for x lie within the range from 1 to 20, in particular from 6 to 15.
As described above, each R3 in the above formula may be different if x >_ 2. By this means it is possible to vary the alkylene oxide unit in the square brackets. If x, for example, is 3, the radical R3 may be selected in order to form ethylene oxide (R3 - H), or propylene oxide (R3 -CH3) units, which may be added on to one another in any sequence, examples being (EO)(PO)(EO), (EO)(EO)(PO), (EO) (EO) (EO) , (PO) (EO) (PO) , (PO) (PO) (EO) and (PO)(PO)(PO). The value of 3 for x has been chosen by way of example in this case and it is entirely possible for it to be larger, the scope for variation increasing as the values of x go up and embracing, for example, a large number of (EO) groups, combined with a small number of (PO) groups, or vice versa.
Particularly preferred endgroup-capped poly(oxyalkylated) alcohols of the above formula have values of k = 1 and j - 1, thereby simplifying the above formula to R10 [ CHZCH ( R3 ) O ] XCHZCH ( OH ) CHzOR2 .
In the last-mentioned formula, R1, RZ and R3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20, and in particular from 6 to 18.
Particular preference is given to surfactants wherein the radicals R1 and R2 have 9 to 14 carbon atoms, R3 is H, and x adopts values from 6 to 15.
Summarizing the last-mentioned statements, preference is given to detergent components of the invention comprising as ingredient a) endgroup-capped poly(oxyalkylated) nonionic surfactants of the formula R10 [CHZCH (R3) O] X [CHZ] kCH (OH) [CHZ] ~ORz in which R1 and Rz are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 3 0 carbon atoms, R3 is H or a methyl , ethyl , n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5, particular preference being given to surfactants of the type R10 [ CHZCH ( R3 ) O ] XCHZCH ( OH ) CH20R2 where x is from 1 to 30, preferably from 1 to 20, and in particular from 6 to 18.
As ingredient b), the detergent components of the invention comprise one or more meltable substances which have a melting point above 30°C, and possess little or no solubility in water. These substances form the "matrix"
in which the ingredient a) of the detergent components of the invention is present in fine distribution, this distribution being stabilized by means of the special ingredient c). In the context of the present invention, preferred detergent components are those comprising as ingredient b) from 15 to 85, preferably from 20 to 80, with particular preference from 25 to 75, and in particular from 30 to 70% by weight of meltable substance ( s ) .
The temperature at which the detergent components of the invention release the ingredients a) and, optionally, d) may be varied within wide limits through the choice of the melting point of the ingredient b). Below this temperature, the other ingredients are protected against ambient influences.

The meltable substances used in the detergent components of the invention are subject to a variety of requirements, relating on the one hand to the melting behavior or, respectively, solidification behavior but on the other hand also to the material properties of the melt in the solidified state, i.e., in the detergent components of the invention. Since the detergent component is to be durably protected against ambient influences in transit or storage, the meltable substance must possess a high stability with respect, for example, to impacts occurring in the course of packaging or transport. The meltable substance should, therefore, have either at least partially elastic or at least plastic properties, in order to react by elastic or plastic deformation to any impact that does occur, and not to become crushed. The meltable substance should have a melting range (solidification range) situated within a temperature range in which other ingredients of the detergent components of the invention are not exposed to any excessive thermal load. On the other hand, however, the melting range must be sufficiently high still to offer effective protection for the active substances at least at slightly elevated temperature. In accordance with the invention, the meltable substances have a melting point above 30°C, preference being given to detergent components comprising only meltable substances having melting points above 40°C, preferably above 45°C, and in particular above 50°C. Particularly preferred detergent components comprise as ingredient b) one or more substances having a melting range between 30 and 100°C, preferably between 40 and 80°C, and in particular between 50 and 75°C.
It has proven advantageous for the meltable substance not to exhibit a sharply defined melting point, as encountered commonly with pure, crystalline substances, but instead to have a melting range which covers, in some cases, several degrees Celsius.
The meltable substance preferably has a melting range which lies between about 52.5°C and about 80°C. In the present case that means that the melting range occurs within the stated temperature interval, and does not denote the width of the melting range. The width of the melting range is preferably at least 1°C, more preferably from about 2 to about 3°C.
The abovementioned properties are in general possessed by what are called waxes. The term "waxes" is applied to a range of natural or synthetic substances which melt without decomposition, generally at above 50°C, and are of comparatively low viscosity, without stringing, at just a little above the melting point. They have a highly temperature-dependent consistency and solubility.
According to their origin, the waxes are divided into three groups: the natural waxes, chemically modified waxes, and the synthetic waxes.
The natural waxes include, for example, plant waxes such as candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or uropygial grease, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or microcrystalline waxes.
The chemically modified waxes include, for example, hard waxes such as montan ester waxes, sassol waxes, or hydrogenated jojoba waxes.

By synthetic waxes are meant, in general, polyalkylene waxes or polyalkylene glycol waxes. As coating materials it is also possible to use compounds from other classes of substance which meet the stated requirements in terms of softening point. Examples of synthetic compounds which have proven suitable are higher esters of phthalic acid, especially dicyclohexyl phthalate, which is available commercially under the name Unimoll~ 66 (Bayer AG). Also suitable are synthetically prepared waxes from lower carboxylic acids and fatty alcohols, an example being dimyristyl tartrate, which is available under the name Cosmacol~ ETLP (Condea).
Preferably, the coating substance present in the detergent components of the invention includes a paraffin wax fraction. That means that at least 10% by weight of the total meltable substances present, preferably more, consist of paraffin wax. Particularly suitable are paraffin wax contents (based on the total amount of meltable substance) of approximately 12.5% by weight, approximately 15% by weight or approximately 20% by weight; even higher proportions, of, for example, more than 30% by weight may be particularly preferred. In one particular embodiment of the invention, the total amount of the meltable substance used consists exclusively of paraffin wax.
Relative to the other, natural waxes mentioned, paraffin waxes have the advantage in the context of the present invention that in an alkaline detergent environment there is no hydrolysis of the waxes (as is to be expected, for example, with the wax esters), since paraffin wax contains no hydrolyzable groups.
Paraffin waxes consist primarily of alkanes, with small fractions of isoalkanes and cycloalkanes. The paraffin for use in accordance with the invention preferably contains essentially no constituents having a melting point above 70°C, with particular preference above 60°C.
Below this melting temperature, in the detergent liquor, fractions of high-melting alkanes in the paraffin may leave unwanted wax residues on the surfaces to be cleaned or on the ware to be cleaned. Wax residues of this kind lead in general to an unattractive appearance of the cleaned surface and should therefore be avoided.
Preferred detergent components comprise as ingredient b) at least one paraffin wax having a melting range of from 30°C to 65°C.
Preferably, the amount of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally from about 10 to about 30°C) in the paraffin wax used is as high as possible. The larger the amount of solid wax constituents in a wax at room temperature, the more useful that wax is in the context of the present invention. As the proportion of solid wax constituents increases, there is an increase in the resistance of the detergent component to impacts or friction against other surfaces, resulting in a longer-lasting protection of the active substances. High proportions of oils or liquid wax constituents may cause weakening as a result of which pores are opened and the active substances are exposed to the ambient influences mentioned at the outset.
In addition to paraffin, the meltable substance may further comprise one or more of the abovementioned waxes or waxlike substances. Preferably, the mixture forming the meltable substance should be such that the detergent component is at least substantially water-insoluble. At a temperature of about 30°C, the solubility in water should not exceed about 10 mg/1 and preferably should be below mg/l.
In any case, however, the coating should preferably have 5 as low a solubility in water as possible, even in water at elevated temperature, in order as far as possible to avoid temperature-independent release of the active substances. Preferred detergent components are, therefore, those wherein the water solubility of ingredient b) at 20°C is less than 15 g/1, preferably less than 10 g/l, with particular preference less than 5 g/1, and in particular less than 2 g/l. It is particularly preferred if the water solubility of ingredient b) at 20°C is below the measurement limit, i.e., if substance b) is to all intents and purposes "insoluble" in water.
As ingredient c), the detergent components of the invention contain from 0.1 to 15% by weight of one or more solids, at least 90% by weight of the particles of c) having sizes below 300 Vim. In preferred detergent components, the amounts of c) lie within a narrower range, and the particle sizes as well are also, preferably, even finer. Thus, firstly, preference is given to detergent components comprising ingredient c) in amounts of from 0.15 to 12.5, preferably from 0.2 to 10, with particular preference from 0.25 to 7.5, and in particular from 0.3 to 5% by weight; secondly, at least 90% by weight of the particles of c) in further-preferred detergent components have sizes below 200 ~,m, preferably below 190 Vim, with particular preference below 175 ~,m, in particular below 150 Vim, and with very particular preference below 100 Vim.
It is particularly preferred if the ingredient c) possesses no particles at all having a size above 200 Vim;

preferably, the particle size is even further below this limit. In particularly preferred detergent components, ingredient c) consists entirely of particles having sizes below 200 Vim, preferably below 175 Vim, with particular preference below 150 Vim, and in particular below 100 Vim.
Appropriate ingredients c) are all substances which are solid and which satisfy the aforementioned particle size criterion. The term "solid" in this context denotes that the ingredient c) remains solid even at the processing temperatures of ingredients a) to d) and does not, for instance, melt during the preparation of melts or become dissolved in other ingredients. Preference is given to the use as ingredient c) of substances whose melting point lies well above the melting point of the detergent component, for example, at least 10°C above, preferably at least 25°C above, and in particular at least 50°C
above. It may also be preferable to use substances which are unmeltable at conventional temperatures as ingredient c) .
Compounds which have proven particularly suitable as ingredient c), in addition to inorganic solvents, mineral substances such as silicates, silicas, alumino-silicates, organic solids, etc., are the alkali metal salts of organic acids, preference being given to the sodium and potassium salts. Examples of suitable organic acids whose salts are preferred ingredients c) are formic acid, acetic acid, propionic acid, succinic acid, citric acid, fumaric acid, oxalic acid, malonic acid, tartaric acid, etc. Particularly preferred detergent components comprise as ingredient c) alkali metal salts of organic acids, preferably alkali metal acetates, and in particular potassium acetate.

A further preferred group of substances which may be used as ingredient c) are clay minerals. In this context, the natural, or chemically modified, clay minerals may be used. Particularly preferred clay minerals are the bentonites, which in the context of the present invention are highly suitable ingredients c).
Bentonites are impure clays formed through the weathering of volcanic tuffs. The properties of the bentonites may be modified to accord with the intended use. Bentonites occur frequently as a clay constituent in tropical soils and are extracted as sodium bentonite, for example, in V,lyoming. Sodium bentonite has the most favorable performance properties, and so its use is preferred in the context of the present invention. Naturally occurring calcium bentonites come, for example, from Mississippi or Texas, or from Landshut, Germany. The Ca bentonites obtained from nature are converted artificially, by exchanging Ca for Na, into the more swellable Na bentonites.
The principal constituents of the bentonites are formed by what are known as montmorillonites, which may also be used in pure form in the context of the present invention. Montmorillonites are clay minerals which belong to the phyllosilicates and, among these, to the dioctahedral smectites, and crystallize in monoclinic pseudohexagonal forms. Montmorillonites form predominantly white, grayish white to yellowish compositions which appear completely amorphous, are readily friable, swell in water but do not become plastic, and may be prescribed by the general formulae A12 [ (OH) 2/Si401o1 ~ nHzO or A1203 ~ 4Si02 ~ Hz0 ~ nHzO or A12 [ (OH) 2/Si401o1 (dried at 150°) .

Montmorillonites possess a three-layer structure consisting of two tetrahedron layers which are electrostatically crosslinked via the cations of an intermediate octahedron layer. The layers are not connected rigidly but instead are able to swell by reversible intercalation of water (from 2-7 times the amount) and other substances such as, for example, alcohols, glycols, pyridine, a-picoline, ammonium compounds, hydroxy-aluminosilicate ions, etc. Th.e formulae indicated above represent only approximate formulae, since montmorillonites possess a high ion exchange capacity. Thus A1 may be exchanged for Mg, Fez+, Fe3+, Zn, Cr, Cu and other ions . As a consequence of such substitution, there is a resulting negative charge in the layers, which is compensated by other cations, especially Na+ and Caz+ .
The structure of the phyllosilicates, in which a central layer of octahedrally coordinated cations is surrounded by 2 layers of [(Si,Al)04] tetrahedra, like a sandwich, may be varied widely by means of numerous substitutions in the octahedron layer. Thus the octahedron layer may include, in addition to the usually predominant A13+
(montmorillonite - dioctahedral phyllosilicate), for example, also Mgz+ (saponite -trioctahedral phyllosilicate) or Fe3+ (nontronite - dioctahedral phyllosilicate). Also present, in addition, are cations such as Znz+ (in the case of sauconite - trioctahedral phyllosilicate), Niz+ (nickel sauconite - trioctahedral phyllosilicate), and Li+ (hectorite - trioctahedral phyllosilicate). Substitutions in the tetrahedron layer as well may be observed; for instance, Si4+ may be replaced in part by A13+ (in the case of beidellite -dioctahedral phyllosiliate) and also by Fe3+ (in the case of nontronite - dioctahedral phyllosilicate). These substitutions result in a charge imbalance, which is compensated by exchangeable cations, commonly sodium, calcium and potassium, and also magnesium, between the layer assemblies.
General formulae which may be given are, therefore, for dioctahedral phyllosilicates (K, Ca, Na, Mg) i+ [Si4_X (A1, Fe3+) XOlo] [ (A1, Fe3+) z_Y (Mg, Fez') y+Z
(OH) zl where i - approximately 0.6 to 0.2 per Olo(OH)2 and also i - x + y - 2z, and for trioctahedral phyllosilicates (K, Ca, Na, Mg) 1+ [Si4_XAlXOlol [Mg, Fe2+) 3_y (Al, Fe3+) y_Z (OH) 2l where i - x - y + 3 z and 0 . 6 < i < 0 . 2 .
Preference is given in the context of the present invention to the use of bentonites in the classic sense, i.e., clays having a high montmorillonite content.
Preferred ingredients c) are phyllosilicates having a montmorillonite content of more than 60% by weight, preferably more than 75% by weight, and in particular more than 90% by weight, based in each case on the weight of the phyllosilicate.
Where this is undesirable for reasons of cost, it is also possible with preference to use pure montmorillonites.
Detergent components comprising, as bentonite, pure montmorillonites are likewise preferred in accordance with the invention.
The layer spacing of phyllosilicates may be modified by the incorporation of certain compounds, since they are able - depending on the charge of the elementary layers and on the intermediate-layer canons - to swell, i.e., to increase the basic spacing of their three-layer assemblies to more than 15 A through intercalation of water molecules or long-chain organic molecules. Thus it is also possible, in accordance with the invention, to use chemically modified bentonites as ingredient c), preference being given to detergent components comprising bentonites modified by quaternary ammonium compounds.
Detergent components which are preferred in the context of the present invention comprise as ingredient c) substances from the group of the clay minerals, preferably of the chemically modified clay minerals, and in particular of the hydrophobicized bentonites.
Further solids preferred for use as ingredient c) in the context of the present invention are ionic surfactants, provided they have a sufficiently high melting point and may be brought to the stated particle size range. These surfactants were described in detail earlier on above.
Fatty alcohol sulfates, in particular, are preferred ingredients c) , so that preference is given to detergent components comprising as ingredient c) anionic surfactant(s), preferably fatty alcohol sulfates, and in particular Cla-is fatty alcohol sulfates.
The detergent components of the invention may preferably comprise, as ingredient d), further active substances and/or auxiliaries from the groups of the dyes, fragrances, soil release polymers, corrosion inhibitors, enzymes, bleaches, bleach activators, and complexing agents, in amounts of from 0 to 10% by weight, preferably from 0.25 to 7.5% by weight, with particular preference from 0.5 to 5% by weight, and in particular from 0.75 to 2.5% by weight. Dyes and fragrances, and the other substances mentioned, are customary ingredients of detergents and are described in detail later on below.

As already mentioned earlier on above, the physical and chemical properties of the detergent components of the invention may be varied through a suitable choice of the ingredients a) to d). If, for example, only ingredients that are liquid at the melting temperature of the mixture are used, then it is easy to prepare single-phase mixtures, which are notable for particular storage stability even in the molten state. The addition of solids, such as color pigments or substances having higher melting points, for example, leads automatically to two-phase mixtures, which, however, likewise exhibit excellent storage stability and an extremely low propensity to separate.
Independently of the composition of the detergent components of the invention, preference is given to detergent components having a melting point of between 50 and 80°C, preferably between 52.5 and 75°C, and in particular between 55 and 65°C.
At room temperature, the detergent components of the invention are solidified mixtures of the abovementioned ingredients, which may take on any external form whatsoever. It is also possible to apply the mixtures in melt form to support materials and so provide support-based detergent components which consist at room temperature of support materials) and a melt solidified on said support materials. Suitable support materials are all solids which do not soften at the temperature of the melt and which, furthermore, have a sufficiently great absorption capacity for the melt. Particularly preferred support materials are builders, which are described in detail later on below.

The present invention additionally provides a process for preparing particulate detergent components, which comprises applying a melt comprising a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substances) having a melting point above 30°C
and a water solubility of less than 20 g/1 at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries to one or more support materials and shaping the mixture.
In this process variant, first of all a melt is prepared, which may include further active substances and auxiliaries. This melt is applied to a support material and shaped as a mixture with said support material.
With the abovementioned preparation process for the rinse aid particles of the invention, preferred process variants are those wherein the meltable substance accounts for from 25 to 85% by weight, preferably from 30 to 70% by weight, and in particular from 40 to 50% by weight of the melt.
The application of the melt to the support material may be conducted in all customary mixing equipment. The shaping step for the mixture of melt and support material is likewise not subject to any technical restriction, so that here as well the skilled worker is able to select from the processes customary to him or her. In the course of experiments conducted by the applicant, processes which have proven preferable are those wherein the shaping takes place by granulating, compacting, pelletizing, extruding, or tableting.

The process of the invention embraces the application of melts comprising the ingredients a) to d) to support materials. In principle, melt and support materials) may be present in varying amounts in the resultant rinse aid particles. In preferred processes, the mixture shaped comprises from 5 to 50% by weight, preferably from 10 to 45% by weight, with particular preference from 15 to 40%
by weight, and in particular from 20 to 35% by weight of a melt comprising the ingredients a) to d), and from 50 to 95% by weight, preferably from 55 to 90% by weight, with particular preference from 60 to 85% by weight, and in particular from 65 to 80% by weight, of support material ( s ) .
Regarding the ingredients which are used in the process of the invention and are processed to the support-based detergent components of the invention, the comments made earlier on above apply analogously.
The detergent components of the invention may also be formulated without support material, so that they consist solely of the ingredients a) to d). In this case, for the preparation of particulate detergent components of the invention, grilling, pelletizing and flaking by means of cooling rolls have proven particularly suitable.
The present invention therefore additionally provides, in a first embodiment, a process for preparing grilled detergent components, which comprises spraying a melt comprising a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substances) having a melting point above 30°C
and a water solubility of less than 20 g/1 at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries into a cold gas stream.
The process of the invention, which is referred to for short as prilling, comprises the production of granular elements from meltable substances, the melt comprising the ingredients a) to d) being sprayed in defined droplet size at the top of a tower, solidifying in free fall, and being obtained as prill granules at the base of the tower.
As the cold gas stream it is possible in very general terms to use all gases, the temperature of the gas being below the melting temperature of the melt. In order to avoid long falling sections, use is frequently made of cooled gases, for example, supercooled air or even liquid nitrogen, which is injected through a nozzle into the spray towers.
The particle size of the resulting prills may be varied by way of the choice of droplet size, with particle sizes which are easy to realize technically lying within the range from 0.5 to 2 mm, preferably around 1 mm.
An alternative process to prilling is pelletizing. A
further embodiment of the present invention therefore envisages a process for preparing pelletized detergent components, which comprises metering a melt comprising a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substances) having a melting point above 30°C
and a water solubility of less than 20 g/1 at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries onto cooled pelletizing plates.
Pelletizing comprises the metering of the melt comprising the respective ingredients onto a (cooled) belt or onto rotating, inclined plates which have a temperature below the melting temperature of the melt and are preferably cooled to below room temperature. Here again, process variants may be practiced in which the pelletizing plates are supercooled. In this case, however, measures must be taken to counter the condensation of atmospheric moisture.
Pelletizing produces relatively large particles, which in standard industrial processes have sizes of between 2 and 10 mm, preferably between 3 and 6 mm.
As an even more cost-effective variant for producing particulate detergent components of the stated composition from melts, the use of cooling rolls is appropriate. A further subject of the present invention is therefore a process for preparing particulate detergent components, which comprises applying a melt comprising a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substances) having a melting point above 30°C
and a water solubility of less than 20 g/1 at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries by spraying or otherwise to a cooling roll, scraping off the solidified melt, and comminuting the scrapings if necessary.

The use of cooling rolls permits ready establishment of the desired particle size range, which in this process of the invention may also be below 1 mm, for example from 200 to 700 ~,m.
Of course, it is also possible in accordance with the invention to compress the particulate compositions to a tablet or a region thereof. This tablet may then be dosed by the user, for example; alternatively, it may be added to compositions which are in powder form. Another possibility is to use the particulate compositions, especially the prills, pellets or products from the cooling roll, as a tabletable premix and to use this in the preparation of multiphase tablets. Here, compressing then gives, for example, multilayer tablets of which one layer has the composition of a conventional detergent tablet, the other layer the composition of the detergent component of the invention, which displays its advantageous nature in this commercial form as well.
Multiphase tablets may also be prepared by producing tablets having cavities, for example, depressions or continuous holes, and then filling these cavities with other tablets. In the present case, it has been found appropriate for the "base tablet", i.e., the tablet having a cavity, to possess the composition of a detergent tablet while the tablet present in the cavity is a tablet which has been pressed from prills, pellets or flakes. The adhesion of the two tablets to one another may be achieved by adhesive bonding of the two tablets;
alternatively, it is possible to press the tablets onto or into one another. Also possible is plugging, where adhesion is brought about by the geometric design of cavity and filling.

A preferred preparation process is, for example, the preparation of the tablets by separate preparation (compressing) of a base tablet a) and a core tablet b), which is preferably pressed from prills of the detergent components of the invention, followed by the joining and the final compression of both parts.
The preparation of tablets from particulate detergent components of the invention may take place in accordance with common tableting procedures. These are described in detail later on below.
The tablets may be produced in predetermined three-dimensional forms and predetermined sizes. Suitable three-dimensional forms are virtually any practicable designs, i.e., for example, bar, rod or ingot form, cubes, blocks and corresponding three-dimensional elements having planar side faces, and in particular cylindrical designs with a circular or oval cross section. This latter design covers forms ranging from tablets through to compact cylinders having a height-to-diameter ratio of more than 1.
The produced tablet may take on any geometric form whatsoever, with particular preference being given to concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder-segmentlike, discoid, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal-, heptagonal- and octagonal-prismatic, and rhombohedral forms. It is also possible to realize completely irregular outlines such as arrow or animal forms, trees, clouds, etc. If the produced tablet has corners and edges, these are preferably rounded off. As an additional visual differentiation, an embodiment having rounded corners and beveled (chamfered) edges is preferred.

The detergent components of the invention may be given directly to the consumer, who then doses them into the detergent additionally as required. On the basis of this additional dosing step, however, apart from the solid supply form and the addition in the same dosing draw, the advantages relative to liquid rinse aids would be minimized. It is therefore preferred to admix the detergent components of the invention to particulate machine dishwashing compositions or to incorporate them into tablets.
The present invention therefore additionally provides for the use of particulate detergent components comprising a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substances) having a melting point above 30°C
and a water solubility of less than 20 g/1 at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries in detergents for machine dishwashing.
The present invention further provides a particulate machine dishwashing composition, comprising builders and also, optionally, further detergent ingredients, said composition comprising particulate detergent components comprising, based on their weight, a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substances) having a melting point above 30°C
and a water solubility of less than 20 g/1 at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries.
The ingredients of the machine dishwashing compositions are described hereinbelow. In some cases, they may also be present as ingredient d) or support materials in the detergent components of the invention.
The most important ingredients of machine dishwashing compositions are builders. The machine dishwashing detergents of the invention may comprise all of the builders commonly used in detergents, i.e., in particular, zeolites, silicates, carbonates, organic cobuilders, and - where there are no ecological prejudices against their use - the phosphates as well.
The builders mentioned below are all suitable as support materials for the detergent components of the invention, as set out earlier on above.
Suitable crystalline, layered sodium silicates possess the general formula NaMSIXO2x+1'yF'~2~~ where M is sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20, and preferred values for x are 2, 3 or 4.
Crystalline phyllosilicates of this kind are described, 2.5 for example, in European Patent Application EP-A-0 164 514. Preferred crystalline phyllosilicates of the formula indicated are those in which M is sodium and x adopts the value 2 or 3. In particular, both (3- and 8-sodium disilicates Na2Si205~yHz0 are preferred, (3-sodium disilicate, for example, being obtainable by the process described in International Patent Application WO-A-91/08171.
It is also possible to use amorphous sodium silicates having an Na20:Si02 modulus of from 1:2 to 1:3.3, preferably from 1:2 to 1:2.8, and in particular from 1:2 to 1:2.6, which are dissolution-retarded and have secondary washing properties. The retardation of dissolution relative to conventional amorphous sodium silicates may have been brought about in a variety of ways - for example, by surface treatment, compounding, compacting, or overdrying. In the context of this invention, the term "amorphous" also embraces "X-ray-amorphous". This means that in X-ray diffraction experiments the silicates do not yield the sharp X-ray reflections typical of crystalline substances but instead yield at best one or more maxima of the scattered X-radiation, having a width of several degree units of the diffraction angle. However, good builder properties may result, even particularly good builder properties, if the silicate particles in electron diffraction experiments yield vague or even sharp diffraction maxima. The interpretation of this is that the products have microcrystalline regions with a size of from 10 to several hundred nm, values up to max. 50 nm and in particular up to max. 20 nm being preferred. So-called X-ray-amorphous silicates of this kind, which likewise possess retarded dissolution relative to the conventional waterglasses, are described, for example, in German Patent Application DE-A-44 00 024. Particular preference is given to compacted amorphous silicates, compounded amorphous silicates, and overdried X-ray-amorphous silicates.
The finely crystalline, synthetic zeolite used, containing bound water, is preferably zeolite A and/or P.
A particularly preferred zeolite P is Zeolite MAP~
(commercial product from Crosfield). Also suitable, however, are zeolite X and also mixtures of A, X and/or P. Another product available commercially and able to be used with preference in the context of the present invention, for example, is a cocrystallizate of zeolite X

and zeolite A (approximately 80% by weight zeolite X), which is sold by CONDEA Augusta S.p.A. under the brand name VEGOBOND AX~ and may be described by the formula nNa20~ (1-n) KZO~A12O3~ (2-2 . 5) Si02~ (3 . 5-5. 5) H20.
Suitable zeolites have an average particle size of less than 10 ~,m (volume distribution; measurement method:
Coulter counter) and contain preferably from 18 to 22% by weight, in particular from 20 to 22% by weight, of bound water.
Of course, the widely known phosphates may also be used as builder substances provided such a use is not to be avoided on ecological grounds . Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference being given to pentasodium and pentapotassium triphosphate (sodium and potassium tripolyphosphate, respectively), possess the greatest importance in the detergents industry.
Alkali metal phosphates is the collective term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, among which metaphosphoric acids (HP03)n and orthophosphoric acid H3P04, in addition to higher-molecular-mass representatives, may be distinguished. The phosphates combine a number of advantages: they act as alkali carriers, prevent limescale deposits on machine components, and lime encrustations on fabrics, and additionally contribute to cleaning performance.
Sodium dihydrogen phosphate, NaH2P04, exists as the dehydrate (density 1.91 g cm-3, melting point 60°) and as the monohydrate (density 2.04 g cm-3). Both salts are white powders of very ready solubility in water which lose the water of crystallization on heating and undergo conversion at 200°C into the weakly acidic diphosphate (disodium dihydrogen diphosphate, Na2H2P20~) and at a higher temperature into sodium trimetaphosphate (Na3P309) and Maddrell's salt (see below). NaH2P04 reacts acidically; it is formed if phosphoric acid is adjusted to a pH of 4.5 using sodium hydroxide solution and the slurry is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, PDP) , KHZP04, is a white salt with a density of 2.33 g cm-3, has a melting point of 253° [decomposition with formation of potassium polyphosphate (KP03)X], and is readily soluble in water.
Disodium hydrogen phosphate (secondary sodium phosphate), Na2HP04, is a colorless, crystalline salt which is very readily soluble in water. It exists in anhydrous form and with 2 mol (density 2.066 g cm-3, water loss at 95°), 7 mol (density 1.68 g cm-3, melting point 48° with loss of 5 Hz0), and 12 mol (density 1.52 g cm-3, melting point 35°
with loss of 5 H20) of water, becomes anhydrous at 100°, and if heated more intensely undergoes transition to the diphosphate Na4P20~. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with sodium carbonate solution using phenolphthalein as indicator.
Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate) , KZHP04, is an amorphous white salt which is readily soluble in water.
Trisodium phosphate, tertiary sodium phosphate, Na3P04, exists as colorless crystals which as the dodecahydrate have a density of 1.62 g cm-3 and a melting point of 73-76°C (decomposition), as the decahydrate (corresponding to 19-20% P205) have a melting point of 100°C, and in anhydrous form (corresponding to 39-40%
Pz05) have a density of 2.536 g cm-3. Trisodium phosphate is readily soluble in water, with an alkaline reaction, and is prepared by evaporative concentration of a solution of precisely 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3P04, is a white, deliquescent, granular powder of density 2.56 g cm-3, has a melting point of 1340°, and is readily soluble in water with an alkaline reaction. It is produced, for example, when Thomas slag is heated with charcoal and potassium sulfate. Despite the relatively high price, the more readily soluble and therefore highly active potassium phosphates are frequently preferred in the detergents industry over the corresponding sodium compounds.
Tetrasodium diphosphate (sodium pyrophosphate), Na4P20~, exists in anhydrous form (density 2.534 g cm-3, melting point 988°, 880° also reported) and as the decahydrate (density 1.815-1.836 g cm-3, melting point 94° with loss of water). Both substances are colorless crystals which dissolve in water with an alkaline reaction. Na4P20-, is formed when disodium phosphate is heated to > 200° or by reacting phosphoric acid with sodium carbonate in stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and water hardeners and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K4P20~, exists in the form of the trihydrate and is a colorless, hygroscopic powder of density 2.33 g cm-3 which is soluble in water, the pH of the 1% strength solution at 25° being 10.4.
Condensation of NaH2P04 or of KHZPO4 gives rise to higher-molecular-mass sodium and potassium phosphates, among which it is possible to distinguish cyclic representatives, the sodium and potassium metaphos-phates, and catenated types, the sodium and potassium polyphosphates. For the latter in particular a large number of names are in use: fused or calcined phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are referred to collectively as condensed phosphates.
The industrially important pentasodium triphosphate, Na5P301o (sodium tripolyphosphate), is a nonhygroscopic, white, water-soluble salt which is anhydrous or crystallizes with 6 H20 and has the general formula Na0-[P(O)(ONa)-O]n-Na where n - 3. About 17 g of the anhydrous salt dissolve in 100 g of water at room temperature, about 20 g at 60°, around 32 g at 100°;
after heating the solution at 100°C for two hours, about 8% orthophosphate and 15% diphosphate are produced by hydrolysis. For the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in stoichiometric ratio and the solution is dewatered by spraying. In a similar way to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves numerous insoluble metal compounds (including lime soaps, etc).
Pentapotassium triphosphate, KSP301o (potassium tripolyphosphate), is commercialized, for example, in the form of a 50% strength by weight solution (> 23% Pz05, 25%
K20). The potassium polyphosphates find broad application in the detergents industry. There also exist sodium potassium tripolyphosphates, which may likewise be used for the purposes of the present invention. These are formed, for example, when sodium trimetaphosphate is hydrolyzed with KOH:
(NaP03) 3 + 2 KOH -~ Na3K2P301o + H20 They can be used in accordance with the invention in precisely the same way as sodium tripolyphosphate, potassium tripolyphosphate, or mixtures of these two;
mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate, or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate, or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphospate, may also be used in accordance with the invention.
Organic cobuilders which may be used in the machine dishwashing compositions of the invention are, in particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below), and phosphonates. These classes of substance are described .L5 below.
Organic builder substances which may be used are, for example, the polycarboxylic acids usable in the form of their sodium salts, the term polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. Examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, malefic acid, fumaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable on ecological grounds, and also mixtures thereof. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, and mixtures thereof.
The acids per se may also be used. In addition to their builder effect, the acids typically also possess the property of an acidifying component and thus also serve to establish a lower and milder pH of detergents. In this context, mention may be made in particular of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any desired mixtures thereof.
Also suitable as builders are polymeric poly-carboxylates; these are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, examples being those having a relative molecular mass of from 500 to 70,000 g/mol.
The molecular masses reported for polymeric poly-carboxylates, for the purposes of this document, are weight-average molecular masses, MW, of the respective acid form, determined basically by means of gel permeation chromatography (GPC) using a W detector. The measurement was made against an external polyacrylic acid standard, which owing to its structural similarity to the polymers under investigation provides realistic molecular weight values. These figures differ markedly from the molecular weight values obtained using poly-styrenesulfonic acids as the standard. The molecular masses measured against polystyrenesulfonic acids are generally much higher than the molecular masses reported in this document.
Suitable polymers are, in particular, polyacrylates, which preferably have a molecular mass of from 2000 to 20,000 g/mol. Owing to their superior solubility, preference in this group may be given in turn to the short-chain polyacrylates, which have molecular masses of from 2000 to 10,000 g/mol, and with particular preference from 3000 to 5000 g/mol.
Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with malefic acid.
Copolymers which have been found particularly suitable are those of acrylic acid with malefic acid which contain from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight of malefic acid. Their relative molecular_ mass, based on free acids, is generally from 2000 to 70,000 g/mol, preferably from 20,000 to 50,000 g/mol, and in particular from 30,000 to 40,000 g/mol.
The (co)polymeric polycarboxylates can be used either as powders or as aqueous solutions. The (co)polymeric polycarboxylate content of the compositions is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.
In order to improve the solubility in water, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, for example, as monomers.
Particular preference is also given to biodegradable polymers comprising more than two different monomer units, examples being those comprising, as monomers, salts of acrylic acid and of malefic acid, and also vinyl alcohol or vinyl alcohol derivatives, or those comprising, as monomers, salts of acrylic acid and of 2-alkylallylsulfonic acid, and also sugar derivatives.
Further preferred copolymers have as their monomers preferably acrolein and acrylic asid/acrylic acid salts, and, respectively, acrolein and vinyl acetate.
Similarly, further preferred builder substances that may be mentioned include polymeric amino dicarboxylic acids, their salts or their precursor substances. Particular preference is given to polyaspartic acids and their salts and derivatives, which have not only cobuilder properties bLlt also a bleach-stabilizing action.

Further suitable builder substances are polyacetals, which may be obtained by reacting dialdehydes with polyol carboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and/or glucoheptonic acid.
Further suitable organic builder substances are dextrins, examples being oligomers and polymers of carbohydrates, which may be obtained by partial hydrolysis of starches.
The hydrolysis can be conducted by customary processes;
for example, acid-catalyzed or enzyme-catalyzed processes. The hydrolysis products preferably have average molecular masses in the range from 400 to 500,000 g/mol. Preference is given here to a polysaccharide having a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide in comparison to dextrose, which possesses a DE of 100. It is possible to use both maltodextrins having a DE of between 3 and 20 and dried glucose syrups having a DE of between 20 and 37, and also so-called yellow dextrins and white dextrins having higher molecular masses, in the range from 2000 to 30,000 g/mol.
The oxidized derivatives of such dextrins comprise their products of reaction with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. A
product oxidized at C6 of the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylenediamine N,N'-disuccinate (EDDS) is used preferably in the form of its sodium or magnesium salts. Further preference in this context is given to glycerol disuccinates and glycerol trisuccinates as well. Suitable use amounts in formulations containing zeolite and/or silicate are from 3 to 15% by weight.
Examples of further useful organic cobuilders are acetylated hydroxy carboxylic acids and their salts, which may also, if desired, be present in lactone form and which contain at least 4 carbon atoms, at least one hydroxyl group, and not more than two acid groups.
A further class of substance having cobuilder properties is represented by the phosphonates. The phosphonates in question are, in particular, hydroxyalkane- and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphos-phonate (HEDP) is of particular importance as a cobuilder. It is used preferably as the sodium salt, the disodium salt being neutral and the tetrasodium salt giving an alkaline (pH 9) reaction. Suitable aminoalkanephosphonates are preferably ethylenediamine-tetramethylenephosphonate (EDTMP), diethylenetriamine-pentamethylenephosphonate (DTPMP), and their higher homologs. They are used preferably in the form of the neutrally reacting sodium salts, e.g., as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. As a builder in this case, preference is given to using HEDP from the class of the phosphonates.
Furthermore, the aminoalkanephosphonates possess a pronounced heavy metal binding capacity. Accordingly, and especially if the compositions also contain bleach, it may be preferred to use aminoalkanephosphonates, exper_ially DTPMP, or to use mixtures of said phosphonates.
Furthermore, all compounds capable of forming complexes with alkaline earth metal ions may be used as cobuilders.
Preferred particulate machine dishwashing compositions of the invention comprise builders in amounts of from 20 to 80% by weight, preferably from 25 to 75% by weight, and in particular from 30 to 70% by weight, based in each case on the weight of the composition.
Important ingredients of detergents in addition to the builders are, in particular, substances from the groups of the surfactants, bleaches, bleach activators, enzymes, polymers, fragrances, and dyes. Important representatives from the aforementioned classes of substance are described below, reference being made to the remarks earlier on above in respect of the description of the surfactants.
Preferred particulate machine dishwashing compositions further comprise one or more substances from the groups of the bleaches, bleach activators, bleaching catalysts, surfactants, corrosion inhibitors, polymers, dyes, fragrances, pH modifiers, complexing agents, and enzymes.
Among the compounds used as bleaches which yield H202 in water, particular importance is possessed by sodium percarbonate. Examples of further bleaches which may be used are sodium perborate tetrahydrate and sodium perborate monohydrate, peroxy pyrophosphates, citrate perhydrates, and also Hz02-donating peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid, or diperdodecanedioic acid.

"Sodium percarbonate" is a term used unspecifically for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (i.e., salts of percarbonic acid) but rather hydrogen peroxide adducts onto sodium carbonate. The commercial product has the average composition 2 Na2C03 ~ 3 H202 and is thus not a peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder of density 2.14 g cm-3 which breaks down readily into sodium carbonate and oxygen having a bleaching or oxidizing action.
Sodium carbonate peroxohydrate was first obtained in 1899 by precipitation with ethanol from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as a peroxycarbonate. Only in 1909 was the compound recognized as the hydrogen peroxide addition compound; nevertheless, the historical name "sodium percarbonate" has persisted in the art.
Industrially, sodium percarbonate is produced predominantly by precipitation from aqueous solution (known as the wet process). In this process, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by means of salting agents (predominantly sodium chloride), crystallizing aids (for example polyphosphates, polyacrylates), and stabilizers (for example, Mg2+ ions).
The precipitated salt, which still contains from 5 to 12%
by weight of the mother liquor, is subsequently centrifuged and dried in fluidized-bed driers at 90°C.
The bulk density of the finished product may vary between 800 and 1200 g/1 according to the production process.
Generally, the percarbonate is stabilized by an additional coating. Coating processes, and substances used for the coating, are amply described in the patent literature. Fundamentally, it is possible in accordance with the invention to use all commercially customary percarbonate types, as supplied, for example, by the companies Solvay Interox, Degussa, Kemira or Akzo.
Detergents of the invention may also comprise bleaches from the group of organic bleaches. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide, for example. Further typical organic bleaches are the peroxy acids, particular examples being the alkyl peroxy acids and the aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, s-phthalimidoperoxy caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenyl-amidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxy dicarboxylic acids, such as 1,12-diperoxydecanedicarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid and N,N-terephthaloyldi(6-aminopercaproic acid) may also be used.
Bleaches in the detergents of the invention for machine dishwashing may also be substances which release chlorine or bromine. Among the suitable chlorine- or bromine-releasing materials, examples include heterocyclic N-bromoamides and N-chloroamides, examples being trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or salts thereof with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin, are likewise suitable.
In order to achieve a "post-bleaching" effect, the abovementioned bleaches may also be introduced into the machine dishwashing compositions of the invention in part by way of the detergent components of the invention, where they represent the ingredient d).
Bleach activators, which boost the action of the bleaches, are, for example, compounds containing one or more N-acyl and/or O-acyl groups, such as substances from the class of the anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylene-diamine TAMD, and tetraacetylhexylenediamine TAHD, and also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine DADHT, and isatoic anhydride ISA.
Bleach activators which may be used are compounds which under perhydrolysis conditions give rise to aliphatic peroxo carboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or substituted or unsubstituted perbenzoic acid. Suitable substances are those which carry 0-acyl and/or N-acyl groups of the stated number of carbon atoms, and/or substituted or unsubstituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, N-methylmorpholiniumacetonitrile methyl sulfate (MMA), and the enol esters known from German Patent Applications DE
196 16 693 and DE 196 16 767, and also acetylated sorbitol and mannitol and/or mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactams, for example, N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are likewise used with preference. Combinations of conventional bleach activators may also be used.
In addition to the conventional bleach activators, or instead of them, it is also possible to incorporate what are known as bleaching catalysts into the machine dishwashing detergents. These substances are bleach-boosting transition metal salts or transition metal complexes such as, for example, Mn-, Fe-, Co-, Ru- or Mo-salen complexes or -carbonyl complexes. Other bleaching catalysts which can be used include Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands, and also Co-, Fe-, Cu- and Ru-ammine complexes.
Preference is given to the use of bleach activators from the group of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acyl imides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), N-methylmorpholiniumacetonitrile methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular from 0.1% by weight to 8% by weight, more particularly from 2 to 8% by weight, and with particular preference from 2 to 6% by weight, based on the overall composition.
Bleach-boosting transition metal complexes, especially those with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, preferably selected from the group of manganese and/or cobalt salts and/or complexes, with particular preference from cobalt ammine complexes, cobalt acetate complexes, cobalt carbonyl complexes, the chlorides of cobalt or manganese, and manganese sulfate, are used in customary amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight, and with particular preference from 0.01% by weight to 0.25% by weight, based in each case on the overall composition. In specific cases, however, it is also possible to use a greater amount of bleach activator.
Suitable enzymes in the detergents of the invention include in particular those from the classes of the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases, and mixtures of said enzymes. All of these hydrolases contribute to removing stains, such as proteinaceous, fatty or starchy marks. For bleaching, it is also possible to use oxidoreductases. Especially suitable enzymatic active substances are those obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens, and also from genetically modified variants thereof. Preference is given to the use of proteases of the subtilisin type, and especially to proteases obtained from Bacillus lentus. Of particular interest in this context are enzyme mixtures, examples being those of protease and amylase or protease and lipase or lipolytic enzymes, or of protease, amylase and lipase or lipolytic enzymes, or protease, lipase or lipolytic enzymes, but especially protease and/or lipase-containing mixtures or mixtures with lipolytic enzymes.
Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proven suitable in some cases. The suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases, and pectinases.
The enzymes may be adsorbed on carrier substances or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules may be, for example, from about 0 . 1 to 5 % by weight, preferably from 0.5 to about 4.5% by weight.
Dyes and fragrances may be added to the machine dishwashing compositions of the invention in order to enhance the esthetic appeal of the products which are formed and to provide the consumer with not only the performance but also a visually and sensorially "typical and unmistakable" product. As perfume oils and/or fragrances it is possible to use individual odorant compounds, examples being the synthetic products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon types. Odorant compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethyl-benzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allyl cyclo-hexylpropionate, styrallyl propionate, and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, a-isomethylionone and methyl cedryl ketone; the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol, and terpineol; the hydrocarbons include primarily the terpenes such as limonene and pinene. Preference, however, is given to the use of mixtures of different odorants, which together produce an appealing fragrance note. Such perfume oils may also contain natural odorant mixtures, as obtainable from plant sources, examples being pine oil, citrus oil, jasmine oil, patchouli oil, rose oil or ylang-ylang oil.
Likewise suitable are clary sage oil, camomile oil, clove oil, balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniperberry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and also orange blossom oil, neroli oil, orange peel oil, and sandalwood oil.
The fragrances may be incorporated directly into the detergent of the invention; alternatively, it may be advantageous to apply the fragrances to carriers.
Materials which have become established as such carriers are, for example, cyclodextrins, it being possible in addition for the cyclodextrin-perfume complexes to be additionally coated with further auxiliaries.
Incorporating the fragrances as ingredient d) into the detergent components of the invention is also possible, and results in a fragrance sensation when the machine is opened.
In order to enhance the esthetic appeal of the compositions of the invention, they (or parts thereof) may be colored with appropriate dyes. Preferred dyes, whose selection presents no difficulty whatsoever to the skilled worker, possess a high level of storage stability and insensitivity to the other ingredients of the compositions or to light and possess no pronounced affinity for the substrates to be treated with the compositions, such as glass, ceramic, or plasticware, so as not to stain them.
The detergents of the invention may include corrosion inhibitors for protecting the ware or the machine, with special importance in the field of machine dishwashing being possessed, in particular, by silver protectants.
The known substances of the prior art may be used. In general it is possible to use, in particular, silver protectants selected from the group consisting of triazoles, benzotriazoles, bisbenzotriazoles, amino-triazoles, alkylaminotriazoles, and transition metal salts or transition metal complexes. Particular preference is given to the use of benzotriazole and/or alkylaminotriazole. Frequently encountered in cleaning formulations, furthermore, are agents containing active chlorine, which may significantly reduce corrosion of the silver surface. In chlorine-free cleaners, use is made in particular of oxygen-containing and nitrogen-containing organic redox-active compounds, such as divalent and trivalent phenols, e.g. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol, and derivatives of these classes of compound.
Inorganic compounds in the form of salts and complexes, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, also find frequent application. Preference is given in this context to the transition metal salts selected from the group consisting of manganese and/or cobalt salts and/or complexes, with particular preference cobalt ammine complexes, cobalt acetato complexes, cobalt carbonyl complexes, the chlorides of cobalt or of manganese and manganese sulfate. Similarly, zinc compounds may be used to prevent corrosion on the ware.

The particulate machine dishwashing compositions of the invention may comprise the detergent components of the invention in varying amounts, the amount being higher or lower depending on the composition of the detergent components and on the desired success. Preferred particulate machine dishwashing compositions comprise the particulate detergent component in amounts of from 0.5 to 30% by weight, preferably from 1 to 25% by weight, and in particular from 3 to 15% by weight, based in each case on overall composition.
In terms of their composition, the detergent components of the invention may be designed so that they dissolve to a minor extent, if at all, in the main wash cycle (and also in optional prewash. cycles). This ensures that the surfactants are not released until the rinse cycle, where they develop their action. In addition to this chemical formulation, a physical formulation may be necessary depending on the type of dishwasher, so that the rinse aid particles are not pumped off in the machine when the water is changed and hence are no longer available for the rinse cycle. Standard domestic dishwashers, upstream of the detergent-liquor pump, which pumps the water or cleaning solution from the machine after the individual cleaning cycles, comprise a sieve insert, intended to prevent clogging of the pump by food residues. If the user cleans heavily soiled kitchen- and tableware, then this sieve insert requires regular cleaning, which is a simple operation owing to the ease of access and removability. The detergent components of the invention, then, are preferably designed in terms of their size and shape such that they do not pass through the sieve insert of the dishwasher even after the cleaning cycle, i.e., after exposure to agitation in the machine and to the detergent solution. This ensures that detergent components are present in the dishwasher in the rinse cycle, these detergent components releasing the active substance (s) under the action of the warmer water and so bringing the desired rinse effect. Particulate machine dishwashing compositions that are preferred in the context of the present invention are those wherein the particulate detergent component has particle sizes of between 1 and 40 mm, preferably between 1.5 and 30 mm, and in particular between 2 and 20 mm.
In the dishwashing compositions of the invention, the detergent components, having the sizes stated above, may project from the matrix of the other particulate ingredients; alternatively, the other particles may likewise have sizes within the stated range, so that, overall, a detergent is formulated that comprises large detergent particles and detergent-component particles.
Especially if the detergent components of the invention are colored, i.e., have red, blue, green, or yellow color, for example, it is advantageous for the appearance of the product, i.e., of the overall detergent, if the detergent components are visibly larger than the matrix comprising the particles of the other ingredients of the detergent. Here, preference is given to inventive particulate machine dishwashing compositions which (without taking into account the particulate detergent component) have particle sizes of between 100 and 3000 ~,m, preferably between 300 and 2500 ~,m, and in particular between 400 and 2000 ~.m.
If the detergents of the invention are formulated as a powder mixture, then - especially if there are large differences between the size of detergent component and detergent matrix - on the one hand partial separation may occur when the pack is shaken, and on the other hand dosing may be different in two successive washing operations, since the user does not always automatically dose equal quantities of the detergent and detergent component. If it is desired technically to use an identical quantity for each washing operation, this can be realized by the packaging - familiar to the skilled worker - of the compositions of the invention in water-soluble film bags. The present invention also provides a particulate machine dishwashing composition wherein one dose unit is welded in a water-soluble film bag.
By this means, the user need only insert a bag, containing for example a detergent powder and a plurality of visually distinctive detergent-component particles, into the dosing drawer of his or her dishwasher. This embodiment of the present invention is therefore a visually attractive alternative to conventional detergent tablets.
Since the user does not use only particulate detergents for machine dishwashing, but would also like to have recourse to tablets, these are further provided by the present invention. For this purpose, the melt comprising the ingredients a) to d) may be formulated as a phase of a tablet, said phase possessing, for example, the form of layer, corelike insert, etc.
The present invention thus further provides a multiphase detergent tablet for machine dishwashing, comprising builders and also, optionally, further detergent ingredients, wherein at least one phase comprises a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substances) having a melting point above 30°C
and a water solubility of less than 20 g/1 at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries.
In the context of the present invention, the individual phases of the tablet may have different three-dimensional forms. The simplest embodiment is that of two-layer or multilayer tablets, each layer of the tablet constituting one phase. In accordance with the invention, however, it is also possible to prepare multiphase tablets in which individual phases have the form of inclusions into (an)other phase(s). In addition to so-called "ring-core"
tablets, possible examples include laminated tablets or combinations of the stated embodiments. Examples of multiphase tablets can be found in the figures of EP-A-055 100 (Jeyes), which describes toilet cleaning blocks. The most widespread three-dimensional form in the art at present for multiphase tablets is the two-layer or multilayer tablet. In the context of the present invention, therefore, it is preferred for the phases of the tablet to have the form of layers and for the tablet to have 2, 3 or 4 phases.
The tablets of the invention may take on any geometric form whatsoever, with particular preference being given to concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder-segmentlike, discoid, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal-, heptagonal- and octagonal-prismatic, and rhombohedral forms. It is also possible to realize completely irregular outlines such as arrow or animal forms, trees, clouds, etc. If the tablets of the invention have corners and edges, these are preferably rounded off. As an additional visual differentiation, an embodiment having rounded corners and beveled (chamfered) edges is preferred.

_ CA 02318000 2000-09-11 Instead of the layer structure, it is also possible to prepare tablets which comprise the detergent component of the invention in the form of other phases. Here, it has been found suitable to prepare base tablets which have one or more cavities, and to insert the melt comprising ingredients a) to d) of the detergent component of the invention into the cavity and allow it to solidify therein. This preparation process produces preferred multiphase detergent tablets comprising a base tablet, which has a cavity, and a part present at least partially in the cavity.
The cavity in the compressed part of such tablets of the invention may have any form whatsoever. It may go right through the tablet, i.e., have an opening on different sides, for example, at the top and bottom side, of the tablet; alternatively, it may be a cavity which does not go through the entire tablet, and whose opening is visible only on one tablet side. The form of the cavity may also be chosen freely within wide limits. For reasons of process economy, continuous holes whose openings are located on opposite faces of the tablets, and depressions having an opening at one tablet side, have become established. In preferred detergent tablets, the cavity has the form of a continuous hole whose openings are located on two opposite tablet surfaces. The form of a continuous hole of this kind may be chosen freely, preference being given to tablets wherein the continuous hole has circular, ellipsoid, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal horizontal sections. It is also possible to realize completely irregular hole shapes, such as arrow or animal forms, trees, clouds, etc. As with the tablets, preference is given, in the case of angular holes, to those having rounded corners and edges or having rounded corners and chamfered edges.

The abovementioned geometric embodiments may be combined with one another as desired. For instance, it is just as possible to prepare tablets having a rectangular or square outline and circular holes as it is to prepare circular tablets having octagonal holes, there being no limits on the diversity of possible combinations. For reasons of process economy and the esthetic perception of the user, particular preference is given to tablets with a hole, where the tablet outline and the hole cross section have the same geometric form, examples being tablets having a square outline and a square hole made centrally therein. Particular preference is given in this context to annular tablets, i.e., circular tablets with a circular hole.
If the aforementioned principle of the hole open at twc opposite tablet sides is reduced to an opening, depression tablets are obtained. Detergent tablets of the invention wherein the cavity has the form of a depression are likewise preferred. With this embodiment, as with the "hole tablets", the tablets of the invention may take on any geometric form whatsoever, with particular preference being given to concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder-segmentlike, discoid, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal-, heptagonal- and octagonal-prismatic, and rhombohedral forms. It is also possible to realize completely irregular outlines such as arrow or animal forms, trees, clouds, etc. If the tablet has corners and edges, these are preferably rounded off. As additional visual differentiation, an embodiment having rounded corners and beveled (chamfered) edges is preferred.

The form of the depression may also be chosen freely, preference being given to tablets in which at least one depression may take on a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder-segmentlike, discoid, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal-, heptagonal- and octagonal-prismatic, or rhombohedral form. It is also possible to realize completely irregular depression forms, such as arrow or animal forms, trees, clouds, etc. As with the tablets, depressions having rounded corners and edges or having rounded corners and chamfered edges are preferred.
In the case set out above, the part present at least partially in the cavity consists solely of ingredients a) to d) of the detergent components. It is, however, also possible to introduce support material-based detergent components into the cavity (cavities). For reasons of process economy, however, preference is given to multiphase detergent tablets wherein the part present in the cavity comprises a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substances) having a melting point above 30°C
and a water solubility of less than 20 g/1 at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries.
The size of the depression or continuous hole in comparison to the total tablet is guided by the desired end use of the tablets. Depending on with how much further active substance the remaining void volume is to be filled, and on whether a smaller or larger amount of detergent component is to be present, the size of the cavity may vary. Irrespective of the end use, in preferred detergent tablets the volume ratio of compressed part ("base tablet") to detergent component is from 2:1 to 100:1, preferably from 3:1 to 80:1, with particular preference from 4:1 to 50:1, and in particular from 5:1 to 30:1.
Besides the stated volume ratio, it is also possible tc state a mass ratio of the two parts, the two values correlating to one another by way of the densities of the base tablet and, respectively, of the detergent component. Irrespective of the density of the individual parts, preference is given to detergent tablets of the invention wherein the weight ratio of base tablet to detergent component is from 1:1 to 100:1, preferably from 2:1 to 80:1, with particular preference from 3:1 to 50:1, and in particular from 4:1 to 30:1.
Analogous details may also be given for the surfaces visible in each case of the base tablet and, respectively, of the detergent component. Here, preference is given to detergent tablets wherein the outwardly visible surface area of the detergent component accounts for from 1 to 25%, preferably from 2 to 20%, with particular preference from 3 to 15%, and in particular from 4 to 10%, of the total surface area of the tablet.
The detergent component and the base tablet are preferably colored so as to be visually distinguishable.
In addition to visual differentiation, performance advantages may be obtained by virtue of different solubilities of the different regions of the tablet.
Detergent tablets in which the detergent component dissolves more rapidly than the base tablet are preferred in accordance with the invention. By incorporating certain constituents, on the one hand, it is possible to accelerate specifically the solubility of the detergent component; secondly, the release of certain ingredients from the detergent component may lead to advantages in the washing or cleaning process.
Preference is also given, of course, to detergent tablets of the invention wherein the detergent component dissolves later in the wash program than the base tablet.
Performance advantages from this retarded release may be achieved, for example, by using a slower-dissolving detergent component to release active substances) only in later cycles. Thus in the case of machine dishwashing, for example, it can be ensured by means of slower-dissolving detergent components that further active substances) is(are) available in the rinse cycle. By means of additional substances such as nonionic surfactants, acidifiers, soil release polymers, etc., it is possible in this way to enhance the rinse results. The incorporation of perfume is also readily possible; by means of its retarded release it is possible in the case of dishwashers to eliminate the "alkali odor" when the machine is opened, which is a frequent occurrence. In relation to the detergent components of the invention, the acidifier, soil release polymer, etc. ingredients are in this case ingredients d).
In preferred embodiments of the present invention the base tablet possesses a high specific weight. The invention prefers detergent tablets wherein the base tablet has a density of more than 1000 g dm-3, preferably more than 1025 g dm-3, with particular preference more than 1050 g dm-3, and in particular more than 1100 g dm-3.
In order to facilitate the disintegration of highly compacted tablets, it is possible to incorporate disintegration aids, known as tablet disintegrants, intc the tablets in order to reduce the disintegration times.
Tablet disintegrants, or disintegration accelerators, are understood in accordance with Rompp (9th Edition, Vol. 6, p. 4440) and Voigt "Lehrbuch der pharmazeutischen Technologie" [Textbook of pharmaceutical technology] (6th Edition, 1987, pp. 182-184) to be auxiliaries which ensure the rapid disintegration of tablets in water or gastric fluid and the release of the drugs in absorbable form.
These substances increase in volume on ingress of water, with on the one hand an increase in the intrinsic volume (swelling) and on the other hand, by way of the release of gases, the generation of a pressure which causes the tablets to disintegrate into smaller particles. Examples of established disintegration aids are carbonate/citric acid systems, with the use of other organic acids also being possible. Examples of swelling disintegration aids 20. are synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers and/or modified natural substances such as cellulose and starch and their derivatives, alginates, or casein derivatives.
Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight, and in particular from 4 to 6% by weight, of one or more disintegration aids, based in each case on the tablet weight. If only the base tablet comprises disintegration aids, then these figures are based only on the weight of the base tablet. If disintegration aids are incorporated into the detergent components of the invention, they count as ingredient d).
Preferred disintegrants used in the context of the present invention are cellulose-based disintegrants and so preferred detergent tablets comprise a cellulose-based disintegrant of this kind in amounts from 0.5 to 10°s by weight, preferably from 3 to 7°s by weight, and in particular from 4 to 6% by weight. Pure cellulose has the formal empirical composition (C6H1o05) n and, considered formally, is a (3-1,4-polyacetal of cellobiose, which itself is constructed of two molecules of glucose.
Suitable celluloses consist of from about 500 to 5000 glucose units and, accordingly, have average molecular masses of from 50,000 to 500,000. Cellulose-based disintegrants which can be used also include, in the context of the present invention, cellulose derivatives obtainable by polymer-analogous reactions from cellulose.
Such chemically modified celluloses include, for example, products of esterifications and etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxy groups have been replaced by functional groups not attached by an oxygen atom may also be used as cellulose derivatives. The group of the cellulose derivatives embraces, for example, alkali metal celluloses, carboxymethyl-cellulose (CMC), cellulose esters and cellulose ethers and aminocelluloses. Said cellulose derivatives are preferably not used alone as cellulose-based disintegrants but instead are used in a mixture with cellulose. The cellulose derivative content of these mixtures is preferably less than 50°s by weight, with particular preference less than 20% by weight, based on the cellulose-based disintegrant. The particularly preferred cellulose-based disintegrant used is pure cellulose, free from cellulose derivatives.
The cellulose used as disintegration aid is preferably not used in finely divided form but instead is converted into a coarser form, for example, by granulation or compaction, before being admixed to the premixes intended for compression. Detergent tablets comprising . CA 02318000 2000-09-11 disintegrants in granular or optionally cogranulated form are described in German Patent Applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in International Patent Application W098/40463 (Henkel). These documents also provide further details on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 Vim, preferably between 300 and 1600 ~m to the extent of at least 90% by weight, and in particular between 400 and 1200 ~,m to the extent of at least 90% by weight. The abovementioned, relatively coarse cellulose-based disintegration aids, and those described in more detail in the cited documents, are preferred for use as disintegration aids in the context of the present invention and are available commercially, for example, under the designation Arbocel~
TF-30-HG from the company Rettenmaier.
As a further cellulose-based disintegrant or as a constituent of this component it is possible to use microcrystalline cellulose. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack only the amorphous regions (approximately 30% of the total cellulose mass) of the celluloses and break them up completely but leave the crystalline regions (approximately 70%) intact.
Subsequent deaggregation of the microfine celluloses resulting from the hydrolysis yields the microcrystalline celluloses, which have primary particle sizes of approximately 5 ~m and can be compacted, for example, to granules having an average particle size of 200 Vim.
Detergent tablets which are preferred in the context of the present invention further comprise a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight, and in particular from 4 to 6% by weight, based in each case on the tablet weight.
The detergent tablets of the invention may further comprise, both in the base tablet and in the detergent component, a gas-evolving effervescent system. Said gas-evolving effervescent system may consist of a single substance which on contact with water releases a gas.
Among these compounds mention may be made, in particular, of magnesium peroxide, which on contact with water releases oxygen. Normally, however, the gas-releasing effervescent system consists in its turn of at least two constituents which react with one another and, in so doing, form gas. Although a multitude of systems which release, for example, nitrogen, oxygen or hydrogen are conceivable and practicable here, the effervescent system used in the detergent tablets of the invention will be selectable on the basis of both economic and environmental considerations. Preferred effervescent systems consist of alkali metal carbonate and/or alkali metal hydrogen carbonate and of an acidifier apt to release carbon dioxide from the alkali metal salts in aqueous solution.
Among the alkali metal carbonates and/or alkali metal hydrogen carbonates, the sodium and potassium salts are much preferred over the other salts on grounds of cost.
It is of course not mandatory to use the pure alkali metal carbonates or alkali metal hydrogen carbonates in question; rather, mixtures of different carbonates and hydrogen carbonates may be preferred from the standpoint of wash technology.
In preferred detergent tablets, the effervescent system used comprises from 2 to 20% by weight, preferably from 3 to 15% by weight, and in particular from 5 to 10% by weight, of an alkali metal carbonate or alkali metal hydrogen carbonate, and from 1 to 15, preferably from 2 to 12, and in particular from 3 to 10% by weight of an acidifier, based in each case on the total tablet.
As examples of acidifiers which release carbon dioxide from the alkali metal salts in aqueous solution it is possible to use boric acid and also alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates, and other inorganic salts. Preference is given, however, to the use of organic acidifiers, with citric acid being a particularly preferred acidifier. However, it is also possible, in particular, to use the other solid mono-, oligo- and polycarboxylic acids. Preferred among this group, in turn, are tartaric acid, succinic acid, malonic acid, adipic acid, malefic acid, fumaric acid, oxalic acid, and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid may likewise be used. A
commercially available acidifier which is likewise preferred for use in the context of the present invention is Sokalan°' DCS (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).
In the context of the present invention, preference is given to detergent tablets where the acidifier used in the effervescent system comprises a substance from the group of the organic di-, tri- and oligocarboxylic acids, or mixtures thereof.
Following production, the particulate detergents and/or detergent tablets of the invention, and the novel detergent components per se, may be packed, the use of certain packaging systems having proven particularly useful. The present invention additionally provides a combination comprising (a) particulate detergents) and/or (a) detergent tablets) of the invention and a packaging system containing said detergent and/or said detergent tablet(s), said packaging system having a moisture vapor transmission rate of from 0.1 g/m2/day to less than 20 g/mz/day if said packaging system is stored at 23°C and a relative equilibrium humidity of 850.
The packaging system of the combination of detergent component and/or detergent and/or detergent tablets) and packaging system has, in accordance with the invention, a moisture vapor transmission rate of from 0.1 g/m2/day to less than 20 g/m2/day when said packaging system is stored at 23°C and a relative equilibrium humidity of 85%. These temperature and humidity conditions are the test conditions specified in DIN Standard 53122, which allows minimal deviations (23 ~ 1°C, 85 ~ 2% relative humidity). The moisture vapor transmission rate of a given packaging system or material may be determined in accordance with further standard methods and is also described, for example, in ASTM Standard E-96-53T ("Test for measuring water vapor transmission of materials in sheet form") and in TAPPI Standard T464 m-45 ("4~later vapor permeability of sheet materials at high temperature and humidity"). The measurement principle of common techniques is based on the water uptake of anhydrous calcium chloride which is stored in a container in the appropriate atmosphere, the container being closed at the top face with the material to be tested. From the surface area of the container closed with the material to be tested (permeation area), the weight gain of the calcium chloride, and the exposure time, the moisture vapor transmission rate may be calculated as follows:
MVTR = 24 ~ 10,000 , x A -[g/mz /24 h) Y

where A is the area of the material to be tested in cm2, x is the weight gain of the calcium chloride in g, and y is the exposure time in h.
The relative equilibrium humidity, often referred to as "relative atmospheric humidity~~, is 85% at 23°C when the moisture vapor transmission rate is measured in the context of the present invention. The ability of air to accommodate water vapor increases with temperature up to a particular maximum content, the so-called saturation content, and is specified in g/m3. For example, 1 m3 of air at 17° is saturated with 14.4 g of water vapor; at a temperature of 11°, saturation is reached with just 10 g of water vapor. The relative atmospheric humidity is the ratio, expressed as a percentage, of the actual water vapor content to the saturation content at the prevailing temperature. If, for example, air at 17° contains 12 g/m3 water vapor, then the relative atmospheric humidity (RH) - (12/14.4)100 - 83%. If this air is cooled, then saturation (100% RH) is reached at what is known as the dew point (in the example: 14°), i.e., on further cooling a precipitate is formed in the form of mist (dew). The humidity is determined quantitatively using hygrometers and psychrometers.
The relative equilibrium humidity of 85% at 23°C can be established precisely, for example, in laboratory chambers with humidity control, to +/-2% RH depending on the type of apparatus. In addition, constant and well-defined relative atmospheric humidities are formed in closed systems at a given temperature over saturated solutions of certain salts, these humidities deriving from the phase equilibrium between water partial pressure, saturated solution, and sediment.

The combinations of the invention may of course in turn be packaged in secondary packaging, examples being cardboard packaging or trays, there being no need to impose further requirements on the secondary packaging.
The secondary packaging, accordingly, is possible but not necessary.
Packaging systems which are preferred in the context of the present invention have a moisture vapor transmission rate of from 0.5 g/m2/day to less than 15 g/m2/day.
Depending on the embodiment of the invention, the packaging system of the combination of the invention contains a defined amount of novel detergent component, a defined amount of a particulate detergent composition, or one or more detergent tablets. In accordance with the invention it is preferred either to design a tablet such that it comprises one application unit of the detergent, and to package this tablet individually, or to pack into one packaging unit the number of tablets which totals one application unit. In the case of an intended dose of 80 g of detergent, therefore, it is possible in accordance with the invention to produce and package individually one detergent tablet weighing 80 g, but in accordance with the invention it is also possible to package two detergent tablets each weighing 40 g into one pack in order to arrive at a combination in accordance with the invention. This principle can of course be extended, so that, in accordance with the invention, combinations may also comprise three, four, five or even more detergent tablets in one packaging unit. Of course, two or more tablets in a pack may have different compositions. In this way it is possible to separate certain components spatially from one another in order, for example, to avoid stability problems.

The packaging system of the combination of the invention may consist of a very wide variety of materials and may adopt any desired external forms. For reasons of economy and of greater ease of processing, however, preference is given to packaging systems in which the packaging material has a low weight, is easy to process, and is inexpensive. In combinations which are preferred in accordance with the invention, the packaging system consists of a bag or pouch of single-layer or laminated paper and/or polymer film.
The detergent tablets may be filled unsorted, i.e. as a loose heap, into a pouch made of said materials. On esthetic grounds and for the purpose of sorting the combinations into secondary packaging, however, it is preferred to fill the detergent tablets individually, or sorted into groups of two or more, into bags or pouches .
For individual application units of the detergent tablets which are located in a bag or pouch, a term which has become established in the art is that of the "flow pack".
Flow packs of this kind may optionally then - again, preferably sorted - be packaged into outer packaging, which underscores the compact commercial form of the tablet.
The single-layer or laminated paper or polymer film bags or pouches preferred for use as packaging systems may be designed in a very wide variety of ways : for example, as inflated pouches without a center seam or as pouches with a center seam which are sealed by means of heat (heat sealing), adhesives, or adhesive tapes. Single-layer pouch and bag materials include the known papers, which may if appropriate be impregnated, and also polymer films, which may if appropriate be coextruded. Polymer films that can be used as a packaging system in the context of the present invention are specified, for example, in Hans Domininghaus, "Die Kunststoffe and ihre Eigenschaften", 3rd edition, VDI Verlag, Diisseldorf, 1988, page 193. Figure 111 shown therein also gives indications of the water vapor permeability of the materials mentioned.
Combinations which are particularly preferred in the context of the present invention comprise as packaging system a bag or pouch of single-layer or laminated polymer film having a thickness of from 10 to 200 ~,m, preferably from 20 to 100 ~,m, and in particular from 25 to 50 ~,m.
Although it is possible in addition to the abovementioned films and papers also to use wax-coated papers in the form of cardboard packaging as a packaging system for the detergent tablets, it is preferred in the context of the present invention for the packaging system not to comprise any cardboard boxes made of wax-coated paper. In the context of the present invention, the term "packaging system" always relates to the primary packaging of the detergent component, composition or tablets, i.e., to the packaging whose inner face is in direct contact with the detergent component, composition or tablet surface. No requirements whatsoever are imposed on any optional secondary packaging, so that all customary materials and systems can be used in this case.
As already mentioned earlier on above, the detergent components, detergent compositions, or detergent tablets of the combination in accordance with the invention comprise further ingredients of detergents, in varying amounts, depending on their intended use. Independently of the intended use of the compositions or tablets, it is preferred in accordance with the invention for the detergent compositions) or tablets) to have a relative equilibrium humidity of less than 30% at 35°C.
The relative equilibrium humidity of the detergent compositions or tablets may be determined in accordance with common methods, the following procedure having been chosen in the context of the present investigations: a water-impermeable 1 liter vessel with a lid which has a closable opening for the introduction of samples was filled with a total of 300 g of detergent tablets and held at a constant 23°C for 24 h in order to ensure a uniform temperature of vessel and substance. The water vapor pressure in the space above the tablets can then be determined using a hygrometer (Hygrotest 6100, Testoterm Limited, England). The water vapor pressure is then measured every 10 minutes until two successive values show no deviation (equilibrium humidity). The abovementioned hygrometer permits direct display of the recorded values in % relative humidity.
Likewise preferred are embodiments of the combination in accordance with the invention wherein the packaging system is of resealable configuration. Combinations wherein the packaging system has a microperforation may also be realized with preference in accordance with the invention.
As mentioned earlier on above, detergent components, detergent compositions or detergent tablets for machine dishwashing may be prepared by the processes of the invention. Accordingly, the present invention additionally provides a method of cleaning kitchen- and tableware in a dishwasher, which comprises placing one or more particulate detergents and/or one or more detergent tablets of the invention in the dispensing compartment of the dishwasher and running a wash program in the course of which the dispensing compartment opens and the detergents) and/or tablets) is or are dissolved.
With the cleaning method of the invention as well it is possible to forego the dispensing compartment and to place the detergent components and/or detergent compositions or the tablets) of the invention, for example, in the cutlery basket. Here again, of course, the use of a dosing aid, for example, a basket insert which is placed in the washing compartment, is possible without problems. Accordingly, the present invention further provides a method of cleaning kitchen- and tableware in a dishwasher, which comprises placing one or more particulate detergents of the invention and/or one or more detergent tablets of the invention, with or without a dosing aid, in the washing compartment of the dishwasher and running a wash program in the course of which the detergents) and/or the tablets) is or are dissolved.
Examples:
Melt dispersions and melt emulsions of the following composition [% by weight] were prepared:
V1 V2 El E2 E3 Paraffin 57-60C 50.0 45.0 50.0 45.0 45.0 Nonionic surfactant* 45.0 45.0 42.5 45.0 49.7 Potassium acetate** - - 2.5 - -Mod. bentonite*** - - - - 0.3 FAS dust **** 5.0 5.0 Auxiliary***** 5.0 5.0 5.0 5.0 5.0 L~~~y-~dYpeu polyoxyalkylated alcohol softening point 25-45°C
** 100% < 100 ~.m *** Thixogel~ MP250, Sudchemie **** E2: Clz-la fatty alcohol sulfate, 90% < 200 ~m V2: Clz-is fatty alcohol sulfate, 90% > 200 ~,m, average particle size 300 ~,m ***** Polyglycerol poly-12-hydroxystearate This was done by heating the nonionic surfactant to 85°C, adding the paraffin with stirring, and finally adding the remaining ingredients. The stability of the suspension/emulsion was evaluated at 85°C by switching off the stirrer and examining it visually.
The evaluation was based on the following scheme:
++ visible separation after > 60 s + visible separation after > 30 s - visible separation after < 30 s -- visible separation after switching off the stirrer < 10 s The following table shows the resu7rs V1 v2 E1 E1 E3 -_ -- ++

Claims (91)

1. A detergent component composition comprising a) from 10 to 89.9% by weight of one or more surfactants, b) from 10 to 89.9% by weight of one or more meltable substances having a melting point above 30°C and a water solubility of less than 20 g/l at 20°C, c) from 0.1 to 15% by weight of one or more particulate solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries, with the proviso that at least 90% by weight of the particles c) have sizes below 300 µm.

2. The detergent component composition as claimed in claim 1, comprising as ingredient a) from 15 to 80%, by weight of surfactants.

3. The detergent component composition as claimed in claim 2, wherein from 20 to 70% by weight of surfactant is present.

4. The detergent component composition as claimed in claim 2, wherein from 25 to 60% by weight of surfactant is present.

5. The detergent component composition as claimed in claim 2, wherein from 30 to 50% by weight of surfactant is present.

6. The detergent component composition as claimed in any of claims 1 to 5, comprising as ingredient b) from 15 to 85% by weight of meltable substances.

7. The detergent component composition as claimed in claim 6, wherein from 20 to 80% by weight of meltable substance is present.

8. The detergent component composition as claimed in claim 6, wherein from 25 to 75% by weight of meltable substance is present.

9. The detergent component composition as claimed in claim 6, wherein from 30 to 70% by weight of meltable substance is present.

10. The detergent component composition as claimed in any of claims 1 to 9, comprising ingredient c) in amounts of from 0.15 to 12.5% by weight.

11. The detergent component composition as claimed in claim 10, wherein from 0.2 to 10% by weight of ingredient c) is present.

12. The detergent component composition as claimed in claim 10, wherein from 0.25 to 7.5% by weight of ingredient c) is present.

13. The detergent component composition as claimed in claim 10, wherein from 0.3 to 5% by weight of ingredient c) is present.

14. The detergent component composition as claimed in any of claims 1 to 14, comprising as ingredient a) anionic and/or nonionic surfactants.

15. The detergent component composition as claimed in claim 14, wherein nonionic surfactant is present.

16. The detergent component composition as claimed in any of claims 1 to 15, comprising as ingredient a) nonionic surfactants having a melting point above 20°C.

17. The detergent component composition as claimed in claim 16, wherein the melting point is above 25°C.

18. The detergent component composition as claimed in claim 16, wherein the melting point is between 25 and 60°C.

19. The detergent component composition as claimed in claim 16, wherein the melting point is between 26.6 and 43.3°C.

20. The detergent component composition as claimed in any of claims 1 to 19, comprising as ingredient a) ethoxylated nonionic surfactants obtained from C6-20 monohydroxyalkanols or C6-20 alkylphenols or C16-20 fatty alcohols and more than 12 mol of ethylene oxide per mole of alcohol.

21. The detergent component composition as claimed in claim 20, wherein more than 15 mol of ethylene oxide per mole of alcohol is present.

22. The detergent component composition as claimed in claim 20, wherein more than 20 mol of ethylene oxide per mole of alcohol is present.

23. The detergent component composition as claimed in any of claims 1 to 22, comprising as ingredient a) ethoxylated and propoxylated nonionic surfactants wherein the propylene oxide units in the molecule account for up to 25% by weight, of the total molecular mass of the nonionic surfactant.

24. The detergent component composition as claimed in claim 23, wherein up to 20% by weight of propylene oxide units are present in the molecule.

25. The detergent component composition as claimed in claim 23, wherein up to 15% by weight of propylene oxide units are present in the molecule.

26. The detergent component composition as claimed in any of claims 1 to 25, comprising as ingredient a) nonionic surfactants of the formula R1O[CH2CH(CH3)O]X[CH2CH2O]y[CH2CH(OH)R2]
in which R1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms, or mixtures thereof, R2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms, or mixtures thereof, and x is between 0.5 and 1.5, and y is at least 15.

27. The detergent component composition as claimed in any of claims 1 to 26, comprising as ingredient a) endgroup-capped poly(oxyalkylated) nonionic surfactants of the formula R1O[CH2CH(R3)O]x[CH2]k CH(OH) [CH2] j OR2 in which R1 and R2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are between 1 and 12, particular preference being given to surfactants of the type R1O[CH2CH(R3)O]x CH2CH(OH)CH2OR2 in which x stands for numbers from 1 to 30.

28. The detergent component composition as claimed in claim 27, wherein k and j are between 1 and 5.

29. The detergent component composition as claimed in claim 27, wherein the surfactants are of the type R1O[CH2CH(R3)O]x CH2CH(OH)CH2OR2 in which x stands for numbers from 1 to 30.

30. The detergent component composition as claimed in claim 29, wherein x is from 1 to 20.

31. The detergent component composition as claimed in claim 29, wherein x is from 6 to 18.

32. The detergent component composition as claimed in any of claims 1 to 31, comprising as ingredient b) one or more substances having a melting range between 30 and 100°C.

33. The detergent component composition as claimed in claim 32, wherein the melting range if between 40 and 80°C.

34. The detergent component composition as claimed in claim 32, wherein the melting range if between 50 and 75°C.

35. The detergent component composition as claimed in any of claims 1 to 34, comprising as ingredient b) at least one paraffin wax having a melting range of from 30°C to 65°C.

36. The detergent component composition as claimed in any of claims 1 to 35, wherein the water solubility of ingredient b) at 20°C is less than 15 g/l.

37. The detergent component composition as claimed in claim 36, wherein the water solubility is less than to g/l.

38. The detergent component composition as claimed in claim 36, wherein the water solubility is less than 5 g/l.

39. The detergent component composition as claimed in claim 36, wherein the water solubility is less than 2 g/l.

40. The detergent component composition as claimed in any of claims 1 to 39, wherein at least 90% by weight of the particles of c) have sizes below 190 µm.

41. The detergent component composition as claimed in claim 40, wherein the particles have sizes below 175 µm.

42. The detergent component composition as claimed in claim 40, wherein the particles have sizes below 150 µm.

43. The detergent component composition as claimed in any of claims 1 to 42, wherein ingredient c) consists entirely of particles having sizes below 200 µm.

44. The detergent component composition as claimed in claim 43, wherein the particles have sizes below 175 µm.

45. The detergent component composition as claimed in claim 43, wherein the particles have sizes below 150 µm.

46. The detergent component composition as claimed in claim 40, wherein the particles have sizes below 100 µm.

47. The detergent component composition as claimed in any of claims 1 to 46, comprising as ingredient c) alkali metal salts of organic acids.

48. The detergent component composition as claimed in claim 48, wherein ingredient c) is an alkali metal acetates.

49. The detergent component composition as claimed in claim 48, wherein ingredient c) is potassium acetate.

50. The detergent component as claimed in any of claims 1 to 49, comprising as ingredient c) substances from the group of the clay minerals.

51. The detergent component composition as claimed in claim 50, wherein ingredient c) is selected from the group of chemically modified minerals.

52. The detergent component composition as claimed in claim 50, wherein ingredient c) is selected from hydrophobicized bentonites.

53. The detergent component composition as claimed in any of claims 1 to 52, comprising as ingredient c) anionic surfactants.

54. The detergent component composition as claimed in claim 53, wherein ingredient c) is a fatty alcohol sulfates.

55. The detergent component composition as claimed in claim 53, wherein ingredient c) is a C12-18 fatty alcohol sulfate.

56. The detergent component composition as claimed in any of claims 1 to 55, comprising as ingredient d) further active substances and/or auxiliaries from the groups of the dyes, fragrances, soil release polymers, corrosion inhibitors, enzymes, bleaches, bleach activators, and complexing agents, in amounts of from 0 to 10% by weight.

57. The detergent component composition as claimed in claim 56, wherein the amounts are from 0.25 to 7.5%
by weight.

58. The detergent component composition as claimed in claim 56, wherein the amounts are from 0.5 to 2.5%
by weight.

59. The detergent component composition as claimed in claim 56, wherein the amounts are from 0.75 to 2.5%
by weight.

60. The detergent component composition as claimed in any of claims 1 to 59, which has a melting point of between 50 and 80°C.

61. The detergent component composition as claimed in claim 60, wherein the melting point is between 52.5 and 75°C.

62. The detergent component composition as claimed in claim 60, wherein the melting point is between 55 and 65°C.

63. A process for preparing a particulate detergent component composition, which comprises applying a melt comprising a) from 10 to 89.9% by weight of surfactants, b) from 10 to 89.9% by weight of meltable substances having a melting point above 30°C and a water solubility of less than 20 g/l at 20°C, c) from 0.1 to 15% by weight of one or more particulate solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries, to one or more support materials and shaping the mixture.

64. The process as claimed in claim 63, wherein shaping takes place by granulating, compacting, pelletizing, extruding, or tableting.

65. A process for preparing a prilled detergent component composition, which comprises spraying a melt comprising a) from 10 to 89.9% by weight of surfactants, b) from 10 to 89.9% by weight of meltable substances having a melting point above 30°C and a water solubility of less than 20 g/l at 20°C, c) from 0.1 to 15% by weight of one or more particulate solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries, into a cold gas stream.

66. A process for preparing a pelletized detergent component composition, which comprises metering a melt comprising a) from 10 to 89.9% by weight of surfactants, b) from 10 to 89.9% by weight of meltable substances having a melting point above 30°C and a water solubility of less than 20 g/l at 20°C, c) from 0.1 to 15% by weight of one or more particulate solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries, onto cooled pelletizing plates.

67. A process for preparing a particulate detergent component composition, which comprises applying a melt comprising a) from 10 to 89.9% by weight of surfactants, b) from 10 to 89.9% by weight of meltable substances having a melting point above 30°C and a water solubility of less than 20 g/l at 20°C, c) from 0.1 to 15% by weight of one or more particulate solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries, by spraying or otherwise to a cooling roll, scraping off the solidified melt, and comminuting the scrapings if necessary.

68. The use of a particulate detergent component composition comprising a) from 10 to 89.9% by weight of surfactants, b) from 10 to 89.9% by weight of meltable substances having a melting point above 30°C and a water solubility of less than 20 g/l at 20°C, c) from 0.1 to 15% by weight of one or more particulate solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries, in detergents for machine dishwashing.

69. A particulate machine dishwashing composition, comprising builders and also, optionally, further detergent ingredients, which comprises particulate detergent components comprising, based on their weight, a) from 10 to 89.9% by weight of surfactant(s), b) from 10 to 89.9% by weight of meltable substance(s) having a melting point above 30°C
and a water solubility of less than 20 g/l at 20°C, c) from 0.1 to 15% by weight of one or more solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries.

70. The particulate machine dishwashing composition as claimed in claim 69, comprising builders in amounts of from 20 to 80% by weight, based in each case on the weight of the composition.

71. The composition as claimed in claim 71, wherein from 25 to 75% by weight is present.

72. The composition as claimed in claim 71, wherein from 30 to 70% by weight is present.

73. The particulate machine dishwashing composition as claimed in any of claims 69 to 72, further comprising one or more substances from the groups of the bleaches, bleach activators, bleaching catalysts, surfactants, corrosion inhibitors, polymers, dyes, fragrances, pH modifiers, complexing agents, and enzymes.

74. The particulate machine dishwashing composition as claimed in any of claims 69 to 73, comprising the particulate detergent component in amounts of from 0.5 to 30% by weight, based in each case on overall composition.

75. The particulate machine dishwashing composition as claimed in claim 74, wherein the amounts are from 1 to 25% by weight.

76. The particulate machine dishwashing composition as claimed in claim 74, wherein the amounts are from 3 to 15% by weight.

77. The particulate machine dishwashing composition as claimed in any of claims 69 to 76, wherein the particulate detergent component has particle sizes of between 1 and 40 mm.

78. The particulate machine dishwashing composition as claimed in claim 77, wherein the particle sizes are between 1.5 and 30 mm.

79. The particulate machine dishwashing composition as claimed in claim 77, wherein the particle sizes are between 2 and 20 mm.

80. The particulate machine dishwashing composition as claimed in any of claims 69 to 79, which has (without taking into account the particulate detergent component) particle sizes of between 100 and 3000 µm.

81. The particulate machine dishwashing composition as claimed in claim 80, wherein the particle sizes are between 300 and 2500 µm.

82. The particulate machine dishwashing composition as claimed in claim 80, wherein the particle sizes are between 400 and 2000 µm.

83. The particulate machine dishwashing composition as claimed in any of claims 69 to 82, wherein one dose unit is welded in a water-soluble film pouch.

84. A multiphase detergent tablet for machine dishwashing, comprising builders and also, optionally, further detergent ingredients, wherein at least one phase comprises a) from 10 to 89.9% by weight of surfactants, b) from 10 to 89.9% by weight of meltable substances having a melting point above 30°C and a water solubility of less than 20 g/l at 20°C, c) from 0.1 to 15% by weight of one or more particulate solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries.

85. The multiphase detergent tablet as claimed in claim 84, wherein the phases have the form of layers and the tablet has 2, 3 or 4 phases.

86. The multiphase detergent tablet as claimed in claim 84, comprising a base tablet, which has a cavity, and a part present at least partially in the cavity.

87. The multiphase detergent tablet as claimed in claim 86, wherein the part present in the cavity comprises a) from 10 to 89.9% by weight of surfactants, b) from 10 to 89.9% by weight of meltable substances having a melting point above 30°C and a water solubility of less than 20 g/l at 20°C, c) from 0.1 to 15% by weight of one or more particulate solids, d) from 0 to 15% by weight of further active substances and/or auxiliaries.

88. A combination comprising (a) particulate detergent(s) as claimed in any of claims 66 to 74 and/or (a) detergent tablet(s) as claimed in any of claims 77 to 84 and a packaging system containing said detergent and/or said detergent tablet(s), said packaging system having a moisture vapor transmission rate of from 0.1 g/m2/day to less than 20 g/m2/day if said packaging system is stored at 23°C and a relative equilibrium humidity of 85%.

89. A process for washing kitchen- and tableware in a dishwashing machine, which comprises placing one or more particulate detergents as claimed in any of claims 66 to 74, and/or one or more detergent tablets as claimed in any of claims 77 to 84, in the dispensing compartment of the dishwasher and running a wash program in the course of which the dispensing

90 compartment opens and the detergent(s) and/or tablet (s) is or are dissolved.
90. A process for cleaning kitchen- and tableware in a dishwasher, which comprises placing one or more particulate detergents as claimed in any of claims 66 to 74, and/or one or more detergent tablet(s) as claimed in any of claims 77 to 84, with or without a dosing aid, in the washing compartment of the dishwasher and running a wash program in the course of which the detergent(s) and/or the tablet(s) is or are dissolved.

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