EP1870447B1 - Solid tensides in granular form - Google Patents

Description

The present invention relates to solid granular compositions containing surfactants characterized by a specific particle size distribution and the use of such compositions in detergents and cleaners.
Surfactant components for use in detergents and cleaners are usually offered in the form of a solid block, as a molten paste or liquid, or as a powdered product. The surfactant raw materials offered in solid block form usually have to be melted before further processing, which necessitates an additional operation and an increased energy input. Powdered goods had the disadvantage that more dust can be formed and the effect of the surfactant is lost, for example, by too fast dissolution in the water. If the surfactant is offered as a pre-molten liquid, it must be pumped out consuming, heated and usually processed quickly. Also from this way costs arise for the manufacturer. There is therefore a fundamental need to obtain surfactant raw materials in non-dusting, easily pourable solid form. For this purpose, granular forms are suitable. Although such granules are known in principle, it is found in practice that such granules often during further processing can lead to disadvantageous performance properties, for example problems with the solubility of detergents or cleaning agents or a reduction in the final rinse performance of detergents.
The object of the present invention was to transfer surfactant raw materials into a granular supply form that is easy to store, transport and process further, without causing any disadvantages during subsequent incorporation and further processing into detergents and cleaners.
Surprisingly, it has been found that granules which have a certain selected particle size distribution solve the above object.

1. a) Verbindungen der allgemeinen Formel (I)
   
           R¹O[CH₂CH₂O]xCH₂CH(OM)R²     (I)
   
   in der R¹ für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen bedeutet, oder für einen Rest R²-CH(OH)CH₂ steht, wobei R² für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 8 bis 16 Kohlenstoffatomen, x für eine Zahl von 40 bis 80 steht, und M für ein Wasserstoffatom oder einen gesättigten Alkylrest mit 1 bis 18 Kohlenstoffatomen;
2. b) Verbindungen der Formel (II)
   
           R³O[CH₂CH₂O]_y[CH₂CHCH₃O],CH₂CH(OH)R⁴      (II)|
   
   in der R³ für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen, R⁴ für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 8 bis 16 Kohlenstoffatomen, y für eine Zahl von 10 und 35 steht, z Null bedeutet oder eine Zahl von 1 bis 5, mit der Maßgabe, dass wenn R³ = R¹ und gleichzeitig R⁴ = R² ist, dass dann z mindestens 1 sein muss;
3. c) ethoxylierten Fettalkoholen der allgemeinen Formel (III)
   
           R⁵-(OC₂H₄)_z-OH
   
   in der R⁵ für lineare oder verzweigte Alkyl- und/oder Alkenylreste mit 8 bis 22 Kohlenstoffatomen steht und z eine Zahl von 1 bis 20 steht; und die dadurch gekennzeichnet sind, dass die granulare Zusammensetzung nach Siebanalyse mit einem Sieb gemäß DIN ISO 3310-1 eine Korngrößeverteilung aufweisen, wobei die Korngrößeverteilung die graphisch mittels RRSB-Diagramms nach DIN 66145 ermittelt wird, die folgenden Kenngrößen erfüllen muss:
   • d_m liegt im Bereich von 0,5 bis 1,5 mm;
   • d₆₃,₃ liegt im Bereich von 0,5 bis 1,5 mm und
   • n liegt im Bereich von 1 bis 10.

Surfactants in granular forms with selected particle size distribution are known from the prior art. Reference is made by way of example to the EP 0 249 163 A2 , which relates to granular, agglomerated sodium metasilicate-containing detergent. Preferred cleaning agents within the meaning of the technical teaching of this document are distinguished by the fact that the particle fraction is <0.4 mm and the mean particle diameter (determined according to DIN 66145) is in the range from 0.9 to 1.3 mm, the slope of the RRSB straight line N = 2 to 2.5.
However, this document does not disclose purely surface-active granular raw materials but rather ready-agglomerated compounds which furthermore contain exclusively sodium metasilicate and builders, but no surfactants. Further surfactant-containing granules are made EP 1279725 A2 . EP 816485 A1 . DE 10015289 A1 and DE 4127323 A1 The first subject of the present invention is therefore solid granular compositions consisting of nonionic surfactants selected from at least one member of group a) to d), where:

1. a) Compounds of the general formula (I)
   
   R ¹ O [CH ₂ CH ₂ O] x CH ₂ CH (OM) R ² (I)
   
   in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R ^{2 is} -CH (OH) CH ₂ , where R ^{2 is} a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x represents a number from 40 to 80, and M represents a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms;
2. b) Compounds of the formula (II)
   
   R ³ O [CH ₂ CH ₂ O] _{y [} CH ₂ CHCH ₃ O], CH ₂ CH (OH) R ⁴ (II) |
   
   in the R ^{3 is} a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R ^{4 is} a linear or branched alkyl and / or alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35 is, z is zero or a number from 1 to 5, with the proviso that when R ³ = R ¹ and at the same time R ⁴ = R ² then z must be at least 1;
3. c) ethoxylated fatty alcohols of the general formula (III)
   
   R ⁵ - (OC ₂ H ₄ ) _z -OH
   
   in which R ^{5 is} linear or branched alkyl and / or alkenyl radicals having 8 to 22 carbon atoms and z is a number from 1 to 20; and which are characterized in that the granular composition after sieve analysis with a sieve according to DIN ISO 3310-1 have a grain size distribution, wherein the grain size distribution is determined graphically by means of RRSB diagram according to DIN 66145, which must meet the following characteristics:
   • d _m is in the range of 0.5 to 1.5 mm;
   • d ₆₃ , ₃ is in the range of 0.5 to 1.5 mm and
   • n is in the range of 1 to 10.

It is known that so-called sieve analysis represents a tried-and-tested means of characterizing granules. For the characterization of particle systems and in particular their size distribution, a large number of methods are known to the experts. The particle size distribution of real material systems is usually determined metrologically. Thereafter, there are first measured value pairs that are stored in digital form in modern measuring devices. Plotting the value pairs in the form of a diagram yields the distribution density or distribution sum function. The number of pairs of values is determined by the measuring method or by specifications and may be up to a few hundred in some measuring methods. It usually makes sense to process the results directly in digital form. Frequently, however, one also strives to detect the particle size distribution by means of a suitable distribution function, which at the same time should represent a compensation function for the measured values. A commonly used empirical distribution function is the so-called RRSB function.

The determination of whether a particle collective has an RRSB distribution or not according to the methodology of DIN 66145. Key parameters used to describe a Grain size distribution according to RRSB serve, are the average diameter d _m , the characteristic grain size d ₆₃ , ₃ and the so-called uniformity coefficient _n . From Applicant's study, it has been found that particulate surfactant systems having a mean diameter in the range of 0.5 to 1.5 mm and a characteristic grain size in the range of 0.5 to 1.5 mm and at the same time a coefficient of uniformity in the range from 1 to 10, have advantageous performance properties.

Particularly preferred are those granular compositions in which d _{m is} in the range of 0.5 to 1.2 mm, d ₆₃ , ₃ in the range of 0.5 to 1 mm and n in the range of 1 to 5.

Granules are usually called aggregates of granules. A granule (granule) is an asymmetric aggregate of powder particles (whole crystals or crystal fragments). It has - in contrast to the pellet, but similar to an agglomerate - no harmonious geometric shape; the shape of a sphere, a rod, a cylinder, etc. is only roughly and implicitly preserved. The surface is usually uneven and jagged, the mass in many cases more or less porous. Granulating is understood as meaning the transfer of powder particles into granules. Technical designs often make use of fluidized bed processes - today one often speaks of prills - use.

With regard to the surfactants present or consisting of the compositions according to the invention, all surfactants known to those skilled in the art which are present in solid form at room temperature (21 ° C.) are initially suitable.

The granules according to the invention consist of nonionic surfactants. In this case, such granules of the invention contain the surfactant in its technically-related quality, so that, if necessary, impurities or residues of starting compound in the technical qualities can be included.

The nonionic surfactants may be present in rinsing and cleaning agents according to the invention in amounts of from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, in particular from 1 to 8% by weight, calculated as the active substance on the means.

Preferred substances for the granules according to the invention are nonionic surfactants selected from the classes a) to d):
The substances of class a) are selected from compounds of general formula (I)

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OM) R ² (I)

in which R ^{1 is} a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R ^{2 is} -CH (OH) CH ₂ , where R ^{2 is} a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x represents a number from 40 to 80, and M represents a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms. These are so-called hydroxy mixed ethers or their derivatives. Hydroxy mixed ethers (HMEs) follow the general formula R'O [AO] _x CH ₂ CH (OM) R 'in which R' represents a linear or branched alkyl and / or alkenyl group containing 4 to 22 carbon atoms, R "is a linear or branched alkyl and / or alkenyl radical having 2 to 22 carbon atoms x is 10 to 80 and AO represents an ethylene oxide, propylene oxide or butylene oxide radical and M can stand for a hydrogen atom or an alkyl or alkenyl radical.

Such hydroxy mixed ethers are known from the literature and are described, for example, in the German application DE 19738866 described. They are prepared, for example, by reaction of 1,2-epoxyalkanes (R "CHOCH ₂ ), where R" is an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols. Preferred for the purposes of the invention are those hydroxy mixed ethers which are derived from alkoxylates of monohydric alcohols of the formula R'-OH having 4 to 18 carbon atoms, where R 'is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands. Examples of suitable straight-chain alcohols are butanol-1, caproic, eananthic, caprylic, pelargonic, capric alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, nonadecanol- 1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as obtained in the high pressure hydrogenation of technical methyl esters based on fats and oils. Examples of branched alcohols are so-called oxo alcohols, which are usually 2 to 4 Wear methyl groups as branches and are prepared by the Oxoprozeß and so-called Guerbet alcohols which are branched in the 2-position with an alkyl group. Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol. The alcohols are used in the form of their alkoxylates, which are prepared by reaction of the alcohols with ethylene oxide in a known manner.
In addition, other hydroxy mixed ethers are known, namely those which have more than one free hydroxyl group in the molecule. Such compounds can be prepared, for example, by reacting diols, preferably alkylene glycols and their derivatives, preferably polyethylene glycols, each with two moles of an alkyl epoxide (R-CHOCH ₂ ) per mole of the diol.

The likewise suitable substances of the class b) are selected from the group of the compounds of the formula (II)

R ³ O [CH ₂ CH ₂ O] _y [CH ₂ CHCH ₃ O] _z CH ₂ CH (OH) R ⁴ (II)

in which R ^{3 is} a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R ^{4 is} a linear or branched alkyl and / or alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35, Z is zero or a number from 1 to 5, with the proviso that if R ³ = R ¹ and at the same time R ⁴ = R ² , then that z must be at least 1, and.

These compounds are also HME, but they have a different structure than the HME of the general formula (I). The compounds of the type b) follow the formula (II)

R ³ O [CH ₂ CHCH ₃ O] _z [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ⁴ (II)

in which R ^{3 is} a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R ^{4 is} a linear or branched alkyl and / or alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35, z is zero or must be a number from 1 to 5. It may be advantageous if R ³ = R ¹ and at the same time R ⁴ = R ² those compounds of the formula b) are selected in which the index z is at least 1. Particularly preferred compounds of type b) are, for example, those in which, in the formula (II), the index y is a number from 20 to 30, preferably from 20 to 25.

Preference is furthermore given to those compounds of the type b) in which R ³ in the formula (II) represents an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms, R ^{4 is} an alkyl radical having 10 to 12, preferably 10 carbon atoms, y a number from 15 to 35, preferably 20 to 30 and z is a number from 1 to 3, preferably 1 means.

Also suitable are c) ethoxylated fatty alcohols of the general formula (III)

R ⁵ - (OC ₂ H ₄ ) _z -OH

in which R ^{5 is} linear or branched alkyl and / or alkenyl radicals having 8 to 22 carbon atoms and z is a number from 1 to 20.

These compounds are known per se fatty alcohol ethoxylates of the general formula (III) R ⁵ - (OC ₂ H ₄ ) _z -OH in which R ^{5 is} linear or branched alkyl and / or alkenyl radicals having 8 to 22 carbon atoms and z is a number from 1 to 20, and preferably from 1 to 15, and especially from 1 to 10. Typical examples are the adducts of on average 1 to 20 moles of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and Brassidyl alcohol and their technical mixtures, for example, in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols incurred. Preferred are adducts of 10 to 40 mol ethylene oxide with technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or preferably tallow fatty alcohol. Particularly preferred fatty alcohol ethoxylates are based on tallow alcohols ethoxylated with 2 to 10 and preferably 2 to 5 moles of ethylene oxide per mole of alcohol.

Also suitable are compounds of the type d), namely the alkyl (oligo) glycosides of the general formula R ⁸ O- [G] _p in the R ⁸ for an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical 5 or 6 carbon atoms and p stands for numbers from 1 to 10.

These compounds are also known as alky (oligo) glycosides. Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the above formula R ⁸ O- [G] _p . They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and above all the values p = 1 to 6, the value p for a given alkyloligoglycoside is an analytically determined arithmetic size, which is usually a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ⁸ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and in a proportion of less than 6% by weight C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁸ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.

Particular preference is given to those compositions which contain only surfactants of class a) and / or b).

It may be advantageous for the composition to contain, in addition to the surfactants described above, further additives, preferably polymers. In general, the proportion of these additives is at most 10% by weight, based on the granular compositions, and is preferably between 1 and 5% by weight.

The granulated preparations according to the present technical teaching are preferably used as a precursor for the production of solid detergents and cleaners.

The fully formulated detergents and cleaners contain, in addition to the granulated preparations as further constituents, preferably further surfactants, preferably anionic surfactants, soaps, inorganic builders, such as phosphates, zeolites, crystalline layered silicates, amorphous silicates, compounds of amorphous silicates and carbonates, organic cobuilders, bleaching agents and bleach activators, foam inhibitors, enzymes, optical brighteners, soil repellents and grayness inhibitors.

Solid cleaning agents within the meaning of the present technical teaching, d. H. those containing solid compositions as described above contain this composition in amounts of from 0.1 to 25% by weight, preferably in amounts of from 0.5 to 15% by weight, in particular in amounts of from 1.0 to 5 , 0 wt .-% each based on the total weight of the cleaning agent. Particularly preferred cleaning agents in the context of the present technical teaching are cleaners for hard surfaces and, in particular, cleaners for use in automatic dishwashing processes.

The solid preparations according to the invention can in principle be prepared in any manner known to the person skilled in the art. Particularly preferred is the granulation in the fluidized bed and the extrusion.

A fluidized-bed or SKET granulation means granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed. The nonionic surfactants may preferably be introduced in the form of aqueous pastes simultaneously or successively via one or more nozzles in the fluidized bed. Preferably used fluidized bed plants have bottom plates with dimensions of 0.4 to 5 m. Preferably, the SKET granulation is carried out at fluidized air velocities in the range of 1 to 8 m / s. The discharge of the Granules from the fluidized bed are preferably carried out by size classification of the granules. The classification can be carried out, for example, by means of a sieve device or by a countercurrent air stream (classifier air), which is regulated in such a way that only particles above a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. Usually, the incoming air is composed of the heated or unheated classifier air and the heated bottom air. The soil air temperature is between 60 and 400, preferably 60 and 350 ° C. Advantageously, an organic polymeric carrier material or a SKET granulate from an earlier experimental batch is initially introduced as the starting material at the beginning of the SKET granulation. In the fluidized bed, the water evaporates from the surfactant paste, which also contains the polymer in addition to the surfactant, to dried or dried germs arise, which are coated with other amounts of surfactant / polymer mixture, granulated and dried again at the same time. The result is a surfactant / polymer grain having a surfactant gradient across the grain, which is particularly soluble in water. The granulation with simultaneous drying can be carried out without the addition of inorganic salts, such as zeolite and soda.

In a preferred embodiment, a solid preparation according to the invention is prepared by means of an extrusion. In this case, a solid premix is extruded under pressure strand and cut the strand after exiting the hole shape by means of a cutting device to the predeterminable granule dimension. The homogeneous and solid premix optionally contains a plasticizer and / or lubricant, which causes the premix under the pressure or under the entry of specific work plastically softens and extrudable. Preferred plasticizers and / or lubricants are surfactants and / or polymers.

Preferably, the premix is fed to a planetary roller extruder or twin-screw or co-rotating screw extruder whose housing and extruder granulating head may be heated to the predetermined extruding temperature. Under the shearing action of the extruder screws, the premix under pressure, which is preferably at least 25 bar, but at extremely high throughputs depending on the apparatus used but also may be underneath, compacted, plasticized, in the form of fine strands through the Lochdüsenplatte extruded in the extruder head and finally the extrudate by means of a rotating blasting knife preferably reduced to approximately spherical to cylindrical granules. The hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension. Thus, it is possible to produce granules of a particle size which can be determined substantially uniformly beforehand, wherein in detail the absolute particle sizes can be adapted to the intended use. In general, particle diameters of at most 0.8 cm are preferred. It may just be preferable to stop drying after the compaction step. Alternatively, extrusions / compression can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in Bexx Bextruder. Preferably, the temperature control in the transition region of the screw, the predistributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least achieved, but preferably exceeded. The duration of the action of temperature in the compression region of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.

The compositions according to the invention can also be prepared by means of roll compaction. Here, the premix is selectively metered between two smooth or provided with wells of defined shape rollers and rolled between the two rollers under pressure to form a leaf-shaped Kompaktat, the so-called Schülpe. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. The sling strip is subsequently broken by a tee and crushing process into smaller pieces and can be processed in this way to granules, which can be refined by further known surface treatment methods. Also in the case of roll compaction, the temperature of the pressing tools, ie the rolls, is preferably not more than 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C.

The preparation according to the invention can also be prepared by means of pelleting. Here, the premix is applied to a perforated surface and pressed by means of a pressure-emitting body under plasticization through the holes. At usual In embodiments of pellet presses, the premix is compacted under pressure, plasticized, forced through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted to granules with a stripping device. Here are the most diverse designs of pressure roller and perforated die conceivable. For example, flat perforated plates are used as well as concave or convex ring matrices, through which the material is pressed through one or more pressure rollers. Also in the case of pelleting, the temperature of the pressing tools, ie the pressure rollers or press rollers, is preferably not more than 150 ° C., preferably not more than 100 ° C. and in particular not more than 75 ° C.

The present application also relates to a process for the preparation of solid detergents and cleaners, which comprises first preparing a premix in a manner known per se, containing builders, bleaches, complexing agents and additives and then adding to this premix a granular solid composition as described above inflicts.

Furthermore, the use of the composition described above for the production of solid detergents and cleaning agents is claimed, as well as the use of the composition for improving the rinsing performance of cleaners for cleaning hard surfaces, in particular for automatic dishwashing detergents. It has surprisingly been found that the use of granular compositions in the sense of the above technical teaching in the production of cleaning agents leads to advantageous performance properties. In particular, the better filming and mocking behavior of such cleaning agents should be mentioned. These two terms refer to deposits on hard surfaces after contact with detergents. Spotting occurs as a result of drying water droplets, with calcium and magnesium salts in particular precipitating and forming corresponding disruptive deposits. The term filming refers to layers that result from the drying of thin films of water. With regard to these two essential deposits, the Applicant has been able to show that the use of selected granules in the sense of the above description always brings about an improvement when they are used in the production of cleaning agents. In particular, there was an improvement in the rinse performance on glass surfaces. Of Furthermore, it is found that the use of the granular compositions in the production of detergents and cleaners, and in particular detergents, results in products which foam less and thus can not exert a negative influence on the flushing performance in an automatic dishwashing process.

In a preferred embodiment of the invention, these surfactant granules have a particle size distribution between 0.02 and 2.0 and in particular between 0.2 and 1.6 mm. In a further preferred embodiment of the invention, at least 70, particularly preferably 75 and in particular 85% by weight of the granules consist of round grains.

Examples

• Siebmaschine: AS 200 control, Fa. Retsch
• Analysensiebe nach DIN ISO 3310-1, Fa. Retsch
• h = 25 mm; Ø 200 mm
• Amplitude: 0,6
• Siebzeit: 2 min

Several surfactant granules were prepared. The particle size distributions of the granules used in the examples were determined by sieve analysis:

• Screening machine: AS 200 control, Retsch
• Test sieves according to DIN ISO 3310-1, Retsch
• h = 25 mm; Ø 200 mm
• Amplitude: 0.6
• Screening time: 2 min

d_ν

= mittlerer Korndurchmesser der v-ten Fraktion

m_ν

= Masse einer Kornfraktion

Z

= Gesamtmasse aller Kornfraktionen

ν

= Kornfraktion

d_m

= mittlerer Durchmesser

From the particle size distributions obtained by the sieve analysis, the parameters d _m ; d ₆₃ , ₃ and n, which describe the granulometry of the example granules, the following formula being used: $$d_m=\frac{{\displaystyle \underset{\upsilon =1}{\overset{n}{\Sigma }}{m}_{\upsilon }\widetilde{d_{\upsilon }}}}{Z}$$

d _ν

= mean grain diameter of the vth fraction

m _ν

= Mass of a grain fraction

Z

= Total mass of all grain fractions

ν

= Grain fraction

d _m

= average diameter

d_63,3 = d'

charakteristische Korngröße

n

Gleichmäßigkeitskoeffizient (Exponent n)

From the graphical evaluation of the particle size distribution using a Rosin, Rammler, Sperling and Bennet diagram (RRSB distribution)

d _63.3 = d '

characteristic grain size

n

Uniformity coefficient (exponent n)

In the case where the granulometric state of the aggregate can not be described by an RRSB distribution, eg in mixtures of aggregates of different granulometry, the above parameters also apply to sections of the distribution following the RRSB distribution.

Surfactant granules with different particle size distributions were mixed in an atomatic dish detergent (ADD) formulation and used for dishwasher testing at 25 g to test properties in ADD applications.

Basic formulation:

substance Wt .-% surfactant Up to 4 Sodium silicate (SKS-6) 7 Na ₅ tripolyphosphate 51 TAED (tetraacetylethylenediamine) 2.5 sodium 27.5 sodium 8th

Test conditions:

• Glasplatten
• Porzellanplatten
• Polypropylenplatten (PP)
• Melaminplatten
• Styrol-Acrylo-Nitril (SAN) Platten
• Rostfreie Stahlplatten

Miele dishwasher type G 661 SC program: 55 ° C - Universal Plus
Water hardness: 16 ° dH, substrates / machine load:

• glass plates
• porcelain plates
• Polypropylene plates (PP)
• melamine panels
• Styrene-acrylo-nitrile (SAN) plates
• Stainless steel plates

The test soil was 46.55 g standard soiling (= based on 1000 g: mixture of 25 g ketchup, mustard and gravy, 300 g margarine, 150 g drinking milk, 15 g potato starch, 9 g egg yolk, 3 g benzoic acid, balance: water) added.
After completion of the dishwasher program, the substrates were removed and evaluated by digital image analysis for rinse performance "filming" and "spotting". The method of digital image analysis follows the description of European patent application no. 04021958.6 (Cognis).

Glass, steel and plastic as well as melamine are evaluated from the common substrates. The obtained measurements for spotting and filming are given in relative degrees of coverage on the surface. The higher the value, the worse the rinse performance.

C16/18 40EO

Hydroxymischether auf Basis eines mit 40 Mol Ethylenoxid pro Mol Fettalkohol umgesetzten Fettalkohols mit 16 bis 18 C-Atomen (Fa. Cognis)

C18 80 EO

C18-Fettalkohol mit 80 Mol Ethylenoxid pro Mol Fettalkohol

C16/18 FA F0 EO

Mit 20 Mol Ethylenoxid pro Mol Fettalkohol umgesetzter Fettalkohol mit 16 bis 18 C-Atomen

C 22 FA 10 EO

Mit 20 Mol Ethylenoxid pro Mol Fettalkohol umgesetzter Fettalkohol mit 16 bis 18 C-Atomen

Alkylglycosid

C_12-16-Fettalkohol-1,4-glucosid (Fa. Cognis)

Table 1 gives the results obtained for different surfactant granules. All surfactants are each contained at 2% in the formulation:
The following surfactants were investigated:

C16 / 18 40EO

Hydroxymix ethers based on a fatty alcohol having 16 to 18 C atoms (Cognis) reacted with 40 mol of ethylene oxide per mole of fatty alcohol

C18 80 EO

C18 fatty alcohol with 80 moles of ethylene oxide per mole of fatty alcohol

C16 / 18 FA F0 EO

With 20 moles of ethylene oxide per mole of fatty alcohol reacted fatty alcohol having 16 to 18 carbon atoms

C 22 FA 10 EO

With 20 moles of ethylene oxide per mole of fatty alcohol reacted fatty alcohol having 16 to 18 carbon atoms

alkylglycoside

C _12-16 -fatty alcohol-1,4-glucoside (Cognis)

In the following Table 1 are compared in Examples 1 to 5 granules according to the invention with a non-inventive granules (Example 6), which was prepared by a granules of the frame formulation has been applied to the surfactant in molten form.

In terms of spotting and filming, this granulate of Example 6 showed inferior performance characteristics than the inventive granules 1 to 5. <b> Table 1 </ b> example surfactant Granulometry of the surfactant granules Filming in% * Spotting in% 1 C16 / 18 40 EO d <0.4 mm: 29.8% Glass: 68 Glass: 3 d ≥ 1.6 mm: 10.6% Steel: 0.9 d _m = 0.71 mm Melamine: 0.8 d '= 0.79 mm n = 1.49 2 C16 / 18 40 EO d <0.4 mm: 99.3% Glass: 88 Glass: 4 d ≥ 1.6 mm: 0% Steel: 1.4 d _m = 0.13 mm Melamine: 5.7 d '= 0.09 mm n = 8.5 3 C16 / 18 40 EO d <0.4 mm: 0% Glass: 86 Glass: 3.8 d ≥ 1.6 mm: 42.1% Steel: 0.8 d _m = 1.28 mm Melamine: 4.3 d '= 1.32 mm n = 13 4 C16 / 18 40 EO d <0.4 mm: 22.6% Glass: 99 Glass: 4.5 d ≥ 1.6 mm: 0% Steel: 1,2 d _m = 0.69 mm Melamine: 5,8 d '= 0.80 mm n = 2.0 5 C16 / 18 40 EO d <0.4 mm: 50.0% Glass: 82 Glass: 4.1 d ≥ 1.6 mm: 19.6% Steel: 1 d _m = 0.69 mm Melamine: 4,8 1: 1 mixture of Tensidfraktionen 2 and 3 6 C16 / 18 40 EO Melted and on Glass: 85 Glass: 5.2 ADD granules Melamine: 4.2 sprayed

In Table 2, the results for a granule according to the invention (Example 7) and a non-inventive granules (Example 6) are reproduced. Example 6 represents a granulate whose characteristic values d _m and d 'are below the limits according to the invention. As can be seen, this leads to a significant difference in the performance properties of the granules. <b> Table 2 </ b> example surfactant Granulometry of the surfactant granules Filming in% * Spotting in% 7 C18 80 EO d <0.4 mm:?% Glass: 81 Glass: 5 d ≥ 1.6 mm:?% PP: 11.6 d _m = 0.16 mm Melamine: 3,5 d '= 0.17 mm n = 5.3 8th C18 80 EO d <0.4 mm: 33.6% Glass: 17.5 Glass: 3.7 d ≥ 1.6 mm: 19.3% PP: 6.5 d _m = 0.75 mm Melamine: 0.9 d '= 0.82 mm n = 1.25

Table 3 gives the data of two granules, wherein an alkyl (oligo) glycoside was used as the nonionic surfactant. The granules of Example 9 show good performance properties, whereas the granules in Example 10, which has been prepared by spraying the APG / fatty alcohol mixture on the granulated frame formulation, disadvantages in the application properties. <b> Table 3 </ b> example surfactant Granulometry of the surfactant granules Filming in% * Spotting in% 9 Alkyl polyglucoside / C22 fatty alcohol mixture d <0.4 mm: 29.9% Glass: 38 Glass: 3,5 d ≥ 1.6 mm: 21.4% Steel: 3.9 d _m = 0.79 mm Melamine: 2.5 d '= 0.90 mm n = 1.3 10 Alkyl polyglucoside / C22 fatty alcohol mixture Melted and sprayed onto the ADD granules Glass: 85 Glass: 7 Steel: 5.9 Melamine: 8,3

In Table 4, the results for a non-inventive granules (Example 11) compared with a granulate in the context of the invention. Again, it clearly shows that selecting a particular granulometry leads to better performance results. <b> Table 4 </ b> example surfactant Granulometry of the surfactant granules Filming in% * Spotting in% 11 C22 FA 10 EO Melted and sprayed onto the ADD granules Glass: 33 Glass: 4.7 PP: 4.9 Melamine: 11.1 12 C22 FA 10 EO d <0.4 mm: 1.6% Glass: 8,3 Glass: 2 d ≥ 1.6 mm: 43.6% PP: 4.5 d _m = 1.25 mm Melamine: 1,8 d '= 1.40 mm n = 2.79

Table 5 gives the data for granules containing ethoxylated fatty alcohols. <b> Table 5 </ b> example surfactant Granulometry of the surfactant granules Filming in% * Spotting in% 13 C16 / 18 FA 20 EO Melted and sprayed onto the ADD granules Glass: 75 Glass: 5.1 PP: 5.2 Melamine: 14.5 14 C16 / 18 FA 20 EO d <0.4 mm: 10.8% Glass: 8 Glass: 3.1 d ≥ 1.6 mm: 21.0% PP: 3.0 d _m = 0.94 mm Melamine: 2.0 d '= 1.07 mm n = 2.67 * Filming is only possible with the digital evaluation due to the measuring arrangement with glass

It is clear from the examples given that the granular form obtained by the production process has a significantly better rinsing performance than larger or smaller particle particles.
The result of the rinse performance also indicates that no foam problems occurred during the cleaning cycle. A visual check 10, 20, 30 and 40 minutes after the start of the cleaning program showed that the foam level had at no time reduced the performance of the dishwasher.

Claims (5)

1. A solid granular composition consisting of nonionic surfactants selected from at least one member of the group a) to d) as follows:

   a) compounds of the general formula (I)
   
           R¹O[CH₂CH₂O]_xCH₂CH(OM)R²     (I)
   
   in which R¹ is a linear or branched alkyl and/or alkenyl radical having 4 to 22 carbon atoms, or is a radical R²-CH(OH)CH₂ where R² is a linear or branched alkyl and/or alkenyl radical having 8 to 16 carbon atoms, x is a number from 40 to 80, and M is a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms;

   b) compounds of the formula (II)
   
           R³O[CH₂CH₂O]_y[CH₂CHCH₃O]_zCH₂CH(OH)R⁴     (II)
   
   in which R³ is a linear or branched alkyl and/or alkenyl radical having 8 to 22 carbon atoms, R⁴ is a linear or branched alkyl and/or alkenyl radical having 8 to 16 carbon atoms, y is a number from 10 and 35, z is zero or a number from 1 to 5, with the proviso that if R³ = R¹ and at the same time R⁴ = R², then z must be at least 1;

   c) ethoxylated fatty alcohols of the general formula (III)
   
           R⁵-(OC₂H₄)_z-OH
   
   in which R⁵ is linear or branched alkyl and/or alkenyl radicals having 8 to 22 carbon atoms and z is a number from 1 to 20;

   d) alkyl(oligo)glycosides of the general formula R⁸O-[G]_p in which R⁸ is an alkyl and/or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms, and p is numbers from 1 to 10;

   and mixtures of the compounds a) to d) with one another, wherein the granular composition according to sieve analysis with a sieve according to DIN ISO 3310-1 has a particle size distribution, where the particle size distribution, which is determined graphically by RRSB diagram according to DIN 66145, must fulfill the following parameters:

   d_m is in the range from 0.5 to 1.5 mm;

   d₆₃.₃ is in the range from 0.5 to 1.5 mm;

   and n is in the range from 1 to 10.
2. The composition according to claim 1, wherein the three parameters comprise the following ranges: d_m is in the range from 0.5 to 1.2 mm; d₆₃.₃ is in the range from 0.5 to 1.0 mm; and n is in the range from 1 to 5.
3. The composition according to claims 1 to 2, wherein it comprises nonionic surfactants of classes a) and/or b).
4. The use of a composition according to claims 1 to 3 for producing solid laundry detergents and cleaning products.
5. The use of a composition according to claims 1 to 3 for improving the rinse-clear performance of cleaning products for cleaning hard surfaces, especially for cleaning products for automatic dishwashing.