DE19603760A1 - Solid detergent preparations - Google Patents

Abstract

Solid detergent preparations are disclosed for use in dish washing machines in the form of pressed pourable grains with a powder density of at least 700g/l; these preparations can be manufactured using little or no water and with a minimum of drying processes. To that end, solid components, including at least some builders, alkali carriers, oxygen bleaches and/or bleach activators, are used, together with other substances at least some of which are liquid or plastically deformable (fluid phase) at temperatures above 30 DEG C. The fluid phase contains at least one additional component which is solid at temperatures below about 30 DEG C and has a melting point of below 60 DEG C. Also disclosed is a process for manufacturing solid detergent preparations, whereby the components in a homogenous mixture are extruded at a temperature above 30 DEG C, cut into the predetermined dimensions and, if necessary, shaped. The additional component of the fluid phase is allowed to set by cooling.

Description

The invention relates to solid detergent formulations for machine Ge dishwashing and a process for their preparation.

Weakly alkaline agents for machine dishwashing are known. In the DE 42 32 170 are such highly effective means for the machine Geschirreini described in which completely replaced pentaalkalitriphosphate and also the Ge strongly reduces phosphate substitutes such as native and synthetic polymers or completely restricted. Typical cleaning agents can ge According to this teaching sodium citrate, citric acid, soda, sodium silicate, sodium hydrogencarbonate, sodium perborate, sodium percarbonate, bleach activators, Ten contain side and enzymes.

However, processing and use of these agents can cause problems come. The often offered in conventional detergents Darreichungs Form of the powder mixture has the disadvantage that they are in the manufacture and the Use often heavily dusty. In addition, powders tend just like usual Mixed granules, in which the dust is significantly minimized, for Demixing of the individual components, resulting in a reproducible cleaner performance may adversely affect. In addition, in conventional granules tion methods, often using water or aqueous solutions work, gluing and baking of the individual basic body often not enough close, which adversely affects the flowability of the detergent and thus  their metering ability, or their storage stability affects. This can only be done so far elaborate, often multi-stage, drying process can be prevented.

From DE 39 26 253 process for the production of extrudates are known where in a homogeneous, solid premix under pressure extruded pressed and the Strand after emerging from the hole shape by means of a cutting device on the predetermined granule dimension is cut. The homogeneous and solid vor Mixture contains a plasticizer and / or lubricant, which causes the Vor softened under pressure or plastically softened under the entry of specific work and becomes extrudable. Preferred plasticizers and / or lubricants are surfactants and / or polymers, preferably in liquid, pasty or gelatinous Form of preparation can be used. The premix can also powder and / or granules wherein the granules inter alia by granulating Processes or obtained by conventional spray drying processes who the. After exiting the hole form, no shear forces act on the system more and the viscosity of the system is thereby increased so that the extruded strand can be cut to predictable Extrudatdimensionen can. The disadvantages of the powder form are avoided here, but by the Use of aqueous solutions, aqueous plasticizers and lubricants, or strong Hydratwasserhaltiger components, it can be used for bonding and baking the Products come, which drying processes are required.

Against the background of this prior art, it is an object of the invention new, solid detergents for machine dishwashing in the form of press lingen provide that at high bulk density as free-flowing, not ver Bending products can be offered. Another task of Invention is vorzuschla a suitable manufacturing process for such products conditions that are low in water or anhydrous and with a minimum of Drying processes manages.

The invention thus relates to a solid detergent preparation for the Machine dishwashing in the form of compacts in free-flowing granular form, the to bulk weights of at least 700 g / l, containing solid In  ingredients which are at least partially of the class of builders, alkali carriers, sow bleach activators and / or bleach activators and at least continue to belong Partially at temperatures above 30 ° C liquid or plastically deformable Substances (liquid phase), which may belong to the class of surfactants, thereby characterized in that the liquid phase at least one below about 30 ° C in solid form component having a melting point of less than 60 ° C included.

Another object of the invention is a process for the preparation of solid Detergent preparations, characterized in that solid and liquid Mixtures to a homogeneous, formable verpreßbaren mass by Mi prepared this mass via hole shapes with opening widths of vorbe agreed compact dimension at temperatures above 30 ° C stranded ver presses the emerging compacted strands of material by means of a cutting edge direction tailored to the predetermined compact dimension, if desired the resulting still plastic particles changed shape and the between 30 and 60 ° C melting additional component by cooling solidify. This can happen for example in an extruder.

Without the invention being restricted to a particular theory, is assumes that the component used in the products according to the invention with a melting point between 30 and 60 ° C within the scope of the processing pro As a liquid formulating aids is present and their solidification after End of processing contributes to the solidification of the resulting compacts. It is crucial that this component, even when mixed with is present, solidifies, d. H. at least partially crystallized. It is assumed that the continued liquid shares of abge cooled liquid phase are absorbed in the pore volume of the solids, where whereas the hardened fractions contribute to solidification.

In a preferred embodiment, the invention Reini the liquid phase in proportions of 5 to 20 wt .-% particularly preferred in 10 to 15% by weight.  

Preferably, the liquid phase described one or more components which are selected from the group of paraffins, nonionic Surfactants, fatty acid and / or fatty alcohol derivatives. This contains the liquid phase this component or the sum of these components is preferred in amounts of 1 to 15 wt .-% based on the total preparation, in particularly preferred Embodiments in 2 to 5 wt .-%. The melting point of the component or the Components should preferably be between 35 ° C and 45 ° C.

Other parts of the liquid phase can in the sense of the application For example, be selected from the group of surfactants. (anionic surfactants Cationic surfactants, nonionic surfactants).

Particularly preferred for the solution of the present task is the use of nonionic surfactants selected from the group of ethoxylated fatty alcohols, Alkylpolyglycoside and / or the Fettsäureglucamide are selected.

The skilled worker will generally understand the alkoxylated alcohols Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols preferred in the context of the present invention, the longer-chain alcohols. In the Usually arise from n moles of ethylene oxide and one mole of alcohol, depending on the Reaction conditions a complex mixture of addition products different degree of ethoxylation. Another embodiment is in Use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. You can also if desired by a final Etherification with short-chain alkyl groups, such as preferably the butyl group, for Substance class of "closed" alcohol ethoxylates, which also in the Meaning of the invention can be used. Especially preferred in the sense The present invention are highly ethoxylated fatty alcohols or their Mixtures with end-capped fatty alcohol ethoxylates.

Alkyl polyglycosides are surfactants produced by the reaction of sugars and alcohols obtained by the relevant methods of preparative organic chemistry can be, depending on the nature of the preparation to a mixture  monoalkylated, oligomeric or polymeric sugar comes. preferred Alkyl polyglycosides may be alkyl polyglucosides, with particular preference being given to Alcohol is a long-chain fatty alcohols or a mixture of long-chain fatty alcohols and the degree of oligomerization of the sugars is between 1 and 10.

Fatty acid polyhydroxylamides (glucamides) are acylated reaction products of reductive amination of a sugar (glucose) with ammonia, using as Acylating agents usually long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are used. This creates secondary Amides, if instead of being reduced with ammonia with methylamine or ethylamine, like z. In SOFW Journal, 119, (1993), 794-808. Preferably used one carbon chain lengths of C₆ to C₁₂ in the fatty acid residue.

In addition, in the detergent and described below Method even more components are used, as in the following exemplified clarifies.

In the cleaning agents according to the invention, water-soluble and water-insoluble builders especially for binding calcium and magnesium be used. Water-soluble builders are preferred since they are based on dishes and hard surfaces tend to be less susceptible to insoluble residues to build. Usual builders, which in the context of the invention between 10 and 90 wt. % based on the total preparation are the low molecular weight polycarboxylic acids and their salts, the homopolymers and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and Silicates. Water-insoluble builders include the zeolites, which are also used may be, as well as mixtures of the aforementioned builders. For the detergents according to the invention are preferably trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders of the class of Disilikate used.

As further constituents alkali carriers may be present. To be considered as alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates  Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of aforementioned substances, wherein for the purposes of this invention preferably the Alkalicarbonates, in particular sodium carbonate, sodium bicarbonate or Sodium sesquicarbonate in amounts of 2 and 50 wt .-% based on the total Preparation can be used.

Other possible ingredients are oxygen bleaches. typical Oxygen bleaching agents are the alkali metal perborates and their hydrates and the Alkali metal percarbonates, being preferred in the invention Sodium perborate, as mono- or tetrahydrate, or sodium percarbonate and their Hydrates in amounts of 2 to 12 wt .-% based on the total preparation Find use.

Typical components of detergent preparations for the machine Dishwashing, for technical reasons, the preparation of the invention also subsequently in the form of a powder, a granulate or as a liquid bleach activators, enzymes, perfume oils can be mixed Corrosion inhibitors and formulation aids.

Known bleach activators are compounds which have one or more N- or O- Contain acyl groups, such as substances from the class of anhydrides, the ester the imides and the acylated imidazoles or oximes. Examples are tetraacetyl ethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylene diamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexa hydro-1,3,5-triazine DADHT and isatoic anhydride ISA. For the present Bleach activator components have between 1 and 5% by weight proven on the entire preparation.

According to the invention, the cleaning agent can contain between 0 and 5% by weight of enzymes be added to the total preparation to the performance of the To increase cleaning agents or under milder conditions the To ensure cleaning performance of the same quality. Among the most common enzymes used include lipases, amylases, cellulases and proteases.  

Preferred proteases are, for. B. BLAP®140 Fa. Biozym, Optimase® M-440 and Opticlean® M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo. Especially suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T the Fa. Novo Nordisk. Particular use as amylases is Termamyl® 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades but also other enzymes be applied.

Dishwashing agents according to the invention can be used to protect the ware or the Machine contain corrosion inhibitors, with particular silver protectants in the Machine dishwashing are of particular importance, such as they z. As described in DE 43 25 922, DE 41 28 672 or DE 43 38 724 are. In addition, cleaner formulations frequently contain active chlorine-containing compounds Means that can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygenated according to the above publications. and nitrogen-containing organic redox-active compounds such as two and trivalent phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone Gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt- and complex-like inorganic compounds, such as salts of metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Likewise Zinc compounds are used to prevent corrosion on the items to be washed.

Other known components for detergents and cleaners are often made taken from the group of perfume oils. They too can in the invention Detergent compositions may be included.

In addition, other additives can be used for confectioning be used, for example, to dust off the residual moisture in some preparations gen feinteilige reference fittings that the skilled person usually from the Group of precipitated silicas containing alkali carbonates (especially Sodium carbonate), the alkali bicarbonates (especially  Sodium bicarbonate), zeolites and similar suitable agents can.

A preferred detergent formulation according to the present invention contains, for example, 20 to 70 wt .-% sodium citrate, 2 to 10 wt .-% surfactants 2 to 15 wt .-% soda, 10 to 50 wt .-% sodium bicarbonate, 2 to 12 Wt .-% sodium perborate, 0 to 30 wt .-% polycarboxylic acid in each case based on the entire preparation.

It can be the detergent compositions according to the invention as Zumischkomponente also subsequently 1 to 5 wt .-% bleach activator, 0 to 5 % By weight of enzyme and / or 0 to 1% by weight of perfume oil added to the formulation.

For solving the problem of the invention can be described below Process used extrusion plant in various ways with material be charged. So z. B. all components to be extruded in one Premix be fed or mixed in the extruder itself, wherein then preferably the liquid components added through a separate nozzle become. In this case, according to the invention, the further active ingredients, such as in particular Bleach activators, corrosion inhibitors for silver, enzymes and the like, in Granules or be added as liquid or solid additives.

It plasticizes the mixture by pressure build-up in front of the perforated discs, energy Entry through the screws and additional heating by the jacket heating of the extruder. The compression of the extruded to find Detergent mass at pressures above 50 bar instead. The most special preferred embodiment of the method operates at pressures above 100 bar.

The temperature at which the mass plasticizes so that compression by the Perforated plate and cutting to cylindrical moldings is possible without it comes to sticking, depends on the recipe ingredients and lies preferably between 45 and 60 ° C, more preferably above 50 ° C.  

In the extruder is on uniform throughput through all openings of the Perforated disk, so that the strands through the rotating knives can be cut uniformly. A preferred embodiment for Spherical compacts is that the diameter of the material strand corresponds approximately to the height of the particles.

It can be used to control the temperature of the exiting plasticized strands be desired by shock cooling, in particular by means of cold air before and / or at least superficially cool during the fragmentation.

Then followed by a post-processing of the still plastic body in a commercially available Verrunder, whereupon the spherical parts still be made by powdering. It uses finely divided Reference fittings, in particular precipitated silicas, sodium carbonate Sodium hydrogencarbonate, zeolites and the like.

By working in a basically water-free environment while preserving The ability to shape the plasticized mass can usually According to the invention, drying steps are dispensed with. Should but under If there is still residual liquid, a drying step can also be used be performed. After cooling the product to room temperature (below 30 ° C) can be so free-flowing non-caking products with a bulk density of 600 to 1000 g / l can be obtained.

Examples

For the detergent formulations described below were in processed a Leistritz twin-screw laboratory extruder.

example 1 components: 1. trisodium citrate (2 H₂O) 48 2. soda 9.6 3. Sodium hydrogencarbonate 17.7 4. Sodium perborate (1 H₂O) 7.7 5. fatty alcohol (C _12-14 + 4 EO) 3.8 6. fatty alcohol (C _12-14 + 10 EO) butyl ether 1.9 7. Alkylpolyglycoside (C _8-10 ) (70%) 3.8 8. Paraffin 42/44 2.9 9. TAED granules 2.0 10. Enzymes 2.0 11. perfume 0.6

The plasticization of the continuously metered mixture of the components took place in the extruder by the energy input of the screw, if necessary by additional jacket heating and pressure build-up in front of the perforated disc. The Temperature at which the mass plasticized so that compression by the 1.6 mm Holes of the perforated plate and a cutting to cylindrical moldings possible is, without sticking, was in the present case at 54-58 ° C. The cylindrical shaped body with a length to diameter ratio of 1: 1 were processed into spherical particles in a market Under normal temperature became a free-flowing, not prone to caking  Obtained with the components 9-11 to a finished product with a bulk density of 860 g / l was mixed.

If the procedure is carried out with the components in this composition, that the solids 1-4 and the liquid components 5-8 each as a mixture in metered the extruder, then you get after processing also a Finished product with the properties of Example 1.

Example 2 components: 1. trisodium citrate (2 H₂O) 45.0 2. soda 10.0 3. Sodium hydrogencarbonate 22.5 4. Sodium perborate (1 H₂O) 5.0 5. fatty alcohol (C _12-14 + 4 EO) 2.5 6. fatty alcohol (C _16-18 + 25 EO) 2.5 7. fatty alcohol (C _12-14 + 10 EO) butyl ether 6.5 8. TAED granules 2.0 9. enzymes 3.0 10. zeolite 1.0

The production of Rohextrudates carried out by the use of a mixture of Components 1-7 under the same conditions as in Example 1 and a Processing temperature of 50-53 ° C. after rounding under powdering with Component 10 and balance blending with components 8 and 9 became a good one flowable finished product having a bulk density of 920 g / l.

Example 3 components: 1. trisodium citrate (2H₂O) 33.5 2. citric acid (1 H₂O) 8.2 3. soda 10.0 4. Sodium bicarbonate 27.3 5. sodium perborate (1 H₂O) 5.0 6. fatty alcohol (C _12-14 + 4 EO) 2.0 7. fatty alcohol (C _12-14 + 10 EO) butyl ether 6.0 8. Paraffin 40/42 3.0 9. TAED granules 2.0 10. Enzymes 3.0

By using a mixture of components 1-8 in the preparation of the Rohextrudates under the conditions of Example 1 was after residual mixing with the components 9 and 10 a good flowable product with a Bulk density of 880 g / l obtained.

Claims (16)

A solid detergent formulation for machine dishwashing in the form of compacts in free-flowing granular form, which are compacted to bulk densities of at least 700 g / l, containing solid ingredients belonging at least partially to the class of builders, alkali carriers, oxygen bleach and / or bleach activators and further at least partially at temperatures above 30 ° C liquid or plastically deformable substances (liquid phase), which may belong to the class of surfactants, characterized in that the liquid phase at least one component below about 30 ° C in solid form with a component Melting point of less than 60 ° C contains. 2. Solid detergent composition according to claim 1, characterized in that that the liquid phase 5 to 20 wt .-%, preferably 10 to 15 wt .-%, bezo to total preparation. 3. Solid detergent composition according to claims 1 and 2, characterized ge indicates that as a liquid phase partially surfactants, in particular nonionic surfactants, preferably ethoxylated, long-chain alcohols, Alkylpolyglycosides and / or Fettsäureglucamide be used. 4. Solid detergent composition according to claims 1 to 3, characterized ge indicates that belonging to the liquid phase, at temperatures below 30 ° C. solid component, at a melting point of less than 60 ° C in quantities of 1 to 15 wt.%, Preferably from 2 to 5 wt .-%, based on the total Detergent preparation is included. 5. detergent composition according to claims 1 to 4, characterized marked characterized in that as at about 30 ° C solid component with a melting klei at 60 ° C paraffins, nonionic surfactants, fatty acid and / or fatty alcohol derivatives with melting points between 30 and 60 ° C, in particular 35 to 45 ° C, are used.   6. detergent composition according to claims 1 to 5, characterized marked shows that highly ethoxylated fatty alcohols are used as surfactants. 7. detergent composition according to claims 1 to 6, characterized gekenn characterized in that as builders, salts of polyfunctional carboxylic acids, in particular Trisodium citrate and / or pentasodium tripolyphosphate and if desired silicate builders from the class of disilicates are used. 8. detergent composition according to claims 1 to 7, characterized marked records that as alkalizing alkali metal carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate used become. 9. detergent composition according to claims 1 to 8, characterized marked records that as oxygen bleach sodium perborate, as mono- or Tetrahydrate or sodium percarbonate can be used. 10. detergent composition according to claims 1 to 9, characterized marked characterized in that it contains 20 to 70% by weight of sodium citrate, 2 to 10% by weight of surfactants, 2 to 15 wt .-% soda, 10 to 50 wt .-% sodium bicarbonate, 2 to 12 Wt .-% sodium perborate, 0 to 30 wt .-% polycarboxylic acid. 11. detergent composition according to claims 1 to 10, characterized marked records that subsequently as admixing component 1 to 5 wt .-% Bleaching acti vator, 0 to 5 wt .-% enzyme and / or 0 to 1 wt .-% perfume oil for confection be added. 12. A process for the preparation of solid detergent compositions according to Claims 1 to 11, characterized in that solid and liquid Be components to a homogeneous, formable compressible mass by Mi prepared this mass via hole shapes with opening widths of the front certain Presslingdimension at temperatures above 30 ° C stranded pressed, the emerging compacted strands of material by means of a cutting edge  cut device to the predetermined compact dimension, ge if desired, the obtained still plastic particles changed shape and the additional component melting between 30 and 60 ° C Let cool solidify. 13. A process for the preparation of solid detergent compositions according to Claims 1 to 11, characterized in that the compacts with fine-particle reference fittings, in particular precipitated silicas Sodium carbonate, sodium bicarbonate and the like for avoidance powdered from surface tackiness. 14. A process for the preparation of solid detergent compositions according to Claims 1 to 11, characterized in that further active ingredients especially bleach activators, corrosion inhibitors for silver, enzymes and the like in granular form or as liquid or solid additives mixed. 15. A process for the preparation of solid detergent compositions according to Claims 1 to 11, characterized in that one for the removal of introduces a drying step about existing residual liquid quantities. 16. A process for the preparation of solid detergent compositions according to Claims 1 to 11, characterized in that the compression under Use of greatly increased pressure, preferably at above 50 bar, in particular in particular in the range of at least about 100 bar and moderately raised Mass temperatures, for example, in the range of 45 to 60 ° C and performs if desired, by shock cooling, in particular by means of cold air from the passing plasticized strands before and / or during the fragmentation little at the very least superficially cools.