EP0885289B1 - 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 preparations for the machine Dishwashing and a process for their manufacture.

Weakly alkaline agents for machine dishwashing are known. In DE 4232170 describes such highly effective agents for the machine Dishwashing described, in which pentaalkali nitride is completely replaced and also the content of phosphate substitutes such as native and synthetic Reduce polymers significantly or has been completely restricted. Typical According to this teaching, cleaning agents can contain sodium citrate, citric acid, soda, Sodium silicate, sodium hydrogen carbonate, sodium perborate, sodium percarbonate, Contain bleach activators, surfactants and enzymes.

When processing and using these funds, however, it can be too Problems come up. The ones often offered in conventional cleaning agents Dosage form of the powder mixture has the disadvantage that it Manufacturing and use often very dusty. Powders also tend just like usual mixed granules, in which the dust development already is significantly minimized for segregating the individual components, which is based on reproducible cleaning performance can adversely affect. Furthermore is in conventional granulation processes, often using Water or aqueous solutions work, a sticking and caking of the individual body often cannot be excluded, which negatively affects the Free-flowing properties of the detergents and thus their metering ability, or their Storage stability affects. So far, this has only been possible through complex, often multi-stage, Drying processes can be prevented.

Processes for the production of extrudates are known from DE 39 26 253 whereby a homogeneous, solid premix is extruded under pressure and the strand after exiting the hole shape by means of a cutting device is cut to the predetermined granule dimension. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes that the pre-mix under pressure or under the entry of specific work plastically softened and becomes extrudable. Preferred plasticizing and / or Lubricants are surfactants and / or polymers, which are preferably in liquid, pasty or gel-like preparation form can be used. The The premix can also contain powders and / or granules Granules, among other things, through granulation processes or through conventional spray drying processes can be obtained. After leaving the hole shape no longer acts on the system and the The viscosity of the system increases in such a way that the extruded strand can be cut to predeterminable extrudate dimensions. The Disadvantages of the powder form are avoided here, but by the Use of aqueous solutions, aqueous plasticizers and lubricants, or strong components containing hydrate water can be used to glue and bake the Products come, making drying processes necessary.

Against the background of this prior art, it is the object of the invention new, solid detergents for automatic dishwashing in the form of Provide compacts that are free flowing at high bulk density, not products that tend to cake can be offered. Another The object of the invention is a suitable manufacturing process for such To propose products that work with little or no water and with one Minimum drying processes.

"Low water" in this context means a lot of water which, in Depending on the water absorption capacity of the feed materials, none additional drying step is necessary.

The invention thus relates to a process for the production of solid cleaning agent preparations, in which solid and liquid components form a homogeneous, shaping compressible mass prepared by mixing, the mass using hole shapes Opening widths of the predetermined compact size at temperatures above 30 ° C extruded, the emerging compacted material strands by means of a cutting device tailored to the predetermined compact size and if desired the resulting still plastic particles changed shape, characterized, that the ingredients are between 30 ° C and 60 ° C, especially between 35 ° C and 45 ° C, contain melting paraffin as an additional component, and this after the cutting process / or solidify by cooling after further shaping. This can for example in an extruder.

Another object of the invention is a solid detergent preparation for the machine dishwashing in the form of pellets in a poured shape, which on Bulk densities of at least 700 g / l are compressed, containing solid ingredients that at least in part of the class of builders, alkali carriers, oxygen bleaches and / or Bleach activators belong and continue to at least partly at temperatures above 30 ° C liquid or plastically deformable substances (liquid phase) belonging to the class of surfactants can belong, characterized in that the liquid phase between 30 ° C and 60 ° C, especially between 35 ° C and 45 ° C, contains melting paraffin.

Without restricting the invention to any particular theory suspects that the used in the products of the invention Component with a melting point between 30 and 60 ° C within the Processing process is available as a liquid assembly aid and you Solidify after processing to solidify the resulting Pressings contributes. The key is that this component, even if it is in a mixture with other liquid components, solidifies, d. H. at least partially crystallized out. It is believed that the continue liquid portions of the cooled liquid phase in the pore volume of the Solids are sucked up, whereas the hardened parts Contribute to consolidation.

In a preferred embodiment, the cleaning agents according to the invention contain the liquid phase especially in proportions of 5 to 20% by weight preferably in 10 to 15% by weight.

The liquid phase described contains the preferably in quantities from 1 to 15% by weight, based on the entire preparation, in particular preferred embodiments in 2 to 5 wt .-%. The melting point of the Pataffins should preferably be between 35 ° C and 45 ° C.

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

This is particularly preferred for the solution of the present task Use of nonionic surfactants from the group of ethoxylated Fatty alcohols, the alkyl polyglycosides and / or the fatty acid glucamides are selected.

The person skilled in the art generally understands alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arise from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation. Another embodiment exists when using mixtures of the alkylene oxides preferred the mixture of Ethylene oxide and propylene oxide. You can also, if desired, by a final etherification with short-chain alkyl groups, such as the Butyl group, to the substance class of "closed" alcohol ethoxylates arrive, which can also be used in the sense of the invention. All are particularly preferred for the purposes of the present invention highly ethoxylated fatty alcohols or mixtures thereof end-capped fatty alcohol ethoxylates.

Alkyl polyglycosides are surfactants caused by the reaction of sugars and Alcohols according to the relevant procedures of preparative organic Chemistry can be obtained, depending on the type of manufacture to one Mixture of monoalkylated, oligomeric or polymeric sugar comes. Preferred Alkyl polyglycosides can be alkyl polyglucosides, with particular preference the alcohol is a long chain fatty alcohol or a mixture of long chain Is fatty alcohols and the degree of oligomerization of the sugars is between 1 and 10.

Fatty acid polyhydroxylamides (glucamides) are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, whereby long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are generally used as acylating agents. Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, such as. B. in SÖFW-Journal, 119, (1993), 794-808. Carbon chain lengths of C ₆ to C ₁₂ in the fatty acid residue are preferably used.

In addition, the detergent and that described below Other components can also be used as follows is exemplified.

Water-soluble and water-insoluble builders especially for binding calcium and magnesium be used. Water-soluble builders are preferred because they are based on Dishes and hard surfaces tend to be less insoluble To form residues. Usual builders that are within the scope of the invention 10 and 90% by weight, based on the total preparation, can be present, are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the Carbonates, phosphates and silicates. Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances. For the cleaning agents according to the invention are preferred trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of disilicates used.

Alkali carriers can be present as further constituents. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures the abovementioned substances, the preferred being in the sense of this invention Alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or Sodium sesquicarbonate in amounts 2 and 50 wt .-% based on the total Preparation can be used.

Other possible ingredients are oxygen bleaches. Typical Oxygen bleaches are the alkali metal perborates and their hydrates and Alkali metal percarbonates, preferred in the context of 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 Use preparation.

Typical components of detergent preparations for the machine Dishwashing, the technical reasons of the invention Preparation also in the form of a powder, a granulate or as Bleach activators, enzymes, Perfume oils, anti-corrosion agents and packaging aids.

Known bleach activators are compounds that contain one or more N or O-acyl groups, like substances from the class of anhydrides, contain Esters, the imides and the acylated imidazoles or oximes. examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA. For the present invention, bleach activator proportions between 1 and 5% by weight based on the entire preparation.

According to the invention, between 0 and 5% by weight of the cleaning agent Enzymes based on the entire preparation are added to the To increase the performance of the cleaning agents or under milder conditions To ensure cleaning performance of the same quality. The most common Enzymes used include lipases, amylases, cellulases and proteases. Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo. Celluzym® 0.7 T and. Are particularly suitable cellulases and lipases Lipolase® 30 T from Novo Nordisk. Special use as amylases find Termamyl® 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Fa. Solvay Enzymes or Maxamyl® P5000 from Fa. Gist Brocades as well other enzymes can be used.

Dishwashing agents according to the invention can be used to protect the items to be washed or the machine contain corrosion inhibitors, especially Silver protection agent in the field of automatic dishwashing a special one Have meaning as z. B. in DE 43 25 922, DE 41 28 672 or DE 43 38 724 are described. One finds in cleaner formulations In addition, active chlorine-containing agents which corrode the Can significantly reduce the silver surface. In chlorine-free cleaners according to the above writings especially oxygen and nitrogenous organic redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Zinc compounds can also be used to prevent corrosion on the wash ware.

Other known components for detergents and cleaning agents are often made taken from the group of perfume oils. You can also in the detergent compositions according to the invention may be included.

In addition, other additives can be used for assembly such as powdering the residual moisture in some Preparations of finely divided reference fittings, which the person skilled in the art generally from the group of precipitated silicas, the alkali carbonates (especially Sodium carbonate), the alkali hydrogen carbonates (especially Sodium hydrogen carbonate), the zeolites and similar suitable agents can choose.

A preferred detergent preparation according to the present invention contains, for example, 20 to 70% by weight sodium citrate, 2 to 10% by weight Surfactants, 2 to 15% by weight soda, 10 to 50% by weight sodium hydrogen carbonate, 2 up to 12% by weight sodium perborate, 0 to 30% by weight polycarboxylic acid each based on the entire preparation.

You can the detergent preparations according to the invention as Additive component also subsequently 1 to 5% by weight of bleach activator, 0 to 5 % By weight of enzyme and / or 0 to 1% by weight of perfume oil for packaging add.

To solve the problem according to the invention can be described below Process used extrusion line with material in different ways be loaded. So z. B. all components to be extruded in are fed to a premix or mixed in the extruder itself, then preferably the liquid components by a separate Nozzles are added. According to the invention, the others Active substances, such as bleach activators, corrosion inhibitors for silver, Enzymes and the like, in granular form or as liquid or solid Additives are added.

The mixture is plasticized by building up pressure in front of the perforated disks, Energy input by the snails and additional warming up by the Jacket heating of the extruder. The pressing takes place to extruding detergent mass instead at pressures above 50 bar. The particularly preferred embodiment of the method works at pressures above 100 bar.

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

The throughput in the extruder is as uniform as possible through all openings the perforated disc, so that the strands through the rotating knife can be cut uniformly. A preferred embodiment for spherical compacts is that the diameter of the Material strand approximately corresponds to the height of the particles.

It can be used to control the temperature of the emerging plasticized strands these should be desired by flash cooling, in particular by means of cold air and / or to cool at least superficially during the division.

After that, the still plastic bodies are preferably reprocessed in a standard rounder, followed by the spherical parts can still be assembled by powdering. You use finely divided reference fittings, especially precipitated silicas, Sodium carbonate, sodium hydrogen carbonate, zeolites and the like.

By working in a fundamentally water-free environment under simultaneous Maintaining the ability to shape the plasticized mass can usually According to the invention, drying steps can be dispensed with. But should, under Circumstances depending on the water absorption capacity of the feed materials, If there is still residual liquid, a drying step can also be carried out be performed. The amount of water is preferably less than 5% by weight. particularly preferably below 3% by weight and very particularly preferably below 2 % By weight. Such a small amount of water, no additional Drying step requires more control of the Plasticizing ability of the mixture can be very useful. Therefore, at selected Examples if the plastication is not with other known measures is controlled and changed, a water content above 1 wt .-% preferred.

After cooling the product to room temperature (below 30 ° C) you can free-flowing, non-caking products with a bulk density from 600 to 1000 g / l can be obtained.

Examples:

For the cleaning agent preparations described below, in a twin-screw laboratory extruder from Leistritz.

Example 1:

Components 1. Trisodium citrate (2 H ₂ O) 48 2nd soda 9.6 3rd Sodium bicarbonate 17.7 4th Sodium perborate (1 H ₂ O) 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. Alkyl polyglycoside (C _8-10 ) (70%) 3.8 8th. Paraffin 42/44 2.9 9. TAED granules 2.0 10th Enzymes 2.0 11. Perfume 0.6

The plasticization of the continuously metered mixture of components 1-8 was carried out in the extruder by the energy input of the screws, if necessary through additional jacket heating and through pressure build-up in front of the perforated disc. The temperature at which the mass plasticizes so that it is pressed by the 1.6 mm holes in the perforated plate and a cutting to cylindrical Shaped bodies is possible without it sticking, lay in present case at 54 - 58 ° C. The cylindrical shaped body with a Length / diameter ratio of 1: 1 were in a standard market Rounder processed into spherical particles. Under normal temperature received a free-flowing, non-caking product, which with components 9-11 to a finished product with a bulk density of 860 g / l was mixed.

If the process is carried out with the components in this composition, that the solids 1-4 and the liquid components 5-8 each as Mix dosed into the extruder, then you get after processing also a finished product with the properties of Example 1

Example 2:

Components: 1. Trisodium citrate (2 H ₂ O) 33.5 2nd Citric acid (1 H ₂ O) 8.2 3rd soda 10.0 4th Sodium bicarbonate 27.3 5. Sodium perborate (1 H ₂ O) 5.0 6. Fatty alcohol (C _12-14 + 4 EO) 2.0 7. Fatty alcohol (C _12-14 + 10 EO) butyl ether 6.0 8th. Paraffin 40/42 3.0 9. TAED granules 2.0 10th Enzymes 3.0

By using a mixture of components 1-8 in the manufacture of the crude extrudate under the conditions of Example 1 was followed Remaining mix with components 9 and 10 with a good flowable product a bulk density of 880 g / l.

Claims (16)

1. A process for the production of solid detergent formulations, in which solid and liquid components are mixed to form a homogeneous mouldable paste, the paste thus formed is extruded through extrusion dies with bore diameters corresponding to the predetermined size of the extrudate at temperatures above 30°C to form strands, the compacted strands issuing from the extrusion dies are cut by a cutting unit into particles of predetermined size and the still plastic particles obtained are optionally subjected to shaping, characterized in that the ingredients contain a paraffin melting between 30°C and 60°C and more particularly between 35°C and 45°C as an added component and the added component is allowed to solidify by cooling after cutting and/or after further shaping.
2. A process for the production of the solid detergent formulations claimed in claim 1, characterized in that the granules are dusted with fine-particle coating materials, more particularly precipitated silicas, sodium carbonate, sodium hydrogen carbonate and the like, to avoid surface tackiness.
3. A process for the production of the solid detergent formulations claimed in claims 1 and 2, characterized in that other active substances, more particularly bleach activators, silver corrosion inhibitors, enzymes and the like, are added in granular form or as liquid or solid additives.
4. A process for the production of the solid detergent formulations claimed in claims 1 to 3, characterized in that a drying step is introduced to remove any residual liquid present.
5. A process for the production of the solid detergent formulations claimed in claims 1 to 4, characterized in that the extrusion process is carried out under very high pressures, preferably above 50 bar and, more particularly, in the region of at least about 100 bar and at moderately elevated compound temperatures, for example in the range from 45 to 60°C, and if desired the plasticized strands issuing from the extrusion die are at least surface-cooled by shock cooling, more particularly with cold air, before and/or during their size reduction.
6. A process as claimed in claims 1 to 5, characterized in that, to control plasticizing behavior during the process, water is optionally added in a quantity which does not necessitate an additional drying step and which is preferably between 1 and 5% by weight, more preferably between 1 and 3% by weight and most preferably between 1 and 2% by weight.
7. A solid detergent formulation for machine dishwashing in the form of free-flowing granules which are compacted to bulk densities of at least 700 g/l and which contain solid ingredients at least partly belonging to the class of builders, alkali carriers, oxygen bleaching agents and/or bleach activators and, in addition, substances which are at least partly liquid or plastic at temperatures above 30°C (liquid phase) and which may belong to the class of surfactants, characterized in that the liquid phase contains a paraffin melting between 30°C and 60°C and more particularly between 35°C and 45°C.
8. A solid detergent formulation as claimed in claim 7, characterized in that the liquid phase makes up 5 to 20% by weight and preferably 10 to 15% by weight, based on the formulation as a whole.
9. A solid detergent formulation as claimed in claim 7 or 8, characterized in that surfactants, particularly nonionic surfactants, preferably ethoxylated, long-chain alcohols, alkyl polyglycosides and/or fatty acid glucamides are partly used as the liquid phase.
10. A solid detergent formulation as claimed in claims 7 to 9, characterized in that the paraffin melting between 30°C and 60°C is present in quantities of 1 to 15% by weight and preferably in quantities of 2 to 5% by weight, based on the detergent formulation as a whole.
11. A detergent formulation as claimed in claims 7 to 10, characterized in that highly ethoxylated fatty alcohols are used as surfactants.
12. A detergent formulation as claimed in claims 7 to 11, characterized in that salts of polybasic carboxylic acids, more particularly trisodium citrate and/or pentasodium tripolyphosphate, and if desired silicate builders from the class of disilicates are used as builders.
13. A detergent formulation as claimed in claims 7 to 12, characterized in that alkali metal carbonates, more particularly sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, are used as alkalizing agents.
14. A detergent formulation as claimed in claims 7 to 13, characterized in that sodium perborate as monohydrate or tetrahydrate or sodium percarbonate is used as the oxygen bleaching agent.
15. A detergent formulation as claimed in claims 7 to 14, characterized in that it contains 20 to 70% by weight of sodium citrate, 2 to 10% by weight of surfactants, 2 to 15% by weight of soda, 10 to 50% by weight of sodium hydrogen carbonate, 2 to 12% by weight of sodium perborate and 0 to 30% by weight of polycarboxylic acid.
16. A detergent formulation as claimed in claims 7 to 15, characterized in that 1 to 5% by weight of bleach activator, 0 to 5% by weight of enzyme and/or 0 to 1% by weight of perfume oil are subsequently added for compounding.