ES2158487T5 - SOLID PREPARATIONS OF WASHING AGENTS. - 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

Solid preparations of washing agents.

The invention relates to preparations of solid washing agents for mechanical dishwashing as well as a procedure for its manufacture.

Weakly alkaline agents are known for mechanical cleaning of the dishes. DE 4232170 describes highly effective agents of this type for mechanical cleaning of the dishes, in which the pentaalkaline triphosphate and have also greatly reduced the content in phosphate substituents such as polymers natural and synthetic or have been completely limited. Agents of Typical cleaning may contain, according to these teachings, citrate sodium, citric acid, sodium carbonate, sodium silicate, sodium bicarbonate, sodium perborate, sodium percarbonate, bleaching activators, surfactants and enzymes.

However, problems may occur during the development and use of these agents. The way of administration of the powder mixture, frequently marketed in traditional cleaning agents, it has the inconvenience that frequently forms a large amount of dust during manufacturing and use. In addition the powders have trend, exactly like the usual mixed granules, in the which has already significantly reduced dust formation, to the breakdown of individual components, which can have negative effects on a cleaning performance reproducible. In addition, you cannot frequently exclude a paste and a crimp of the individual base bodies in the traditional granulation procedures, which work frequently with the use of water or aqueous solutions, which has a negative effect on the creep capacity of the agent of cleaning and, therefore, about its dosing capacity or Good about its storage stability. This could avoided until now only through procedures costly drying, which often contain several stages.

Procedures are known from DE 39 26 253 for the manufacture of extruded bodies, in which it is pressed into bar shape, under pressure, a homogeneous, solid premix and the bar is chopped, after its exit from the perforated mold, by means of a cutting device, to a granulate dimension pre-determined The homogeneous and solid premix it contains a plasticizing and / or lubricating agent, which acts as such so that the premix softens in a plastic way and can be extruded under pressure or under work application specific. Plasticizing and / or lubricating agents Preferred are surfactants and / or polymers, which are used preferably in liquid, pasty or gel-like compositions. The premix may also contain powders and / or granules, obtaining the granules, among other things, through processes of granulation or also by traditional drying processes by spraying After leaving the perforated mold, it no longer acts on the system no shear force and viscosity of system increases in this way such that the extruded bar It can be cut to predetermined dimensions of the extruded body. In this case the inconveniences of the powdery form are avoided but nevertheless they can take place glued and / or crusted of the products due to the use of aqueous solutions, agents aqueous plasticizers and lubricants or components that they contain a large amount of hydration water, which They do various drying processes.

Based on this state of the art, the task of the invention is to make available new solid cleaning agents for mechanical dishwashing in the form of pressed bodies, which can be marketed, with high bulk weight, in the form of free flowing products, without tendency to crimp. Another task of the invention consists in set up a suitable manufacturing procedure for such products, working with a small amount of water or form anhydrous and that requires only a minimum in processes of dried

In this context "a small amount of water "means an amount of water that no longer requires a stage additional drying depending on the water absorbent capacity of the individual components.

The object of the invention is therefore a Process for manufacturing agent preparations solid cleaning, elaborating, by mixing, the components solids and liquids to give a homogeneous mass, moldable by Pressed, the dough is pressed, rod-shaped, through molds drilled with a hole width of the dimension preset of the pressed body, at temperatures located by above 30 ° C, the bar of compacted material, protrusion, is chop up to the predetermined dimension of the pressed body with a cutting device and, if desired, the particles obtained, still plastic, they are modified by molding, characterized in that the components contain, as an additional component, a paraffin that melts between 30ºC and 60ºC, especially between 35ºC and 45 ° C, and this solidifies by cooling after the process of Chopped after further molding. This can lead to out for example in an extruder.

Another object of the invention is a preparation Solid washing agent for mechanical dishwashing in the form of pressed pieces in scattered granular form, which have compacted up to bulk weights less than 700 g / l, which they contain solid components, which belong, at least in part, to the class of adjuvants, alkali carriers, agents oxygen bleach and / or bleach activators and others liquid or plastic deformable products at least in part at temperatures above 30 ° C (liquid phase), which may belong to the class of surfactants, characterized because the liquid phase contains a paraffin that melts between 30 ° C and 60ºC, especially between 35ºC and 45ºC in quantities from 1 Up to 15% by weight.

Without wanting to limit the invention to a determined theory, the components used in the products according to the invention with a melting point comprised between 30 and 60ºC they are presented, within the scope of the process of processing, by way of liquid auxiliary agent of preparation and its  solidification contributes, after the end of processing, to reinforcement of the pressed pressed bodies. The decisive is that these components, even when present in  mixture form with other liquid components, they solidify, it is say that at least they are partly separated by crystallization. In this case it is assumed that the still liquid parts of the liquid phase refrigerated are absorbed in the volume of the pores of the body solid, contributing to the reinforcement, on the contrary, the parties  hardened

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

The described liquid phase contains the paraffins preferably in amounts from 1 to 15% by weight based on the whole of the preparation, in particularly preferred embodiments from 2 to 5% by weight. The melting point of the paraffin should in this case preferably be between 35 ° C and
45 ° C

Other parts of the liquid phase can be chosen in this case, in the sense of the request, for example of the group of the surfactants (anionic surfactants, surfactants cationic, nonionic surfactants).

For the solution of the problem raised is Especially preferred is the use of non-ionic surfactants, which they are chosen from the group consisting of ethoxylated fatty alcohols, alkyl polyglycolides and / or glucamides of acids fatty

The person skilled in the art understands in this case, in general, by alkoxylated alcohols, the reaction products of alkylene oxides, preferably ethylene oxide with alcohols, preferably within the meaning of the present invention long chain alcohols. As a rule they are formed from of n moles of ethylene oxide and 1 mole of alcohol, depending on reaction conditions, a complex mixture of products from addition with different degrees of ethoxylation. Another way to embodiment consists in the use of mixtures of alkylene oxides preferably from the mixture of ethylene oxide and propylene They can also be obtained, if desired, by subsequent etherified with short chain alkyl groups, such as preferably the butyl group, to classes of substances of "closed" alcoholetoxylates, which can also be used in the sense of the invention. They are very especially preferred in the meaning of the present invention fatty alcohols with a high degree of ethoxylation or mixtures thereof with ethoxylates of closed fatty alcohols in the extreme groups.

The alkyl polyglycolides are surfactants that they can be obtained by reaction of sugars and alcohols according to the procedures of the preparative organic chemistry branch, obtaining, according to the type of manufacturing, a mixture of monoalkylated sugars, oligomers and polymers. The Preferred alkyl polyglycolides may be alkyl polyglycosides, alcohol being especially preferred a fatty alcohol of long chain or a mixture of long chain fatty alcohols and the degree of oligomerization of sugars being included between 1 and 10

The fatty acid polyhydroxylamides (glucamides) are acylated reaction products of the amination reducing a sugar (glucose) with ammonia, using it as acylating agents as a rule chain fatty acids long, long chain fatty acid esters or chlorides of long chain fatty acids. In this case, amides are formed secondary when the reduction with methylamine or with  ethylamine instead of with ammonia, as described for example in SÖFW-Journal, 119, (1993), 794-808. Preferably lengths of carbon chains with 6 to 12 carbon atoms in the rest of fatty acid.

They can also be used in the cleaning agent and in the procedure described below, also others components, which will be shown in an exemplary way then.

In cleaning agents according to the invention water soluble and water insoluble adjuvants can be used first of all for the binding of calcium and magnesium. In this case water soluble adjuvants are preferred since, as a rule In general, they have a lower tendency to leave insoluble residues on the dishes and on hard surfaces. The usual adjuvants, which may be added within the scope of the invention between a 10 and a 90% by weight referred to the whole preparation, are acids low molecular weight polycarboxylic acids and their salts, acids homopolymer polymers and copolymers and their salts, the carbonates, phosphates and silicates. To insoluble adjuvants in water belong the zeolites, which can be used if necessary, as well as mixtures of the adjuvant substances mentioned above. For cleaning agents according to the invention, they will be used preferably trisodium citrate and / or pentasodium polyphosphate and silicate type adjuvants of the disilicate class.

How other components can be added carriers of alkali. As alkali carriers, metal hydroxides are used alkalines, alkali metal carbonates, metal bicarbonates alkaline, alkali metal sesquicarbonates, silicates alkaline, alkaline metasilicate, and product mixtures cited above, being used in the sense of this invention preferably alkali carbonates, especially the sodium carbonate, sodium bicarbonate or sesquicarbonate sodium, in amounts from 2 to 50% by weight based on set of preparation.

Other possible components are agents of oxygen bleaching Typical oxygen bleaching agents are the perborates of alkali metals and their hydrates and the alkali metal percarbonates, finding application in the scope of the invention preferably sodium perborate, in monohydrate or tetrahydrate form, or sodium percarbonate and its hydrates, in amounts of 2 to 12% by weight referred to the whole preparation.

Typical components of preparations for cleaning agents for mechanical dishwashing, which can be combined for technical reasons to the preparation according to the invention, also previously in the form of a powder, of a granulated or of a liquid, they are bleach activators, enzymes, scented essences, agents for protection against corrosion and auxiliary agents for manufacturing.

Known bleach activators are compounds containing one or more N-acyl groups or O-acyl, such as substances of the classes of anhydrides, esters, imides and acylated or oxid imidazoles. For example, they can cite tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, as well as PAG Pentaacetylglucose, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine  DADHT and ISA isatoic acid anhydride. For the present invention have been proven proportions of bleach activator between 1 and 5% by weight, referring to the whole of the preparation. According to the invention, proportions of bleach activator between 1 and 5% by weight, referred to the whole preparation.

According to the invention they can be added to the agents of cleaning between 0 and 5% by weight of enzymes, referred to set of preparation to increase the performance of cleaning agents and to guarantee with the same quality the cleaning performance under milder conditions. To enzymes employees most frequently belong lipases, amylases, cellulases and proteases. Preferred proteases are, for example, BLAP® 140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or also Savinase® from Novo Firm. Cellulases and lipases Especially suitable are Celluzym® 0.7 T and Lipolase® 30 T of the Signature Novo Nordisk. How amylases found especially Termamyl® 60 T application, and Termamyl® 90 T from Signature Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 of the Gist Brocades Firm being able to also use others enzymes

Agents for dishwashing according to the invention may contain corrosion inhibitors for the protection of the items to be scrubbed or of the machine, having a special meaning, in particular the agents for silver protection in the mechanical scrubbing sector of the dishes, such as those described for example in DE 43 25 922, in DE 41 28 672 or in DE 43 38 724. They are also found in cleaning formulations frequently agents that they contain active chlorine, which can significantly reduce the corrosion of silver surfaces. In the cleaning agents chlorine free, will be used, according to publications above, especially compounds with activity Redox, organic, containing oxygen and nitrogen, such as divalent and trivalent phenols, for example hydroquinone, pyrocatechin, hydroxyhydroquinone, gallic acid, floroglucin, pyrogallol or derivatives of these classes of compounds. Too frequently find application of inorganic compounds of type saline and complex type, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce. Similarly, compounds of the zinc, to prevent corrosion of scrubbed products.

Other known components of the agents washing and cleaning are often taken from the group of scented essences. They can also be contained in the compositions of the cleaning agents according to the invention.

In addition, other additives can be used for made, such as, for example, for the dust of the residual moisture in some finely tarnishing preparations divided, which the technician can choose, as a rule general, of the group formed by the silicic acids of precipitation, alkali carbonates, (especially carbonate of sodium), of alkaline bicarbonates (especially bicarbonate sodium) of zeolites or similar suitable agents.

A preferred preparation of the cleaning agent according to the present invention it contains, for example, from 20 to 70% by weight of sodium citrate, from 2 to 10% by weight of surfactants, from 2 to 15% by weight of carbonate of sodium, from 10 to 50% by weight of sodium bicarbonate, from 2 to 12% by weight of sodium perborate, from 0 up to 30% by weight of polycarboxylic acids, referred respectively to the whole preparation.

They can also be added to the preparations of the cleaning agents according to the invention, subsequently, by way of mixing components from 1 to 5% by weight of activator bleaching, from 0 to 5% by weight of enzyme and / or from a 0 to 1% by weight of perfume essence for ready made

To the solution according to the invention of the task can be loaded with material, in various ways, the installation of extrusion used in the procedure described below. From this mode can be added in a premix all components to be extruded, or they can be mixed in the extruder itself, then preferably feeding the liquid components to through an independent tubing. In this case they can combine, according to the invention, the other active products, such such as bleach activators, inhibitors of corrosion for silver, enzymes and the like, in the form of granulated or in the form of liquid or solid additives.

The mixture is plasticized by increasing the pressure in front of perforated discs, energy supply by spindle means and additional heating by heating through the extruder jacket. In this case pressing the mass of the cleaning agent to be extruded, at pressures above 50 bar. The way of Performing the procedure, especially preferred, works at pressures above 100 bars.

The temperature, at which the mass is in a been so plastic that pressing is possible through the perforated plates and a cut of molded bodies cylindrical, without sticking, depends on the components of the recipe and is preferably included between 45 and 60 ° C, especially preferably above 50 ° C

In the extruder, precautions are taken so that verify a step as homogeneous as possible through all the holes of the perforated plate, so that the bars homogeneously by means of a rotating blade. A preferred embodiment of spherical pressed bodies is that the diameter of the material bar corresponds approximately at the height of the particles.

For the control of the temperature of the bars plasticized outgoing it may be desirable to effect your cooling, at least superficial, by cooling instantaneous, especially by cold air, before and / or during shredding.

Then it is preferably carried out a final elaboration of the still plastic bodies in a usual spheronizer in commerce, being able to make then the spherical pieces in addition by sprinkling. In In this case, finely divided opacifying products are used, especially precipitation silicic acids, carbonate sodium, sodium bicarbonate, zeolites and the like.

By working in basically anhydrous medium and simultaneous maintenance of the molding capacity of plasticized masses can be withdrawn, as a rule, according to the invention, to the drying stage. However when present, under certain circumstances, depending on the absorption capacity of water of the individual components, still residual liquid, A drying stage may also be carried out. Preferably the amount of water is below 5% by weight, of especially preferably below 3% by weight and a very especially preferably below 2% by weight. An amount of water so small that it no longer needs any Additional drying stage, can be very useful for controlling the plasticizing capacity of the mixture. Therefore it is preferred in the selected examples, a water content above a 1% by weight when plasticizing is not controlled or modified by means of other known measures.

After product refrigeration until ambient temperature (below 30 ° C) can be obtained from this free flow mode that has no tendency to crusted, with a bulk weight from 600 to 1,000 g / l.

Examples

For cleaning agent preparations described below worked in a laboratory extruder double spindle of the Leistritz Firm.

Example 1 Components

one. Trisodium citrate (2 H 2 O) 48 2. Sodium carbonate 9.6 3. Baking Soda sodium 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. Alkyl polyglycoside (C_ {8-10}) (at 70%) 3.8 8. Paraffin 42/44 2.9 9. Granules of TAED 2.0 10. Enzyme 2.0 11. Perfume 0.6.  \ hskip-0.2cm

The plasticization of the mixture, dosed from continuously, from components 1-8 it takes to out in the extruder through the energy contribution of spindles, if necessary by additional heating by means of the shirt and by increasing the pressure in front of the disc Perforated. The temperature at which the dough is so plasticized that a pressing is possible through the 1.6 mm holes of the perforated plate and a cut of the molded bodies cylindrical without sticking, it was in the present case from 54-58 ° C. Cylindrical molded bodies with a length / diameter ratio of 1: 1 were made in a commercially used spheronizer, to give spherical particles. A free flow product was obtained under normal temperature, no tendency to crimp, which was mixed with the components 9-11 to give a finished product with a weight to bulk of 860 g / l.

If the procedure is carried out with the components in this composition such that the solid products 1-4 and liquid components 5-8 respectively in the form of a mixture, in the extruder, you get, after processing, also a product finished with the properties of example 1.

Example 2 Components

one. Trisodium citrate (2 H 2 O) 33.5 2. Citric Acid (1 H 2 O) 8.2 3. Carbonate of sodium 10.0 4. Baking Soda sodium 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. Granules of TAED 2.0 10. Enzyme 3.0.  \ hskip-0.2cm

By using a mixture of components 1-8 during obtaining the body raw extruded under the conditions of example 1, it was obtained, after the remaining mixing with components 9 and 10, a product perfectly flowable with a bulk weight of 880 g / l.

Claims (16)

1. Procedure for obtaining solid preparations of washing agents, the solid and liquid components being prepared by mixing to give a homogeneous mass, moldable by pressing, the mass is pressed in the form of a bar through perforated molds with hole widths with the predetermined dimension for the pressed part, at temperatures above 30 ° C, the compacted material bar, protruding, is chopped by means of a cutting device up to the predetermined dimension of the pressed part and, if desired, the particles obtained, still plastic, are modified by molding, characterized in that the components contain, as an additional component, a paraffin that melts between 30 ° C and 60 ° C, especially between 35 ° C and 40 ° C and is allowed to solidify, by cooling, after the cutting process / or after additional molding. 2. Method for obtaining solid preparations of washing agents according to claim 1, characterized in that the pressed parts are sprinkled with finely divided opacifying products, especially silica precipitation acids, sodium carbonate, sodium bicarbonate and the like to avoid tackiness. superficial. 3. Method for obtaining solid preparations of cleaning agents according to claims 1 to 2, characterized in that other active products are combined, especially bleaching activators, corrosion inhibitors for silver, enzymes and the like in granulate form or by way of of liquid or solid additives
two. 4. Procedure for obtaining solid preparations of cleaning agents according to claims 1 to 3, characterized in that a drying step is introduced for the elimination of the residual amounts of liquid present in the given case. 5. Method for obtaining solid preparations of cleaning agents according to claims 1 to 4, characterized in that the pressing is carried out using strongly elevated pressures, preferably above 50 bar, especially in the range of at least about 100 bars and at moderately high dough temperatures, for example in the range of 45 to 60 ° C and, if desired, at least superficially cooled by instant cooling, especially by means of cold air, the plasticized bars protruding before and / or during the crumbled. Method according to claims 1 to 5, characterized in that for the control of the plasticizing capacity during the process, water is added in an amount such that it does not require an additional drying stage and is preferably comprised between 1 and 5. % by weight, particularly preferably between 1 and 3% by weight and very especially preferably between 1 and 2% by weight. 7. Solid preparation of cleaning agents for the mechanical scrubbing of dishes in the form of pressed bodies in the form of spreadable grain, which have been compacted to bulk weights of at least 700 g / l, containing solid components, which belong, at least partially, to the class of adjuvants, alkali carriers, oxygen bleaching agents and / or bleaching activators and also liquid or plastically deformable products (liquid phase) at least partially at temperatures above 30 ° C, which may belong to the class of surfactants, characterized in that the liquid phase contains a paraffin that melts between 30 ° C and 60 ° C, especially between 35 ° C and 45 ° C, in amounts from 1 to 15% by weight. 8. Solid preparation of cleaning agents according to claim 7, characterized in that the liquid phase constitutes 5 to 20% by weight, preferably 10 to 15% by weight, based on the whole of the preparation. 9. Solid preparation of washing agents according to claims 7 or 8, characterized in that, as a liquid phase, surfactants, especially non-ionic surfactants, preferably long chain ethoxylated alcohols, alkyl polyglycolides and / or fatty acid glucamides are used. 10. Solid preparation of cleaning agents according to one of claims 7 to 9, characterized in that the paraffin, which melts between 30 ° C and 60 ° C, is contained in amounts from 1 to 15% by weight, preferably from 2 to 5 % by weight, referring to the whole preparation of cleaning agents. 11. Preparation of cleaning agents according to claims 7 to 10, characterized in that fatty alcohols with a high degree of ethoxylation are used as surfactants. 12. Preparation of cleaning agents according to claims 7 to 11, characterized in that they are used as adjuvants, salts of polyfunctional carboxylic acids, especially trisodium citrate and / or penta-sodium tripolyphosphate and, if desired, silicate-type adjuvants of the class of disilicates. 13. Preparation of cleaning agents according to claims 7 to 12, characterized in that alkali carbonates are used as alkaline agents, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. 14. Preparation of cleaning agents according to claims 7 to 13, characterized in that sodium perborate is used as oxygen bleaching agents, in the form of monohydrate or tetrahydrate or sodium percarbonate. 15. Preparation of cleaning agents according to claims 7 to 14, characterized in that it contains from 20 to 70% by weight of sodium citrate, from 2 to 10% by weight of surfactants, from 2 to 15% by weight of sodium carbonate, from 10 to 50% by weight of sodium bicarbonate, from 2 to 12% by weight of sodium perborate, from 0 to 30% by weight of polycarboxylic acids. 16. Preparation of cleaning agents according to claims 7 to 15, characterized in that from 1 to 5% by weight of bleach activator are added as mixing components, from 0 to 5% by weight of enzyme and / or from 0 to 1% by weight of perfume essence for the preparation.