EP0885289A1

EP0885289A1 - Solid detergent preparations

Info

Publication number: EP0885289A1
Application number: EP97902225A
Authority: EP
Inventors: Hans-Friedrich Kruse; Hans-Josef Beaujean; Dirk Gerst; Peter Jeschke
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1996-02-02
Filing date: 1997-01-25
Publication date: 1998-12-23
Anticipated expiration: 2017-01-25
Also published as: ES2158487T3; ATE201713T1; DE19603760A1; ES2158487T5; DE59703675D1; PT885289E; EP0885289B2; WO1997028245A1; EP0885289B1

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 cleaning agents

The invention relates to solid detergent preparations for automatic dishwashing and a process for their production.

Weakly alkaline agents for machine dishwashing are known. DE 4232170 describes such highly effective agents for machine dishwashing in which pentaalkali metal phosphate has been completely replaced and the content of phosphate substitutes such as native and synthetic polymers has been greatly reduced or completely restricted. According to this teaching, typical cleaning agents can contain sodium citrate, citric acid, soda, sodium silicate, sodium hydrogen carbonate, sodium perborate, sodium percarbonate, bleach activators, surfactants and enzymes.

Problems may arise with the processing and use of these agents. The dosage form of the powder mixture that is often offered in conventional cleaning agents has the disadvantage that it is often very dusty during manufacture and use. In addition, like conventional mixing granules, in which dust generation is already significantly minimized, powders tend to separate the individual components, which can have a negative effect on reproducible cleaning performance. In addition, with conventional granulation processes, which often use water or aqueous solutions, sticking and caking of the individual base bodies can often not be ruled out, which has a negative effect on the free-flowing properties of the cleaning agents and thus their metering capacity and their storage stability. So far, this can only be prevented by complex, often multi-stage, drying processes. DE 39 26 253 discloses processes for the production of extrudates, in which a homogeneous, solid premix is extruded under pressure and the strand is cut to the predetermined pellet size after exiting the hole shape by means of a cutting device. The homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under pressure or under the entry of specific work. Preferred plasticizers and / or lubricants are surfactants and / or polymers, which are preferably used in liquid, pasty or gel-like preparation form. The premix can also contain powders and / or granules, the granules being obtained, inter alia, by granulation processes or also by conventional spray drying processes. After exiting the hole shape, the system is no longer subjected to shear forces and 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

The use of aqueous solutions, aqueous plasticizers and lubricants, or components containing a lot of water of hydration can result in the products sticking and caking, which necessitates drying processes.

Against the background of this prior art, it is an object of the invention to provide new, solid detergents for automatic dishwashing in the form of compacts which, with a high bulk density, can be offered as free-flowing products which do not tend to cake. Another object of the invention is to propose a suitable manufacturing process for such products, which works with little or no water and manages with a minimum of drying processes. In this context, "low water" means a quantity of water which, depending on the water absorption capacity of the feed materials, makes an additional drying step unnecessary.

The invention thus relates to a solid detergent preparation for machine dishwashing in the form of compacts in giant-shaped grain form, which are compressed to bulk densities of at least 700 g / l, containing solid ingredients which are at least partly of the class of builders, alkali carriers, oxygen bleaches and / or Bleach activators belong and continue to be at least partly liquid or plastically deformable substances (liquid phase) at temperatures above 30 ° C, which can belong to the class of surfactants, characterized in that the liquid phase contains at least one component below approx. 30 ° C in solid form a melting point of less than 60 ° C includes.

Another object of the invention is a process for the production of solid detergent preparations, characterized in that solid and liquid components are prepared into a homogeneous, compressible mass by mixing, this mass in the form of holes with hole widths of the predetermined compact dimension at temperatures above 30 ° C. veφreßt, the emerging compacted material strands by means of a cutting device to the predetermined compact size, if desired, the resulting plastic particles are changed in shape and the additional component melting between 30 and 60 ° C solidifies by cooling. This can be done in an extruder, for example.

Without restricting the invention to a specific theory, it is assumed that the component used in the products according to the invention with a melting point of between 30 and 60 ° C. is present as a liquid confectioning agent in the course of the processing process and her Solidification after the end of processing contributes to the solidification of the resulting compacts. It is crucial that this component, even if it is mixed with other liquid components, solidifies, ie at least partially crystallizes out. It is assumed that the still liquid portions of the cooled liquid phase are absorbed in the pore volume of the solids, whereas the hardened portions contribute to solidification.

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

The liquid phase described can preferably contain one or more components which are selected from the group of paraffins, nonionic surfactants, fatty acid and / or fatty alcohol derivatives. The liquid phase contains this component or the sum of these components preferably in amounts of 1 to 15% by weight, based on the entire preparation, in particularly preferred embodiments in 2 to 5% by weight. The melting point of the component or of the components should preferably between 35 ^C and C are 45 ° C.

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

For the achievement of the present object, the use of nonionic surfactants selected from the group of ethoxylated fatty alcohols, alkyl polyglycosides and / or fatty acid glucamides is particularly preferred.

The person skilled in the art generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. As a rule, n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used in the context of the invention. Highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates are very particularly preferred for the purposes of the present invention.

Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols using the relevant methods of preparative organic chemistry, with a mixture of monoalkylated, oligomeric or polymeric sugars depending on the type of preparation. Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols and the degree of oligomerization of the sugars being 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, further components can be used in the cleaning agent and the method described below, as will be illustrated below by way of example.

In the cleaning agents according to the invention, water-soluble and water-insoluble builders can be used especially for binding calcium and magnesium. Water-soluble builders are preferred because they generally have less tendency to form insoluble residues on dishes and hard surfaces. Customary builders, which can be present in the scope of the invention between 10 and 90% by weight, based on the entire preparation, 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 the zeolites, which can also be used, as well as mixtures of the abovementioned builder substances. Trisodium citrate and / or pentasodium tripolyphosphate and silicate builders from the class of the disilicates are preferably used for the cleaning agents according to the invention.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers 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, sodium perborate, as the mono- or tetrahydrate, or sodium percarbonate and whose hydrates are used in amounts of 2 to 12% by weight, based on the entire preparation.

Typical components of detergent preparations for machine dishwashing, which can also be added subsequently in the form of a powder, granules or as a liquid, for technical reasons, are bleach activators, enzymes, perfume oils, corrosion protection agents and packaging aids.

Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetyimethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1, 3,5-triazine DADHT and isatoic anhydride ISA. Bleach activator proportions of between 1 and 5% by weight, based on the preparation as a whole, have proven useful for the present invention.

According to the invention, between 0 and 5% by weight of enzymes, based on the entire preparation, can be added to the cleaning agent in order to increase the performance of the cleaning agents or to guarantee the same quality of cleaning performance under milder conditions. The most commonly used enzymes include lipases, amylases, cellulases and proteases. Preferred proteases are e.g. B. BLAPΘ140 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. Particularly suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk. Termamyl® 60 T and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades are particularly used as amylases, but other enzymes can also be used. Dishwashing agents according to the invention can contain corrosion inhibitors to protect the washware or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing, as described, for example, in B. are described in DE 43 25 922, DE 41 28 672 or DE 43 38 724. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Zinc compounds can also be used to prevent corrosion on the wash ware.

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

In addition, other additives can be used for assembly, such as for example to powder off the residual moisture in some preparations, fine-grain reference fittings, which the person skilled in the art usually from the group of precipitated silicas, alkali metal carbonates (especially sodium carbonate), alkali metal bicarbonates (especially

Sodium bicarbonate), which can select zeolites and similar suitable agents.

A preferred cleaning agent preparation according to the present invention thus 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 bicarbonate, 2 up to 12% by weight sodium perborate, 0 to 30% by weight polycarboxylic acid in each case based on the entire preparation.

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 can also be added to the cleaning agent preparations according to the invention as an admixture component.

To achieve the object according to the invention, the extrusion system used in the method described below can be charged with material in various ways. So z. B. all components to be extruded are fed in a premix, or mixed in the extruder itself, in which case the liquid components are preferably added through a separate nozzle. According to the invention, the other active ingredients, such as bleach activators, corrosion inhibitors for silver, enzymes and the like, can be admixed in granular form or as liquid or solid additives.

The mixture is plasticized by pressure build-up in front of the perforated disks, energy input by the screws and additional heating by the jacket heating of the extruder. The detergent mass to be extruded is pressed 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 pressing through the perforated plate and cutting into cylindrical shaped bodies is possible without sticking is dependent on the formulation constituents and is preferably between 45 and 60 ° C., particularly preferably above of 50 ° C. In the extruder, care is taken to ensure that the throughput is as uniform as possible through all openings in the perforated disc, so that the strands can be cut uniformly by the rotating knives. A preferred embodiment for spherical compacts is that the diameter of the strand of material corresponds approximately to the height of the particles.

To control the temperature of the emerging plasticized strands, it may be desirable to cool them at least superficially by shock cooling, in particular by means of cold air, before and / or during the cutting.

After that, the still plastic bodies are then preferably reprocessed in a rounding machine customary on the market, the spherical parts then being able to be made up by powdering. Finely divided reference fittings, in particular precipitated silicas, sodium carbonate, sodium hydrogen carbonate, zeolites and the like are used.

By working in a fundamentally water-free environment while at the same time maintaining the ability to shape the plasticized mass, drying steps can generally be dispensed with according to the invention. If, however, depending on the water absorption capacity of the feedstocks, residual liquid is still present, a drying step can also be carried out. The amount of water is preferably below 5% by weight, particularly preferably below 3% by weight and very particularly preferably below 2% by weight. Such a small amount of water, which no longer requires an additional drying step, can be very useful in controlling the plasticity of the mixture. Therefore, in selected examples, if the plasticization is not controlled and changed by other known measures, a water content above 1% by weight is preferred.

After the product has cooled to room temperature (below 30 ° C.), free-flowing products that do not tend to cake with a bulk density of 600 to 1000 g / l can be obtained in this way. Examples:

The detergent preparations described below were processed in a twin-screw laboratory extruder from Leistritz.

Example 1 :

Components:

1.Trisodium citrate (2 H ₂ O) 48

2. Soda 9.6

3. Sodium hydrogen carbonate 17.7

4. 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. 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 continuously metered mixture of components was plasticized in the extruder by the energy input of the screws, optionally by additional jacket heating and by pressure build-up in front of the perforated disk. The temperature at which the mass plasticizes so that pressing through the 1.6 mm holes in the perforated plate and cutting into cylindrical shaped bodies is possible without causing sticking was 54-58 ° C. in the present case. The cylindrical shaped body with a The length / diameter ratio of 1: 1 was processed into spherical particles in a rounder available on the market. A free-flowing, non-caking product was obtained at normal temperature, which was mixed with components 9-11 to a finished product with a bulk density of 860 g / l.

If the process is carried out with the components in this composition in such a way that the solids 1-4 and the liquid components 5-8 are each metered as a mixture into the extruder, then a finished product with the properties of Example 1 is also obtained after processing

Example 2:

Components:

1. Trisodium citrate (2 H ₂ O) 45.0

2. Soda 10.0

3. Sodium bicarbonate 22.5

4. Sodium perborate (1 H ₂ O) 5.0

5. fatty alcohol _(C12. _14, + 4 EO) 2.5

6. fatty alcohol (C _16- ι ₈ + 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 crude extrudate is produced by using a mixture of components 1-7 under the same conditions as in Example 1 and a processing temperature of 50-53 ° C. after rounding with powdering with Component 10 and residual mixing with components 8 and 9 gave a readily flowable finished product with a bulk density of 920 g / l.

Example 3:

Components;

1. Trisodium citrate (2 H ₂ O) 33.5

2. Citric acid (1 H ₂ O) 8.2

3. Soda 10.0

4. Sodium bicarbonate 27.3

5. Sodium perborate (1 H ₂ O) 5.0

6. fatty alcohol _(C12. _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 production of the crude extrudate under the conditions of example 1, after mixing with the components 9 and 10, a readily flowable product with a bulk density of 880 g / l was obtained.

Claims

claims

1. Solid detergent preparation for machine dishwashing in the form of compacts in giant-shaped grain form, which are compressed to bulk densities of at least 700 g / l, containing solid ingredients which at least partly belong to the class of builders, alkali carriers, oxygen bleaching agents and / or bleach activators, and further at least partly at temperatures above 30 ° C liquid or plastically deformable substances (liquid phase), which can belong to the class of surfactants, characterized in that the liquid phase has at least one component below 30 ° C in solid form with a melting point of less contains than 60 ° C.

2. Solid detergent preparation according to claim 1, characterized in that the liquid phase makes up 5 to 20 wt .-%, preferably 10 to 15 wt .-%, based on the total preparation.

3. Solid detergent preparation according to claims 1 and 2, characterized in that surfactants, in particular nonionic surfactants, preferably ethoxylated, long-chain alcohols, alkyl polyglycosides and / or fatty acid glucamides are used as the liquid phase.

4. Solid detergent preparation according to claims 1 to 3, characterized in that the component belonging to the liquid phase, solid at temperatures below 30 ° C, at a melting point below 60 ° C in amounts of 1 to 15% by weight, preferably of 2 up to 5 wt .-%, based on the total detergent preparation is included.

5. Detergent preparation according to claims 1 to 4, characterized gekenn¬ characterized in that as at about 30 ° C solid component with a melting point less than 60 ° C paraffins, nonionic surfactants, fatty acids and / or Fatty alcohol derivatives with melting points between 30 and 60 ° C, in particular 35 to 45 ° C, are used.

6. Detergent preparation according to claims 1 to 5, characterized gekenn¬ characterized in that highly ethoxylated fatty alcohols are used as surfactants.

7. detergent preparation according to claims 1 to 6, characterized gekenn¬ characterized in that the builders, salts of polyfunctional carboxylic acids, in particular trisodium citrate and / or pentasodium tripolyphosphate and desired folded silicate builders from the class of disilicates are used.

8. Detergent preparation according to claims 1 to 7, characterized gekenn¬ characterized in that alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate are used as alkalizing agents.

9. Detergent preparation according to claims 1 to 8, characterized gekenn¬ characterized in that sodium perborate, as mono- or tetrahydrate or sodium percarbonate are used as oxygen bleach.

10. Detergent preparation according to claims 1 to 9, characterized gekenn¬ characterized in that it contains 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.

11. Detergent preparation according to claims 1 to 10, 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 as confectioning components.

12. A process for the preparation of solid cleaning agent preparations according to claims 1 to 11, characterized in that solid and liquid constituents are prepared into a homogeneous, form-compressible mass by mixing, this mass via hole shapes with opening widths of the predetermined compact dimension at temperatures above 30 ° C extruded into strands, the emerging compacted material strands are cut to the predetermined compact size by means of a cutting device, if desired the shape of the still plastic particles obtained is changed and the additional component, which melts between 30 and 60 ° C., is allowed to solidify by cooling.

13. A process for the preparation of solid cleaning agent preparations according to claims 1 to 11, characterized in that the compacts are powdered with finely divided reference fittings, in particular precipitated silicas, sodium carbonate, sodium hydrogen carbonate and the like to avoid surface stickiness.

14. A process for the preparation of solid cleaning agent preparations according to claims 1 to 11, characterized in that further active ingredients, in particular bleach activators, corrosion inhibitors for silver, enzymes and the like are added in granular form or as liquid or solid additives.

15. A process for the preparation of solid cleaning agent preparations according to claims 1 to 11, characterized in that a drying step is introduced to remove any residual liquid quantities.

16. A process for the preparation of solid cleaning agent preparations according to claims 1 to 11, characterized in that the pressing using a greatly increased pressure, preferably at above 50 bar, in particular in the range of at least about 100 bar and at moderately elevated melt temperatures, for example in the range of 45 to 60 ° C is carried out and, if necessary, by flash cooling, in particular by means of cold air, at least superficially cooling the emerging plasticized strands before and / or during the division.

17. The method according to claims 12 to 16, characterized in that to control the plasticizing during the process, water is optionally added in an amount that no longer requires an additional drying step and preferably between 1-5 wt .-%, particularly preferred is between 1-3% by weight and very particularly preferably between 1-2% by weight.