EP0750662B1 - Breakage-resistant polyfunctional cleaning tablets with a long shelf life, process for producing them and their use - Google Patents

Abstract

PCT No. PCT/EP95/00821 Sec. 371 Date Sep. 13, 1996 Sec. 102(e) Date Sep. 13, 1996 PCT Filed Mar. 6, 1995 PCT Pub. No. WO95/25161 PCT Pub. Date Sep. 21, 1995The process of producing break-resistant and storage-stable detergent tablets comprising coating powdered or crystalline detergent components present in anhydrous form or having a low degree of hydration with a hydrophobicizing agent, and tabletting the resulting mixture under pressure to produce tablets having a breaking strength of at least 150 N.

Description

Machine dishwashing generally consists of a pre-wash cycle a cleaning cycle, one or more intermediate rinse cycles, a rinse cycle and a drying cycle. In principle, this applies to the machine Rinsing both in households and in the commercial sector.

The means used for the automatic cleaning of dishes can be liquid, pasty, powdery and tablet-like. The application in Tablet form is becoming increasingly popular due to its easy handling. A number of manufacturing processes have already been described that lead to tablets with time-controlled dissolution behavior. These tablets are often in the machine room itself and no longer in the boxes in the door room intended for detergent dosing positioned, which allows some of the tablets to already be is dissolved in the pre-rinse cycle and so the effect of the usually additive-free Tap water is chemically supported in this phase. So are for example from DE 35 41 145 uniformly composed alkaline Detergent tablets known for machine dishwashing, which have a broad solubility profile and a mixture of Sodium metasilicate nonahydrate and anhydrous metasilicate as well as anhydrous Pentasodium triphosphate and possibly other ingredients contain. DE 41 21 307 describes stable, bifunctional, phosphate and metasilicate - free alkaline detergent tablets for the machine dishwashing known, the framework components partially used in anhydrous form and in the manufacture with water were sprayed what the desired solubility profile and good compressibility caused.

In all known cases, the ones to be pressed were produced Mix either with components containing high water content that make up their water of crystallization release easily when pressing, or by adding free Water to water-free components for the purpose of hydrating their surfaces. The resulting slight moisture made it easier Baked together and led to a good compressibility.

Since the water in the known tablets is partially or completely unbound was present, but was the installation of water or moisture sensitive Ingredients only limited or not possible. To this Ingredients include Bleaching systems based on per compounds and their activators, enzymes or some corrosion inhibitors.

The object of the present invention was therefore based on a method to look for that not only to break and storage stable, polyfunctional Leads tablets, but especially the incorporation of water or moisture-sensitive components of known detergent tablets allowed and their impairment in manufacture and storage avoids.

It has been found that polyfunctional ones are stable and stable in storage Detergent tablets come when you manufacture them on the Add free water and the use of slightly hydrated water Connections omitted and the powdery or crystalline components of the detergent mixture individually and / or as mutually compatible powdered or optionally granulated partial mixtures hydrophobized, optionally mixed again, further hydrophobized or also adds non-hydrophobic components and the resulting ones the resulting mixture is compressed into tablets.

The present invention thus relates to polyfunctional that is stable and stable in storage Detergent tablets of any composition, where the anhydrous or low hydration used powdery or crystalline components individually or in combination compatible powdered or optionally granulated Mixtures are coated with a hydrophobizing compound and the in addition, other moisture-sensitive components, if necessary with their own hydrophobic coating.

The detergent tablets of the present invention can be strong alkaline with pH values> 11, but also low alkaline with pH values below Be 11. So you can in a known manner Pentaalkalitriphosphate, alkali silicates, Alkali carbonates, bleaches, optionally activators for these as well as alkali hydroxides, zeolites and / or enzymes, wherein again individual constituents or mixtures thereof can be made hydrophobic. But they can also be low alkaline, phosphate and silicate free and oxygen-releasing compounds instead of active chlorine-releasing compounds as bleaching agents Connections and activators for these connections as well as contain enzymes. In both cases, they can also be low-foaming contain non-ionic surfactants.

The present invention preferably relates to fracture-stable and lab-stable, phosphate and preferably alkali silicate free, low alkaline polyfunctional Detergent tablets, especially for machine washing of dishes based on framework substances, non-ionic surfactants, Enzymes, bleaches and activators for this, which are characterized are that the powdery or crystalline constituents individually or as mutually compatible powdered or optionally granulated Mixtures with the same or different hydrophobizing compounds are coated, the hydrophobizing compounds as such still contain liquid or powdered tablet components can.

The hydrophobizing compounds become liquid or liquefied Form via a nozzle which can be regulated in a known manner onto the powdery or crystalline components or mixtures thereof, wherein a thin protective coating forms on the solid fabrics, which the more uniform and stable the more finely divided the liquid particles present after exiting the nozzle. The water repellent Substance is in liquid form during the hydrophobization process. He can a liquid under normal conditions, e.g. be an oil or it can be also a solid, e.g. Be wax, which in the molten state is processed in the hydrophobic stage. The melting range of the hydrophobizing In any case, the substance must be below the desired application temperature lie, with the choice of hydrophobizing Means with different boiling or melting ranges, which also by the liquid or powdered tablet components optionally added to these can be varied, any solubility variants have individual components or component mixtures specified, so that their desired resolution depends on the application on the temperature and time of a mechanical cleaning process can be controlled. Since these hydrophobizing agents are sometimes also used as Tablet pressing aids are known, can be a side effect in this way carry out the pressing of the tablets in a particularly reliable manner. The coating with hydrophobic substances does not only in a simple way incompatible substances excellent mix, but also compress to stable tablets.

Essentially anhydrous trisodium citrate is used as the framework or preferably trisodium citrate dihydrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. The content of trisodium citrate dihydrate is about 20 to 80, preferably about 30 to 60% by weight; it can be wholly or partially, i.e. up to about 80, preferably about 50 wt .-% of its weight by occurring in nature Hydroxycarboxylic acids such as e.g. Mono-, dihydroxysuccinic acid, α-hydroxypropionic acid and gluconic acid are replaced.

The tablets according to the invention may also contain alkali carbonates, alkali hydrogen carbonates, alkali sulfates or polycarboxylates as further framework and / or filling substances. The latter, such as Sokalan ^(R) CP 5 (BASF) or completely biodegradable polymers, such as oxidized starches or dextrin, can also serve as additional tabletting aids.

If the cleaners are to remain label-free, you must adhere to the EC preparation guidelines for detergents and cleaning agents. The amount of alkali metal carbonates which can preferably be used in compact form is then about 0 to about 15, preferably about 2 to 12% by weight. If naturally occurring Na ₂ CO ₃ xNaHCO ₃ (Trona / Solvay) is used, the amount used may have to be doubled. Sodium disilicate (Na ₂ O: SiO ₂ = 1: 2) can expediently be added to inhibit corrosion of the wash ware, in particular aluminum, on-glaze decorations and glasses. The amounts need only be small and are from 0 to about 5, preferably from 0 to about 2,% by weight.

The alkali bicarbonate is preferably sodium bicarbonate. The sodium bicarbonate should preferably be in a coarse compact form with a Grain size used in the main fraction between about 0.4 to 1.0 mm will. Its share in the mean forms the difference between the sum of the other ingredients and 100% by weight of total substance.

It is not necessary to add native or preferably synthetic polymers, but it can be used for cleaning agents which are intended for use in hard water regions, up to a maximum of about 20, preferably 0 to 10% by weight. The native polymers include, for example, oxidized starch (for example DE 42 28 786) and polyamino acids such as polyglutamic acid or polyaspartic acid, for example from the companies Cygnus or SRCHEM. The synthetic poly (meth) acrylates can be used as powder or as a 40% aqueous solution, but preferably in granular form. The usable polyacrylates include Alcosperse ^(R) from Alco: Alcosperse ^(R) 102, 104, 106, 404, 406); Acrylsole ^(R) from Norsohaas: Acrysole ^(R) A 1N, LMW 45 N, LMW 10 N, LMW 20 N, SP 02 N, Norasole ^(R) WL1, WL2, WL3, WL4, Degapas ^(R) from Degussa ; Good-Rite ^(R) K-XP 18 from Goodrich. Copolymers of polyacrylic acid and maleic acid (poly (meth) acrylates) can also be used, for example Sokalane ^(R) from BASF: Sokalan ^(R) CP 5, CP 7; Acrysole ^{(R) from} the company Norsohaas: Acrysol ^(R) QR 1014, Alcosperse ^(R) from Alco: Alcosperse ^(R) 175; granular alkaline cleaning additive according to DE 39 37 469.

0.1 to about 5, preferably about 0.2 to 4,% by weight of extremely low-foaming compounds are used as nonionic surfactants (“nonionic surfactants”), which serve to better detach fatty food residues, as wetting agents and, if appropriate, also as tabletting aids. These preferably include C12-C18-alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. However, it is also possible to use other nonionic surfactants known to be low-foaming, such as, for example, C12-C18-alkylpolyethylene glycol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkylpolyalkylene glycol mixed ethers and the foaming but ecologically attractive C ₈ -C ₁₀ - Alkyl polyglucosides and / or C ₁₂ -C ₁₄ alkyl polyethylene glycols with 3-8 ethylene oxide units in the molecule with a degree of polymerization of about 1-4, these then together with 0 to about 1, preferably 0 to about 0.5% by weight, based on the finished cleaning agent, defoaming agents, such as silicone oils, mixtures of silicone oil and hydrophobized silica, paraffin oil / Guerbet alcohols, bisstearyl acid diamide, hydrophobized silica and other other known commercially available defoamers. C ₈ -C ₁₀ alkyl polyglucoside with a degree of polymerization of about 1-4 can preferably be used. Bleached quality should be used, otherwise brown granules will result.

Enzymes such as proteases, amylases, lipases and cellulases, for example proteases such as BLAP ^(R) 140 from the Henkel company, are used for better detachment of food residues containing protein, starch or, for example, tallow fat. Optimase ^(R) -M-440, Optimase ^(R) -M-330, Opticlean ^(R) -M-375, Opticlean ^(R) -M-250 from Solvay Enzymes; Maxacal ^(R) CX 450,000, Maxapem ^(R) from Ibis, Savinase ^(R) 4.0 T 6.0 T 8.0 T from Novo or Experase ^(R) T from Ibis and amylases such as Termamyl ^(R) 60 T, 90 T from Novo; Amylase-LT ^(R) from Solvay Enzymes or Maxamyl ^(R) P 5000, CXT 5000 or CXT 2900 from Ibis, lipases such as Lipolase ^(R) 30 T from Novo, cellulases like Celluzym ^(R) 0.7 T or Novo Nordisk company. The amounts of the enzymes usually used as a mixture in the total average are each about 0.5 to 5, preferably about 1 to 4 wt .-%.

Active oxygen carriers are currently preferably used as bleaching agents. These include primarily sodium perborate mono- and tetrahydrate and sodium percarbonate. But also the use of, for example Boron compounds stabilized sodium percarbonate (German Offenlegungsschrift 33 21 082) has advantages, since this is particularly favorable on the Corrosion behavior affects glasses. Because active oxygen is only at elevated Temperatures unfold their full effect by themselves its activation at approx. 60 ° C, the approximate temperatures of the cleaning process used in the HGSM, so-called bleach activators. As Bleach activators are preferably used for TAED (tetraacetylethylene diamine), PAG (Pentaacetylglucose), DADHT (1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine) and ISA (isatoic anhydride). In addition, the addition can be lower Amounts of known bleach stabilizers, such as alkali phosphonates, Alkali borates or alkali metaborates and metasilicates be useful. The proportion of bleaching agent in the total is about 1 to 20, preferably about 2 to 12 wt .-%, that of the bleach activator about 1 to 8, preferably about 2 to 4% by weight.

Paraffin oils and solid paraffins are used as hydrophobizing agents Melting ranges from 30 to 60 ° C, preferably 35 and 45 ° C into consideration. Paraffins with melting ranges of 42-44 ° C are preferred.

Finally, you can add other usual ingredients to the agents add such as dyes and fragrances as well as corrosion inhibitors for precious metals, especially silver.

Corrosion inhibitors for precious metals, for example inorganic or organic redox-active substances. These include metal salts and / or metal complexes from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, the metals being in one of the oxidation states II, III, IV, V or VI are present (PCT 94/01386), and ascorbic acid, N-mono- (C ₁ -C ₄ -alkyl) -glycine or N, N-di- (C1-C4-alkyl) -glycine, couplers and / or developing agents such as diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclic hydrazones, tetraaminopyrimidines, Triaminohydroxypyriminide, Diaminodihydropyromidine, Dihydroxyhaphtaline, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, primary aromatic amines in the ortho, meta or para-position, a further free or substituted by C ₁ -C ₄ -alkyl or C2-C4-hydroxyalkyl groups have substituted hydroxy or amino groups, and the di- or trihydroxybenzenes, in particular p-hydroxyphenylglycine, 2,4-diaminophenol, 5-chloro-2,3-pyridinediol, 1- (pAminophenyl) morpholine, hydroquinone, pyrocatechol, hydroxy hydroquinone, gallic acid, phloroglucin and pyrogallol (PCT 94/01387).

The composition of the agents according to the invention can thus be in the following range: Na citrate dihydrate 20-80% by weight, preferably 30-60% by weight Na carbonate 0 - 50% by weight, preferably 1 - 35% by weight Na disilicate 0 - 50% by weight, preferably 1 - 35% by weight Polycarboxylate 0-20% by weight, preferably 0-10% by weight Nonionic surfactants 0.1-5% by weight, preferably 0.2-4% by weight Enzymes, total 0.5-10% by weight, preferably 0.5-7% by weight Silver protection 0.05 - 5% by weight, preferably 0.05 - 3% by weight paraffin 0.5-10% by weight, preferably 1-5% by weight Active oxygen compounds 1 - 20% by weight, preferably 2 - 12% by weight Bleach activators 0 - 8% by weight, preferably 0 - 4% by weight Na hydrogen carbonate pH value of 1% rest aqueous solution 8.5 - 11.5% by weight, preferably 9.0 - 11.0% by weight

The invention also relates to a method for manufacturing breakable and storage-stable, polyfunctional detergent tablets, that is characterized in that the free water and high-hydrate salts free powder and / or crystalline Components alone or together with other readily soluble powder or optionally granulated inorganic constituents by spraying a liquid or liquefied hydrophobicizing compound, which in turn are liquid or powder components, such as non-ionic surfactants, fragrances or corrosion inhibitors added may contain, coated with these, and then the mixture with optionally also mixed hydrophobized other solid components and optionally with the addition of other known tabletting aids such as cellulose ethers, microcrystalline cellulose, Starch and the like, pressed into tablets on conventional tablet presses.

Citric acid or its salts are preferably sprayed alone or as a mixture with other readily soluble inorganic components, such as sodium carbonate and / or sodium bicarbonate, with paraffin oil or paraffin wax with a boiling or melting range of about 20-60 ° C., paraffins with others Melting ranges come into consideration and you can add nonionic surfactants or finely divided solid particles such as corrosion inhibitors to the hydrophobizing liquid. Thereafter, further solid constituents, such as active oxygen compounds and optionally hydrophobized bleach activators, can optionally be mixed in and the nonionic surfactants preferably also be sprayed onto them beforehand, thereby further delaying the dissolution of the tablets. The mixture obtained has a liter weight of about 600-1000 g / l and is compressed on conventional tablet presses with a pressing force of 60 kN to about 25 g heavy tablets with a diameter of 38 mm and a density of 1.6 g / cm ³ .

Eccentric presses, hydraulic presses, for example, can be used as usual tablet presses or rotary presses can also be used. Here are Obtain tablets with a breaking strength> 150 N, preferably> 300 N. Breaking strength is to be understood as the force that occurs when the wedge is loaded is needed to destroy a tablet. It relates on the specified tablet dimensions of 25 g weight and a diameter of 38 mm.

By the choice of the hydrophobic substance, preferably paraffins with different melting points, it is possible to cause a certain amount of the tablet already in the pre-rinse cycle Tap water temperatures is solved and to act on the dirty Dishes come, while the rest only in the cleaning cycle prevailing temperatures is resolved and its effect unfolds there. In addition, by further variations in the melting ranges also the oxidation-sensitive enzymes of oxygen-releasing compounds and their activators are solved separately and thereby one after the other come into effect. Also use such as moisture-sensitive Manganese sulfate as a silver protective agent in the tablet is possible. By incorporating untreated manganese sulfate into the water repellent Premix, expediently as a suspension in paraffin tablets that are stable or free from discoloration.

Finally, the invention also relates to the use of the invention manufactured tablets by introducing them into a fluidic favorable part of the washing machine or dishwasher, preferably in the cutlery basket or in a separately suspended separate Container that together with the tablet (s) also as a sales unit can serve, and the tablets are already exposed to the pre-rinse cycle.

Examples

The following basic composition was used: Sokalan® blend (50% CP5) 20.0% by weight Sodium carbonate, anhydrous 5.7% by weight Na hydrogen carbonate, anhydrous 30.0% by weight Trisodium citrate dihydrate 30.0% by weight Perborate monohydrate 5.0% by weight TAED granules 2.0% by weight Enzymes 2.5% by weight Plurafac® LF 403 (BASF) 0.9% by weight Fragrance 0.6% by weight Paraffin / or paraffin oil (F 42-44 ° C) 3.0% by weight Mn-II sulfate 0.3% by weight The tablets produced from them had: tablet diameter 38 mm density 1.57 - 1.64 g / cm ³ Tablet weight 25-27 g Plurafac® LF 403: fatty alcohol ethoxylate with a cloud point of 41 ° C, a solidification point <5 ° C and a viscosity of 50 mPas at 23 ° C.

example 1

Na-citrate powder was applied with a single-cone nozzle before pressing Drilling 1.6 mm under a pressure of 7 - 8 bar a mixture of paraffin oil and Sprayed on perfume by spraying it with 78% fuller wax (Lunaflex® 902 E 36) Mn-II sulfate was suspended. Then, while simultaneously spraying Plurafac® LF 403 (BASF) with the residual solids with the same nozzle at a pressure of 0.7 - 0.8 MPa mixed. The compression of cylindrical tablets with a diameter of 38 mm was carried out on an eccentric press with press forces of 60 - 70 KN.

Example 2

As example 1, but using coarse crystalline sodium citrate dihydrate.

Example 3

Like example 2, but instead of paraffin oil, paraffin was used with a Melting range from 40 - 42 ° C sprayed. The paraffin was Heated to 85 ° C. The nozzle pressure was about 0.7-0.8 MPa.

Example 4

As example 2; however, free powdered Mn-II sulfate was used.

Example 5

As example 2, but free powdered Mn-II sulfate was mixed with the Na citrate dihydrate mixed and then hydrophobicized both components together.

Example 6

As example 4, but using paraffin with a melting range from 44 - 46 ° C.

Example 7

As example 6, but sodium bicarbonate and TAED granules were combined mixed with the coarse crystalline Na citrate dihydrate and together hydrophobic.

Example 8

Like example 4, but TAED powder was combined with the coarse crystalline Na citrate dihydrate hydrophobic.

Example 9

As example 7, but percarbonate was used instead of perborate monohydrate. Polymer-free basic composition: Sodium carbonate, anhydrous 10.0% by weight Sodium bicarbonate, anhydrous 30.0% by weight Trisodium citrate dihydrate 45.0% by weight Sodium percarbonate 5.0% by weight TAED granules 2.0% by weight Amylase 1.0% by weight Protease 1.0% by weight Lipase 1.0% by weight Plurafac ^(R) LF 403 (BASF) 1.0% by weight Fragrance 0.6% by weight Paraffin (F. 42 - 44 ° C) 3.0% by weight Manganese II sulfate 0.4% by weight The tablets made from it had: Tablet diameter 38 mm density 1.57 - 16.4 g / cm ³ Tablet weight 25-27 g

Example 10

It was worked polymer-free. On a mixture of coarse crystalline Trisodium citrate dihydrate, compacted soda and TAED were used with a Gyro nozzle, bore 1.6 mm, nozzle pressure 0.7 - 0.8 MPa, a 75 to 85 ° C hot paraffin melt (melting range 42 - 44 ° C), in which the manganese-II-sulfate was suspended, blown up. On the remaining components sprayed a mixture of surfactant and fragrance and mixed everything. The The mixture was pressed on a rotary press at one Pressure of 50 - 60 MPa.

Example 11

As example 10, but using a premix of percarbonate and also this sprayed nonionic surfactant.

After a storage period of 6 months, none of the tablets in the examples listed showed changes in cleaning performance, fracture stability or dissolving behavior. The control of the amount of tablets, which dissolves in the pre-rinse and in the cleaning cycle, through the choice of the hydrophobizing agent is clearly recognizable.

Claims (15)

1. Break-resistant and storable, multifunctional detergent tablets of any composition, characterized in that the powder-form or crystalline components used in anhydrous form or with a low degree of hydration are coated with a hydrophobicizing compound either individually or in the form of mutually compatible powder-form or optionally granulated mixtures and in that they may additionally contain other moisture-sensitive components, optionally with their own coating.
2. Tablets as claimed in claim 1, characterized in that they have a low degree of alkalinity, are phosphate- and preferably silicate-free and are suitable for machine dishwashing, their powder-form or crystalline components are coated with the same or different hydrophobicizing compounds either individually or in the form of mutually compatible powder-form or optionally granulated mixtures, the hydrophobicizing compounds as such optionally containing liquid or even powder-form tablet components, and in that they additionally contain bleaching agents, optionally bleach activators, enzymes and low-foaming nonionic surfactants which may also be hydrophobicized either individually or in the form of compatible mixtures with one another.
3. Tablets as claimed in claim 2, characterized in that they contain citric acid or salts thereof, alkali metal carbonates, alkali metal hydrogen carbonates and optionally acrylic acid/maleic acid copolymers hydrophobicized individually or in admixture with one another as builders.
4. Tablets as claimed in claims 1 to 3, characterized in that they contain optionally hydrophobicized enzymes.
5. Tablets as claimed in claim 1, characterized in that they have a high degree of alkalinity with pH values above 11 and contain a mixture of pentaalkali metal triphosphates, alkali metal silicates, alkali metal carbonates, bleaching agents and optionally bleach activators, alkali metal hydroxides, zeolites and/or enzymes and low-foaming nonionic surfactants coated with hydrophobicizing compounds, individual components or mixtures thereof again optionally being hydrophobicized.
6. Tablets as claimed in claim 3, characterized in that they contain nonionic surfactants incorporated in the hydrophobicizing agent.
7. Tablets as claimed in claims 1 and 3 to 6, characterized in that they additionally contain optionally hydrophobicized silver protectors.
8. Tablets as claimed in claims 1 and 3 to 7, characterized in that the silver protectors are suspended in the hydrophobicizing agents.
9. Tablets as claimed in claims 1 to 7, characterized in that they contain paraffin oil with a boiling range of 20 to 30°C as the hydrophobicizing agent.
10. Tablets as claimed in claims 1 to 9, characterized in that they contain paraffin wax with a melting range of 30 to 60°C as the hydrophobicizing agent.
11. A process for the production of the tablets claimed in claims 1 to 10, characterized in that the powder-form and/or crystalline components are coated either on their own or together with other readily soluble powder-form or optionally granulated inorganic components by spraying on a liquid or liquefied hydrophobicizing compound which, in turn, may contain liquid components, for example nonionic surfactants or fragrances, and the mixture is subsequently tabletted in standard tablet presses, optionally in the presence of one or more known tabletting aids.
12. A process as claimed in claim 11, characterized in that liquid components are added to the hydrophobicizing substance before spraying.
13. A process as claimed in claim 11, characterized in that liquid components are applied to the solid carriers before hydrophobicization.
14. A process as claimed in claim 13, characterized in that nonionic surfactants and perfume oil are added as the liquid components.
15. The use of the tablets claimed in claims 1 to 10, characterized in that they are introduced into a dishwashing machine at a place favorably situated from the point of view of flow and are exposed to the prerinse cycle.