CA2185723A1 - Breakage-resistant polyfunctional cleaning tablets with a long shelf life, process for producing them and their use - Google Patents
Breakage-resistant polyfunctional cleaning tablets with a long shelf life, process for producing them and their useInfo
- Publication number
- CA2185723A1 CA2185723A1 CA002185723A CA2185723A CA2185723A1 CA 2185723 A1 CA2185723 A1 CA 2185723A1 CA 002185723 A CA002185723 A CA 002185723A CA 2185723 A CA2185723 A CA 2185723A CA 2185723 A1 CA2185723 A1 CA 2185723A1
- Authority
- CA
- Canada
- Prior art keywords
- tablets
- optionally
- hydrophobicizing
- components
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0082—Coated tablets
Abstract
Breakage-resistant polyfunctional washing and cleaning agent tablets with a long shelf life, of any composition, in which non-aqueous or low hydration powdered or crystalline components or subsequently powdered or possibly granular mixtures compatible with each other are coated with a hydrophobic compound and containing further possibly coated damp-sensitive components, eventually with their own coatings. process for producing them and their use.
Description
- 21257~3 Break-Resistantl Storable Multifunctional Detergent Tablets, a Process for their Production and Their Use Machine dishwashing generally consists of a prerinse cycle, a main wash cycle, one or more intermediate rinse cycles, a clear rinse cycle and a drying cycle. This applies in principle both to domestic dishwashing machines and to institutional dishwashing machines.
Machine dishwashing detergents can be formulated as liquids, pastes, powders and tablets. Tablet-form machine dishwashing detergents are becoming increasingly more popular because they are easy to handle.
Several production processes leading to tablets with controllable dissolving behavior have already been described. These tablets are often positioned in the machine itself rather than in the detergent dispensing compartment in the door which enables the tablets to be dissolved to a certain extent in the prerinse cycle so that the effect of the generally additive-free tap water is chemically supported even in this early phase. Thus, DE 35 41 145, for example, describes alkaline machine dishwashing detergent tablets of uniform composition which have a broad solubility profile and which contain a mixture of sodium metasilicate monohydrate and anhydrous metasilicate and also anhydrous pentasodium triphosphate and, optionally, other constituents. DE 41 21 307 describes stable, bifunctional, phosphate- and metasilicate-free low-alkali machine dishwashing detergent tablets of which the builder components are partly used in water-free form and, during the production process, are sprayed with water which guarantees the required solubility profile and provides for favorable tabletting behavior.
In all known cases, the mixture to be tabletted is produced either with components having a high water of crystallization content, which readily give off their water of crystallization during tabletting, or by addition of free water to water-free components to anhydrize their surfaces. The resulting slight moisture content facilitates agglomeration and ensures good tabletting behavior.
However, since the water in the known tablets is present in z~S7~3 completely or partly free from, the incorporation of water-sensitive or rather moisture-sensitive components was possible to only a limited extent, if at all. These components include inter alia bleaching systems based on per compounds and bleach activators, enzymes or even certain corrosion 5 inhibitors.
Accordingly, the problem addressed by the present invention was to provide a process which would not only lead to break-resistant and storable, multifunctional tablets, but - in particular - would also enable water-sensitiveor moisture-sensitive components of known detergent tablets to be 10 incorporated and would avoid any deterioration therein during production and storage.
It has now been found that break-resistant and storable, multifunc-tional detergent tablets can be obtained providing the production process is carried out without the addition of free water and without the use of 15 compounds which readily eliminate water of hydration and providing the powder-form or crystalline components of the detergent mixture are hydrophobicized individually and/or as mutually compatible powder-form or optionally granulated mixtures, are optionally mixed together again, other hydrophobicized or even non-hydrophobicized constituents are added and 20 the resulting mixture is tabletted.
Accordingly, the present invention relates to break-resistant and storable, multifunctional detergent tablets of any composition, the powder-form or crystalline components used in water-free form or with a low degree of hydration being coated with a hydrophobicizing compound either 25 individually or in the form of mutually compatible powder-form or optionally granulated mixtures. In addition, the powder-form or crystalline components may contain other moisture-sensitive components, optionally with their own hydrophobicizing coating.
The detergent tablets according to the present invention may have 30 a high degree of alkalinity with pH values above 11 or a low degree of alkalinity with pH values below 11. Accordingly, they may contain in known manner pentaalkali metal triphosphates, alkali metal silicates, alkali metal 2 1 ~7~
- carbonates, bleaching agents, optionally bleach activators and alkali metal hydroxides, zeolites and/or enzymes. Individual components or mixtures thereof may again be hydrophobicized. However, they may be phosphate-and silicate-free with a low degree of alkalinity and, instead of compounds 5 eliminating active chlorine, may contain oxygen-yielding compounds as bleaching agents and activators therefor and also enzymes. In both cases, they may also contain low-foaming nonionic surfactants.
In a preferred embodiment, the present invention relates to break-resistant and storable, phosphate-free and preferably alkali-metal-silicate-10 free, low-alkali multifunctional detergent tablets7 more particularly for machine dishwashing, based on builders, nonionic surfactants, enzymes, bleaching agents and bleach activators, characterized in that the powder-form or crystalline components are coated with the same or different hydrophobicizing compounds either individually or the form of mutually 15 compatible, powder-form or optionally granulated mixtures, the hydrophobicizing compounds as such optionally containing liquid or even powder-form tablet components.
The hydrophobicizing compounds are applied to the powder-form or crystalline components or mixtures thereof in liquid or liquefied form through 20 a nozzle controllable in known manner, a thin protective coating being formed on the solids and being more uniform and stable, the more finely the liquid droplets are dispersed after leaving the nozzle. The hydrophobicizing substance is present in liquid form during the hydrophobicizing process. It may be a liquid, for example an oil, under normal conditions or may even 25 be a solid, for example wax, which is applied in molten form in the hydrophobicizing stage. The melting range of the hydrophobicizing substance must always be below the desired in-use temperature. Any solubility variants of the individual constituents or mixtures thereof can be determined in advance through the choice of hydrophobicizing substances 30 with different boiling or melting ranges, which can also be varied through the liquid or powder-form tablet constituents optionally incorporated therein, so that their required dissolution in use can be controlled as a function of the 2 1 857~?3 temperature and the time of a machine dishwashing process. Since some of these hydrophobicizing substances are also known as tabletting aids, the tabletting process can be carried out particularly reliably in this way as a side effect. The coating of hydrophobicizing substances enables 5 incompatible substances not only to be thoroughly mixed with one another in a simple manner, but also to be converted into storage-stable tablets.
The builder used may be substantially water-free trisodium citrate or, preferably, dihydrated trisodium citrate. The dihydrated trisodium citrate may be used in the form of a fine or coarse powder. The trisodium citrate 10 content is between about 20 and 80% by weight and preferably between about 30 and 60% by weight and may be completely or partly replaced, i.e.
to a level of about 80 and preferably about 50% of its weight, by naturally occurring hydroxycarboxylic acids such as, for example, monohydroxysuccinic acid, dihydroxysuccinic acid, a-hydroxypropionic acid 15 and gluconic acid.
The tablets according to the invention may also contain alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sulfates or polycarboxylates as additional builders and/or fillers. The polycarboxylates, for example Sokalan~ CP 5 (BASF), or even completely biodegradable 20 polymers, such as oxidized starches or even dextrin, may also serve as additional tabletting aids.
If the detergents are to remain warning-free after packaging, it is important to keep the EU formulation guidelines for detergents and cleaners.
Accordingly, the quantity of preferably compact alkali metal carbonates 25 which may be used is between about 0 and about 15% by weight and preferably between about 2 and 12% by weight. If naturally occurring Na2CO3xNaHCO3 (Trona, a Solvay product) is used, the quantity in which it is used may have to be doubled. To inhibit corrosion of the machine loads, particularly in the case of aluminium, decorative glazes and glasses, 30 sodium disilicate (Na2O:SiO2 = 1:2) is best incorporated in the tablets. The quantities used need only be small, for example from 0 to about 5% by weight and preferably from 0 to about 2% by weight.
- 2 1 ~S7~3 The alkali metal hydrogen carbonate is preferably sodium bicarbonate. The sodium bicarbonate should preferably be used in coarse compacted form with a particle size in the main fraction of from about 0.4 to 1.0 mm. Its percentage content in the detergent forms the difference 5 between the sum total of the other components and 100% by weight of the detergent as a whole.
Although there is no need for native or preferably synthetic polymers, they may still be added to detergents intended for use in hard water areas in quantities of up to at most about 20% by weight and preferably in 10 quantities of 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 of the type obtainable from Cygnus and SRCHEM. The synthetic poly(meth)acrylates may be used in powder form or in the form of a 40% aqueous solution, although 15 they are preferably used in granulated form. Suitable polyacrylates include Alcosperse~) types 102, 104, 106, 404, 406 (products of Alco); Acrylsol(l~) types A 1N, LMW 45 N, LMW 10 N, LMW 20 N, SP 02 N (products of Norsohaas); Norasol~) types WL1, WL2, WL3, WL4; Degapas(~) (Degussa AG); Good-Rite~) K-XP 18 (Goodrich). Copolymers of polyacrylic acid and 20 maleic acid (poly(meth)acrylates) may also be used, for example Sokalan~
types CP 5 and CP 7 (BASF AG); Acrysol~g) QR 1014 (Norsohaas);
Alcosperse~) 175 (Alco); the granular alkaline detergent additive according to DE 39 37 469.
Extremely low-foaming compounds in quantities of 0.1 to about 5%
25 by weight and preferably in quantities of about 0.2 to 4% by weight are used as nonionic surfactants which improve the removal of fat-containing food remains and which also act as wetting agents and even as tabletting aids.
Preferred nonionic surfactants are C,2 ,8 alkyl polyethylene glycol polypropylene glycol ethers containing up to 8 moles of ethylene oxide units 30 and up to 8 moles of propylene oxide units in the molecule. However, it is also possible to use other nonionic surfactants known for their low-foaming behavior, including for example C,2 ,8 alkyl polyethylene glycol polybutylene ~ 18S7~3 glycol ethers containing up to 8 moles of ethylene oxide units and up to 8 moles of butylene oxi units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming, but ecologically attractive C8 ,0 alkyl polyglucosides and/or C12,4 alkyl polyethylene glycols containing 3 to 8 ethylene oxide units in the molecule with a degree of polymerization of about 1 to 4, together with 0 to about 1% by weight and preferably 0 to about 0.5% by weight, based on the final detergent, of defoamers, for example silicone oils, mixtures of silicone oil and hydrophobicized silica, parafffin oil/Guerbet alcohols, bis-stearic acid diamide, hydrophobicized silicaand other known commercially available defoamers. C8 ~o alkyl polyglucoside with a degree of polymerization of about 1 to 4 is preferably used. A bleached quality should be used because otherwise brown granules are formed.
Enzymes are used to improve the removal of protein-, starch- and tallow-containing food remains. Examples of suitable enzymes are proteases, amylases, lipases and cellulases, for example proteases, such as BLAP~ 140 (Henkel KGaA); Optimase~) M-440, Optimase(g) M-330, Opticlean~ M-375, Opticleantg) M-250 (Solvay Enzymes); Maxacal~ CX
450.000, Maxapem~ (Ibis); Savinase~ 4,0 T, 6,0 T, 8,0 T (Novo) or Experase~ T (Ibis), and amylases, such as Termamyl~ 60 T, 90 T (Novo);
Amylase-LT(E~) (Solvay Enzymes) or Maxamyltg P 5000, CXT 5000 or CXT 2900 (Ibis); lipases, such as Lipolase~ 30 T (Novo); cellulases, such as Celluzym~ 0,7 T (Novo Nordisk). The enzymes generally used in the form of a mixture make up around 0.5 to 5% by weight and preferably around 1 to 4% by weight of the detergent as a whole.
At present, active oxygen carriers are preferably used as bleaching agents. Active oxygen carriers include, above all, sodium perborate monohydrate and tetrahydrate and also sodium percarbonate. However, the use of sodium percarbonate stabilized, for example, with boron compounds (DE-A-33 21 082) also has advantages because it has a particularly favorable effect on the corrosion behavior of glasses. Since active oxygen 7 ~3 - only develops it full effect on its own at elevated temperature, so-called bleach activators are added at around 60C, the approximate temperatures of the domestic machine dishwashing process, for the purposes of activation. Preferred bleach activators are TAED (tetraacetyl 5 ethylenediamine), PAG (pentaacetyl glucose), DADHT (1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine) and ISA (isatoic anhydride). In addition, it can also be useful to add small quantities of known bleach stabilizers, for example alkali metal phosphonates, alkali metal borates or alkali metal metaborates and metasilicates. The bleaching agents make up about 1 to 20% by weight and preferably about 2 to 12% by weight of the detergent as a whole while the bleach activator makes up about 1 to 8% by weight and preferably about 2 to 4% by weight.
Suitable hydrophobicizing substances are paraffin oils and solid paraffins with melting ranges of 30 to 60C and preferably 35 to 45C.
15 Paraffins with melting ranges of 42 to 44C are preferably used.
Finally, other typical components may be added to the dishwashing detergents, including for example dyes and fragrances and also corrosion inhibitors for noble metals, particularly silver.
Examples of suitable corrosion inhibitors for noble metals are 20 inorganic or organic redox-active substances, including metal salts and/or metal complexes from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and/or complexes, the metals being present in one of the oxidation stages ll, Ill, IV, V or Vl (PCT
94/01386), and ascorbic acid, N-mono-(C,4 alkyl)-glycine or N,N-di-(C,4 25 alkyl)-glucine, secondary intermediates and/or primary intermediates, such as diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclichydrazones,tetraaminopyrimidines,triaminohydroxypyrimidines, diaminodihydroxypyrimidines, dihydroxynaphthalenes, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, primary aromatic amines 30 containing another free or C, 4 alkyl- or C2 4-hydroxyalkyl-substituted hydroxy or amino group in the ortho, meta or para position, and dihydroxy or trihydroxy benzenes, more especially p-hydroxyphenyl glycine, 2,4-~18$7Z3 . - diaminophenol, 5-chloro-2,3-pyridine diol, 1-(p-aminophenyl)-morpholine, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol and pyrogallol (PCT 94/01387).
Accordingly, the composition of the detergents according to the 5 invention may lie within the following limits:
Na citrate dihydrate: 20 to 80% by weight, preferably 30 to 60% by weight Na carbonate: 0 to 50% by weight, preferably 1 to 35% by weight Na disilicate: 0 to 50% by weight, preferably 1 to 35% by weight Polycarboxylate: 0 to 20% by weight, preferably 0 to10% by weight Nonionic surfactants: 0.1 to 5% by weight, preferably 0.2 to 4% by weight Enzymes, total: 0.5 to10% by weight, preferably 0.5 to 7% by weight Silver protector: 0.05 to 5 % by weight, preferably 0.05 to 3% by weight Paraffin: 0.5 to 10% by weight, preferably 1 to 5% by weight Active oxygen compounds: 1 to 20% by weight, preferably 2 to 12% by 15 weight Bleach activators: 0 to 8% by weight, preferably 0 to 4% by weight Na hydrogen carbonate: rest pH value of a 1 % aqueous solution: 8.5 to 11.5, preferably 9.0 to 11Ø
In addition, the present invention relates to a process for the 20 production of break-resistant and storable, multifunctional detergent tablets, characterized in that the powder-form and/or crystalline components free from free water and salts of high hydrate content 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 25 hydrophobicizing compound which, in turn, may contain liquid or powder-form components, for example nonionic surfactants, fragrances or corrosion inhibitors, and the mixture is subsequently mixed with other optionally hydrophobicized solid constituents and tabletted in standard tablet presses, optionally in the presence of other known tabletting aids, for example 30 cellulose ethers, microcrystalline cellulose, starch and the like.
Citric acid or salts thereof is/are sprayed either on its/their own or in admixture with other readily soluble inorganic components, for example 2 l ~57~
sodium carbonate and/or sodium hydrogen carbonate, with paraffin oil or paraffin wax having a boiling or melting range of around 20 to 60C, although paraffins with other melting ranges may also be used. Nonionic surfactants or fine-particle solids, such as corrosion inhibitors, may be 5 added to the hydrophobicizing liquid. Other solid constituents, such as active oxygen compounds and optionally hydrophobicized bleach activators, may then be added, preferably after having been sprayed with the nonionic surfactants, so that the dissolution of the tablets is further delayed. The mixture obtained has a weight per liter of around 600 to 1000 g/l and is 10 tabletted under a force of 60 kN in standard tablet presses to form tablets weighing around 25 g for a diameter of 38 mm and a density of 1.6 g/cm3.
The tabletting process may be carried out in standard tablet presses, for example eccentric presses, hydraulic presses or even rotary presses.
Tablets with a breaking strength of > 150 N and preferably > 300 N are 15 obtained. The breaking strength is understood to be the force applied by a wedge which is required to destroy a tablet. It is based on the above-mentioned tablet weight of 25 g and tablet diameter of 38 mm.
Through the choice of the hydrophobicizing substance, including -preferably - paraffins with different melting points, it is possible to ensure 20 that a certain amount of the tablet is actually dissolved in the prerinse cycle at tap water temperatures and acts on the soiled dishes, the rest of the tablet only being dissolved and developing its effect at the temperatures prevailing in the main wash cycle. In addition, the oxidation-sensitive enzymes and oxygen-yielding compounds and their activators can even be 25 dissolved separately from one another and thus successively activated by further variation of the melting ranges. Moisture-sensitive manganese sulfate, for example, may also be incorporated in the tablet as a silver protector. Stable or non-discoloring tablets are obtained by incorporating untreated manganese sulfate in the hydrophobicized compound, preferably 30 in the form of a suspension in paraffin.
Finally, the present invention also relates to the use of the tablets produced in accordance with the invention by introduction thereof into the - 2 1 ~$723 dishwashing machine at a place favorably situated from the point of view of flow, preferably in the cutlery basket or in a separate special container, which may even be sold together with the tablet (or tablets), so that the tablets are exposed to the prerinse cycle.
Examples The following basic composition was used:
Sokalan~) blend (50% CP5) 20.0% by weight Sodium carbonate, anhydrous 5.7% by weight Sodium hydrogen carbonate, anhydrous30.0% 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 and/or paraffin oil (Mp. 42-44C)3.0% by weight Mn(ll) sulfate 0.3% by weight Plurafac(~ LF 403: Fatty alcohol ethoxylate with a cloud point of 41C, a solidification point of <5C and a viscosity of 50 mPas at 23C.
The tablets produced from this composition had a diameter of 38 mm, a density of 1.57 to 1.64 g/cm3 and a tablet weight of 25 to 27 g.
Example 1 Before tabletting, a mixture of paraffin oil and perfume, in which Mn(ll) sulfate sprayed with 78% of filler wax (Lunaflex(l~) 902 E 36) had been suspended, was sprayed onto Na citrate powder through a one-component solid-cone nozzle with a 1.6 mm diameter bore under a pressure of 7 to 8 bar. The powder was then mixed with the remaining solids while was sprayed on through the same nozzle under a pressure of 0.7 to 0.8 MPa. The mixture was tabletted to 38 mm diameter cylindrical tablets in - 2 ~ ~S7~3 an eccentric press under pressures of 60 to 70 KN.
Example 2 As Example 1, but using coarse crystalline Na citrate dihydrate.
Example 3 As Example 2, except that paraffin with a melting range of 40 to 42C
was sprayed on instead of paraffin oil. To this end, the paraffin was heated to 80-85C. The spraying pressure was around 0.7-0.8 MPa.
10 Example 4 As Example 2, except that free powder-form Mn(ll) sulfate was used.
Example 5 As Example 2, except that free powder-form Mn(ll) sulfate was mixed 15 with the Na citrate dihydrate and both components were hydrophobicized together.
Example 6 As Example 4, except that paraffin with a melting range of 44 to 46C
20 was used.
Example 7 As Example 6, except that the Na hydrogen carbonate and the TAED
granules were mixed and hydrophobicized together with the coarse 25 crystalline Na citrate dihydrate.
Example 8 As Example 4, except that the TAED powder was hydrophobicized together with the coarse crystalline Na nitrate dihydrate.
Example 9 As Example 7, except that the perborate monohydrate was replaced 2 1 ~5~3 by percarbonate.
Polymer-free basic composition:
Sodium carbonate, anhydrous10,0% by weight Sodium hydrogen carbonate, anhydrous30.0% by weight Trisodium citrate dihydrate45.0% 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~ LF 403 (BASF) 1.0% by weight Fragrance 0.6% by weight Paraffin (Mp. 42-44C) 3.0% by weight Manganese(ll) sulfate 0.4% by weight The tablets produced from this composition had a diameter of 38 mm, a density of 1.57 to 16.4 g/cm3 and a weight of 25 to 27 g.
Example 10 The polymer-free basic composition was used. A 75 to 85C paraffin melt (melting range 42-44C), in which the manganese(ll) sulfate had been suspended, was sprayed onto a mixture of coarse crystalline trisodium 25 citrate dihydrate, compacted soda and TAED through a circular mist nozzle (bore diameter 1.6 mm) under a pressure of 0.7 to 0.8 MPa. A mixture of surfactant and fragrance was sprayed onto and mixed with the remaining components. The mixture was tabletted in a rotary press under a pressure of 50 to 60 MPa.
~1 ~5723 Example 11 As Example 10, but using a compound of percarbonate and nonionic surfactant sprayed thereon.
After storage for 6 months, none of the tablets produced in 5 accordance with the foregoing Examples showed any changes in performance, in break resistance or in dissolving behavior. The control of the quantities of tablet respectively dissolved in the prerinse cycle and in themain wash cycle through the choice of the hydrophobicizing agent is clearly apparent. Numerous variations are possible and fall within the scope of the 1 0 invention.
~1~57~3 -o ~ o o , '`~
oo C~
~ ~ ~o , ~ ~, U~
u~ cn C~ ~ o o --., D (~ ~D ~D D ~ o~ D
~ ~ m n ~ ~ ~ o
Machine dishwashing detergents can be formulated as liquids, pastes, powders and tablets. Tablet-form machine dishwashing detergents are becoming increasingly more popular because they are easy to handle.
Several production processes leading to tablets with controllable dissolving behavior have already been described. These tablets are often positioned in the machine itself rather than in the detergent dispensing compartment in the door which enables the tablets to be dissolved to a certain extent in the prerinse cycle so that the effect of the generally additive-free tap water is chemically supported even in this early phase. Thus, DE 35 41 145, for example, describes alkaline machine dishwashing detergent tablets of uniform composition which have a broad solubility profile and which contain a mixture of sodium metasilicate monohydrate and anhydrous metasilicate and also anhydrous pentasodium triphosphate and, optionally, other constituents. DE 41 21 307 describes stable, bifunctional, phosphate- and metasilicate-free low-alkali machine dishwashing detergent tablets of which the builder components are partly used in water-free form and, during the production process, are sprayed with water which guarantees the required solubility profile and provides for favorable tabletting behavior.
In all known cases, the mixture to be tabletted is produced either with components having a high water of crystallization content, which readily give off their water of crystallization during tabletting, or by addition of free water to water-free components to anhydrize their surfaces. The resulting slight moisture content facilitates agglomeration and ensures good tabletting behavior.
However, since the water in the known tablets is present in z~S7~3 completely or partly free from, the incorporation of water-sensitive or rather moisture-sensitive components was possible to only a limited extent, if at all. These components include inter alia bleaching systems based on per compounds and bleach activators, enzymes or even certain corrosion 5 inhibitors.
Accordingly, the problem addressed by the present invention was to provide a process which would not only lead to break-resistant and storable, multifunctional tablets, but - in particular - would also enable water-sensitiveor moisture-sensitive components of known detergent tablets to be 10 incorporated and would avoid any deterioration therein during production and storage.
It has now been found that break-resistant and storable, multifunc-tional detergent tablets can be obtained providing the production process is carried out without the addition of free water and without the use of 15 compounds which readily eliminate water of hydration and providing the powder-form or crystalline components of the detergent mixture are hydrophobicized individually and/or as mutually compatible powder-form or optionally granulated mixtures, are optionally mixed together again, other hydrophobicized or even non-hydrophobicized constituents are added and 20 the resulting mixture is tabletted.
Accordingly, the present invention relates to break-resistant and storable, multifunctional detergent tablets of any composition, the powder-form or crystalline components used in water-free form or with a low degree of hydration being coated with a hydrophobicizing compound either 25 individually or in the form of mutually compatible powder-form or optionally granulated mixtures. In addition, the powder-form or crystalline components may contain other moisture-sensitive components, optionally with their own hydrophobicizing coating.
The detergent tablets according to the present invention may have 30 a high degree of alkalinity with pH values above 11 or a low degree of alkalinity with pH values below 11. Accordingly, they may contain in known manner pentaalkali metal triphosphates, alkali metal silicates, alkali metal 2 1 ~7~
- carbonates, bleaching agents, optionally bleach activators and alkali metal hydroxides, zeolites and/or enzymes. Individual components or mixtures thereof may again be hydrophobicized. However, they may be phosphate-and silicate-free with a low degree of alkalinity and, instead of compounds 5 eliminating active chlorine, may contain oxygen-yielding compounds as bleaching agents and activators therefor and also enzymes. In both cases, they may also contain low-foaming nonionic surfactants.
In a preferred embodiment, the present invention relates to break-resistant and storable, phosphate-free and preferably alkali-metal-silicate-10 free, low-alkali multifunctional detergent tablets7 more particularly for machine dishwashing, based on builders, nonionic surfactants, enzymes, bleaching agents and bleach activators, characterized in that the powder-form or crystalline components are coated with the same or different hydrophobicizing compounds either individually or the form of mutually 15 compatible, powder-form or optionally granulated mixtures, the hydrophobicizing compounds as such optionally containing liquid or even powder-form tablet components.
The hydrophobicizing compounds are applied to the powder-form or crystalline components or mixtures thereof in liquid or liquefied form through 20 a nozzle controllable in known manner, a thin protective coating being formed on the solids and being more uniform and stable, the more finely the liquid droplets are dispersed after leaving the nozzle. The hydrophobicizing substance is present in liquid form during the hydrophobicizing process. It may be a liquid, for example an oil, under normal conditions or may even 25 be a solid, for example wax, which is applied in molten form in the hydrophobicizing stage. The melting range of the hydrophobicizing substance must always be below the desired in-use temperature. Any solubility variants of the individual constituents or mixtures thereof can be determined in advance through the choice of hydrophobicizing substances 30 with different boiling or melting ranges, which can also be varied through the liquid or powder-form tablet constituents optionally incorporated therein, so that their required dissolution in use can be controlled as a function of the 2 1 857~?3 temperature and the time of a machine dishwashing process. Since some of these hydrophobicizing substances are also known as tabletting aids, the tabletting process can be carried out particularly reliably in this way as a side effect. The coating of hydrophobicizing substances enables 5 incompatible substances not only to be thoroughly mixed with one another in a simple manner, but also to be converted into storage-stable tablets.
The builder used may be substantially water-free trisodium citrate or, preferably, dihydrated trisodium citrate. The dihydrated trisodium citrate may be used in the form of a fine or coarse powder. The trisodium citrate 10 content is between about 20 and 80% by weight and preferably between about 30 and 60% by weight and may be completely or partly replaced, i.e.
to a level of about 80 and preferably about 50% of its weight, by naturally occurring hydroxycarboxylic acids such as, for example, monohydroxysuccinic acid, dihydroxysuccinic acid, a-hydroxypropionic acid 15 and gluconic acid.
The tablets according to the invention may also contain alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sulfates or polycarboxylates as additional builders and/or fillers. The polycarboxylates, for example Sokalan~ CP 5 (BASF), or even completely biodegradable 20 polymers, such as oxidized starches or even dextrin, may also serve as additional tabletting aids.
If the detergents are to remain warning-free after packaging, it is important to keep the EU formulation guidelines for detergents and cleaners.
Accordingly, the quantity of preferably compact alkali metal carbonates 25 which may be used is between about 0 and about 15% by weight and preferably between about 2 and 12% by weight. If naturally occurring Na2CO3xNaHCO3 (Trona, a Solvay product) is used, the quantity in which it is used may have to be doubled. To inhibit corrosion of the machine loads, particularly in the case of aluminium, decorative glazes and glasses, 30 sodium disilicate (Na2O:SiO2 = 1:2) is best incorporated in the tablets. The quantities used need only be small, for example from 0 to about 5% by weight and preferably from 0 to about 2% by weight.
- 2 1 ~S7~3 The alkali metal hydrogen carbonate is preferably sodium bicarbonate. The sodium bicarbonate should preferably be used in coarse compacted form with a particle size in the main fraction of from about 0.4 to 1.0 mm. Its percentage content in the detergent forms the difference 5 between the sum total of the other components and 100% by weight of the detergent as a whole.
Although there is no need for native or preferably synthetic polymers, they may still be added to detergents intended for use in hard water areas in quantities of up to at most about 20% by weight and preferably in 10 quantities of 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 of the type obtainable from Cygnus and SRCHEM. The synthetic poly(meth)acrylates may be used in powder form or in the form of a 40% aqueous solution, although 15 they are preferably used in granulated form. Suitable polyacrylates include Alcosperse~) types 102, 104, 106, 404, 406 (products of Alco); Acrylsol(l~) types A 1N, LMW 45 N, LMW 10 N, LMW 20 N, SP 02 N (products of Norsohaas); Norasol~) types WL1, WL2, WL3, WL4; Degapas(~) (Degussa AG); Good-Rite~) K-XP 18 (Goodrich). Copolymers of polyacrylic acid and 20 maleic acid (poly(meth)acrylates) may also be used, for example Sokalan~
types CP 5 and CP 7 (BASF AG); Acrysol~g) QR 1014 (Norsohaas);
Alcosperse~) 175 (Alco); the granular alkaline detergent additive according to DE 39 37 469.
Extremely low-foaming compounds in quantities of 0.1 to about 5%
25 by weight and preferably in quantities of about 0.2 to 4% by weight are used as nonionic surfactants which improve the removal of fat-containing food remains and which also act as wetting agents and even as tabletting aids.
Preferred nonionic surfactants are C,2 ,8 alkyl polyethylene glycol polypropylene glycol ethers containing up to 8 moles of ethylene oxide units 30 and up to 8 moles of propylene oxide units in the molecule. However, it is also possible to use other nonionic surfactants known for their low-foaming behavior, including for example C,2 ,8 alkyl polyethylene glycol polybutylene ~ 18S7~3 glycol ethers containing up to 8 moles of ethylene oxide units and up to 8 moles of butylene oxi units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming, but ecologically attractive C8 ,0 alkyl polyglucosides and/or C12,4 alkyl polyethylene glycols containing 3 to 8 ethylene oxide units in the molecule with a degree of polymerization of about 1 to 4, together with 0 to about 1% by weight and preferably 0 to about 0.5% by weight, based on the final detergent, of defoamers, for example silicone oils, mixtures of silicone oil and hydrophobicized silica, parafffin oil/Guerbet alcohols, bis-stearic acid diamide, hydrophobicized silicaand other known commercially available defoamers. C8 ~o alkyl polyglucoside with a degree of polymerization of about 1 to 4 is preferably used. A bleached quality should be used because otherwise brown granules are formed.
Enzymes are used to improve the removal of protein-, starch- and tallow-containing food remains. Examples of suitable enzymes are proteases, amylases, lipases and cellulases, for example proteases, such as BLAP~ 140 (Henkel KGaA); Optimase~) M-440, Optimase(g) M-330, Opticlean~ M-375, Opticleantg) M-250 (Solvay Enzymes); Maxacal~ CX
450.000, Maxapem~ (Ibis); Savinase~ 4,0 T, 6,0 T, 8,0 T (Novo) or Experase~ T (Ibis), and amylases, such as Termamyl~ 60 T, 90 T (Novo);
Amylase-LT(E~) (Solvay Enzymes) or Maxamyltg P 5000, CXT 5000 or CXT 2900 (Ibis); lipases, such as Lipolase~ 30 T (Novo); cellulases, such as Celluzym~ 0,7 T (Novo Nordisk). The enzymes generally used in the form of a mixture make up around 0.5 to 5% by weight and preferably around 1 to 4% by weight of the detergent as a whole.
At present, active oxygen carriers are preferably used as bleaching agents. Active oxygen carriers include, above all, sodium perborate monohydrate and tetrahydrate and also sodium percarbonate. However, the use of sodium percarbonate stabilized, for example, with boron compounds (DE-A-33 21 082) also has advantages because it has a particularly favorable effect on the corrosion behavior of glasses. Since active oxygen 7 ~3 - only develops it full effect on its own at elevated temperature, so-called bleach activators are added at around 60C, the approximate temperatures of the domestic machine dishwashing process, for the purposes of activation. Preferred bleach activators are TAED (tetraacetyl 5 ethylenediamine), PAG (pentaacetyl glucose), DADHT (1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine) and ISA (isatoic anhydride). In addition, it can also be useful to add small quantities of known bleach stabilizers, for example alkali metal phosphonates, alkali metal borates or alkali metal metaborates and metasilicates. The bleaching agents make up about 1 to 20% by weight and preferably about 2 to 12% by weight of the detergent as a whole while the bleach activator makes up about 1 to 8% by weight and preferably about 2 to 4% by weight.
Suitable hydrophobicizing substances are paraffin oils and solid paraffins with melting ranges of 30 to 60C and preferably 35 to 45C.
15 Paraffins with melting ranges of 42 to 44C are preferably used.
Finally, other typical components may be added to the dishwashing detergents, including for example dyes and fragrances and also corrosion inhibitors for noble metals, particularly silver.
Examples of suitable corrosion inhibitors for noble metals are 20 inorganic or organic redox-active substances, including metal salts and/or metal complexes from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and/or complexes, the metals being present in one of the oxidation stages ll, Ill, IV, V or Vl (PCT
94/01386), and ascorbic acid, N-mono-(C,4 alkyl)-glycine or N,N-di-(C,4 25 alkyl)-glucine, secondary intermediates and/or primary intermediates, such as diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclichydrazones,tetraaminopyrimidines,triaminohydroxypyrimidines, diaminodihydroxypyrimidines, dihydroxynaphthalenes, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, primary aromatic amines 30 containing another free or C, 4 alkyl- or C2 4-hydroxyalkyl-substituted hydroxy or amino group in the ortho, meta or para position, and dihydroxy or trihydroxy benzenes, more especially p-hydroxyphenyl glycine, 2,4-~18$7Z3 . - diaminophenol, 5-chloro-2,3-pyridine diol, 1-(p-aminophenyl)-morpholine, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol and pyrogallol (PCT 94/01387).
Accordingly, the composition of the detergents according to the 5 invention may lie within the following limits:
Na citrate dihydrate: 20 to 80% by weight, preferably 30 to 60% by weight Na carbonate: 0 to 50% by weight, preferably 1 to 35% by weight Na disilicate: 0 to 50% by weight, preferably 1 to 35% by weight Polycarboxylate: 0 to 20% by weight, preferably 0 to10% by weight Nonionic surfactants: 0.1 to 5% by weight, preferably 0.2 to 4% by weight Enzymes, total: 0.5 to10% by weight, preferably 0.5 to 7% by weight Silver protector: 0.05 to 5 % by weight, preferably 0.05 to 3% by weight Paraffin: 0.5 to 10% by weight, preferably 1 to 5% by weight Active oxygen compounds: 1 to 20% by weight, preferably 2 to 12% by 15 weight Bleach activators: 0 to 8% by weight, preferably 0 to 4% by weight Na hydrogen carbonate: rest pH value of a 1 % aqueous solution: 8.5 to 11.5, preferably 9.0 to 11Ø
In addition, the present invention relates to a process for the 20 production of break-resistant and storable, multifunctional detergent tablets, characterized in that the powder-form and/or crystalline components free from free water and salts of high hydrate content 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 25 hydrophobicizing compound which, in turn, may contain liquid or powder-form components, for example nonionic surfactants, fragrances or corrosion inhibitors, and the mixture is subsequently mixed with other optionally hydrophobicized solid constituents and tabletted in standard tablet presses, optionally in the presence of other known tabletting aids, for example 30 cellulose ethers, microcrystalline cellulose, starch and the like.
Citric acid or salts thereof is/are sprayed either on its/their own or in admixture with other readily soluble inorganic components, for example 2 l ~57~
sodium carbonate and/or sodium hydrogen carbonate, with paraffin oil or paraffin wax having a boiling or melting range of around 20 to 60C, although paraffins with other melting ranges may also be used. Nonionic surfactants or fine-particle solids, such as corrosion inhibitors, may be 5 added to the hydrophobicizing liquid. Other solid constituents, such as active oxygen compounds and optionally hydrophobicized bleach activators, may then be added, preferably after having been sprayed with the nonionic surfactants, so that the dissolution of the tablets is further delayed. The mixture obtained has a weight per liter of around 600 to 1000 g/l and is 10 tabletted under a force of 60 kN in standard tablet presses to form tablets weighing around 25 g for a diameter of 38 mm and a density of 1.6 g/cm3.
The tabletting process may be carried out in standard tablet presses, for example eccentric presses, hydraulic presses or even rotary presses.
Tablets with a breaking strength of > 150 N and preferably > 300 N are 15 obtained. The breaking strength is understood to be the force applied by a wedge which is required to destroy a tablet. It is based on the above-mentioned tablet weight of 25 g and tablet diameter of 38 mm.
Through the choice of the hydrophobicizing substance, including -preferably - paraffins with different melting points, it is possible to ensure 20 that a certain amount of the tablet is actually dissolved in the prerinse cycle at tap water temperatures and acts on the soiled dishes, the rest of the tablet only being dissolved and developing its effect at the temperatures prevailing in the main wash cycle. In addition, the oxidation-sensitive enzymes and oxygen-yielding compounds and their activators can even be 25 dissolved separately from one another and thus successively activated by further variation of the melting ranges. Moisture-sensitive manganese sulfate, for example, may also be incorporated in the tablet as a silver protector. Stable or non-discoloring tablets are obtained by incorporating untreated manganese sulfate in the hydrophobicized compound, preferably 30 in the form of a suspension in paraffin.
Finally, the present invention also relates to the use of the tablets produced in accordance with the invention by introduction thereof into the - 2 1 ~$723 dishwashing machine at a place favorably situated from the point of view of flow, preferably in the cutlery basket or in a separate special container, which may even be sold together with the tablet (or tablets), so that the tablets are exposed to the prerinse cycle.
Examples The following basic composition was used:
Sokalan~) blend (50% CP5) 20.0% by weight Sodium carbonate, anhydrous 5.7% by weight Sodium hydrogen carbonate, anhydrous30.0% 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 and/or paraffin oil (Mp. 42-44C)3.0% by weight Mn(ll) sulfate 0.3% by weight Plurafac(~ LF 403: Fatty alcohol ethoxylate with a cloud point of 41C, a solidification point of <5C and a viscosity of 50 mPas at 23C.
The tablets produced from this composition had a diameter of 38 mm, a density of 1.57 to 1.64 g/cm3 and a tablet weight of 25 to 27 g.
Example 1 Before tabletting, a mixture of paraffin oil and perfume, in which Mn(ll) sulfate sprayed with 78% of filler wax (Lunaflex(l~) 902 E 36) had been suspended, was sprayed onto Na citrate powder through a one-component solid-cone nozzle with a 1.6 mm diameter bore under a pressure of 7 to 8 bar. The powder was then mixed with the remaining solids while was sprayed on through the same nozzle under a pressure of 0.7 to 0.8 MPa. The mixture was tabletted to 38 mm diameter cylindrical tablets in - 2 ~ ~S7~3 an eccentric press under pressures of 60 to 70 KN.
Example 2 As Example 1, but using coarse crystalline Na citrate dihydrate.
Example 3 As Example 2, except that paraffin with a melting range of 40 to 42C
was sprayed on instead of paraffin oil. To this end, the paraffin was heated to 80-85C. The spraying pressure was around 0.7-0.8 MPa.
10 Example 4 As Example 2, except that free powder-form Mn(ll) sulfate was used.
Example 5 As Example 2, except that free powder-form Mn(ll) sulfate was mixed 15 with the Na citrate dihydrate and both components were hydrophobicized together.
Example 6 As Example 4, except that paraffin with a melting range of 44 to 46C
20 was used.
Example 7 As Example 6, except that the Na hydrogen carbonate and the TAED
granules were mixed and hydrophobicized together with the coarse 25 crystalline Na citrate dihydrate.
Example 8 As Example 4, except that the TAED powder was hydrophobicized together with the coarse crystalline Na nitrate dihydrate.
Example 9 As Example 7, except that the perborate monohydrate was replaced 2 1 ~5~3 by percarbonate.
Polymer-free basic composition:
Sodium carbonate, anhydrous10,0% by weight Sodium hydrogen carbonate, anhydrous30.0% by weight Trisodium citrate dihydrate45.0% 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~ LF 403 (BASF) 1.0% by weight Fragrance 0.6% by weight Paraffin (Mp. 42-44C) 3.0% by weight Manganese(ll) sulfate 0.4% by weight The tablets produced from this composition had a diameter of 38 mm, a density of 1.57 to 16.4 g/cm3 and a weight of 25 to 27 g.
Example 10 The polymer-free basic composition was used. A 75 to 85C paraffin melt (melting range 42-44C), in which the manganese(ll) sulfate had been suspended, was sprayed onto a mixture of coarse crystalline trisodium 25 citrate dihydrate, compacted soda and TAED through a circular mist nozzle (bore diameter 1.6 mm) under a pressure of 0.7 to 0.8 MPa. A mixture of surfactant and fragrance was sprayed onto and mixed with the remaining components. The mixture was tabletted in a rotary press under a pressure of 50 to 60 MPa.
~1 ~5723 Example 11 As Example 10, but using a compound of percarbonate and nonionic surfactant sprayed thereon.
After storage for 6 months, none of the tablets produced in 5 accordance with the foregoing Examples showed any changes in performance, in break resistance or in dissolving behavior. The control of the quantities of tablet respectively dissolved in the prerinse cycle and in themain wash cycle through the choice of the hydrophobicizing agent is clearly apparent. Numerous variations are possible and fall within the scope of the 1 0 invention.
~1~57~3 -o ~ o o , '`~
oo C~
~ ~ ~o , ~ ~, U~
u~ cn C~ ~ o o --., D (~ ~D ~D D ~ o~ D
~ ~ m n ~ ~ ~ o
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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4408718.7 | 1994-03-15 | ||
| DE4408718A DE4408718A1 (en) | 1994-03-15 | 1994-03-15 | Breakage and storage stable, polyfunctional cleaning tablets, process for their preparation and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2185723A1 true CA2185723A1 (en) | 1995-09-21 |
Family
ID=6512817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002185723A Abandoned CA2185723A1 (en) | 1994-03-15 | 1995-03-06 | Breakage-resistant polyfunctional cleaning tablets with a long shelf life, process for producing them and their use |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5854189A (en) |
| EP (1) | EP0750662B1 (en) |
| JP (1) | JPH09510252A (en) |
| AT (1) | ATE170216T1 (en) |
| CA (1) | CA2185723A1 (en) |
| DE (2) | DE4408718A1 (en) |
| DK (1) | DK0750662T3 (en) |
| ES (1) | ES2121352T3 (en) |
| WO (1) | WO1995025161A1 (en) |
Families Citing this family (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19606765A1 (en) * | 1996-02-23 | 1997-08-28 | Henkel Kgaa | Process for the production of dishwasher tablets |
| GB2320254A (en) * | 1996-12-12 | 1998-06-17 | Procter & Gamble | Process for making tabletted detergent compositions |
| US6177393B1 (en) * | 1996-12-12 | 2001-01-23 | The Procter & Gamble Company | Process for making tabletted detergent compositions |
| US6177398B1 (en) | 1996-12-12 | 2001-01-23 | The Procter & Gamble Company | Process for making tabletted detergent compositions |
| GB2320255A (en) * | 1996-12-12 | 1998-06-17 | Procter & Gamble | Process for making tabletted detergent compositions |
| DE19739383A1 (en) * | 1997-09-09 | 1999-03-11 | Henkel Kgaa | Detergent tablets with improved solubility |
| US6175752B1 (en) | 1998-04-30 | 2001-01-16 | Therasense, Inc. | Analyte monitoring device and methods of use |
| US8974386B2 (en) | 1998-04-30 | 2015-03-10 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
| US8688188B2 (en) | 1998-04-30 | 2014-04-01 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
| US8480580B2 (en) | 1998-04-30 | 2013-07-09 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
| US6949816B2 (en) | 2003-04-21 | 2005-09-27 | Motorola, Inc. | Semiconductor component having first surface area for electrically coupling to a semiconductor chip and second surface area for electrically coupling to a substrate, and method of manufacturing same |
| US8346337B2 (en) | 1998-04-30 | 2013-01-01 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
| US9066695B2 (en) | 1998-04-30 | 2015-06-30 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
| US8465425B2 (en) | 1998-04-30 | 2013-06-18 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods of use |
| US6362150B1 (en) * | 1998-11-12 | 2002-03-26 | Corporation Cressida | Detergent composition in the form of a solid detergent containing surfactant and bleaching peroxide |
| US6683043B1 (en) * | 1998-12-08 | 2004-01-27 | The Procter & Gamble Company | Process for manufacturing effervescence components |
| DE59900585D1 (en) * | 1999-03-29 | 2002-01-31 | Dalli Werke Waesche & Koerperp | Dishwasher cleaning tablets containing disintegrant granules |
| DE19919445A1 (en) * | 1999-04-29 | 2000-11-02 | Henkel Kgaa | Detergent tablets with solid binders |
| DE19942287A1 (en) * | 1999-09-04 | 2001-03-15 | Cognis Deutschland Gmbh | Shaped body with improved water solubility |
| US6560471B1 (en) | 2001-01-02 | 2003-05-06 | Therasense, Inc. | Analyte monitoring device and methods of use |
| WO2002078512A2 (en) | 2001-04-02 | 2002-10-10 | Therasense, Inc. | Blood glucose tracking apparatus and methods |
| US20050187132A1 (en) * | 2002-09-12 | 2005-08-25 | Volker Blank | Detergent composition which has been compacted under pressure |
| US7811231B2 (en) | 2002-12-31 | 2010-10-12 | Abbott Diabetes Care Inc. | Continuous glucose monitoring system and methods of use |
| US8066639B2 (en) | 2003-06-10 | 2011-11-29 | Abbott Diabetes Care Inc. | Glucose measuring device for use in personal area network |
| ATE338809T1 (en) * | 2003-06-28 | 2006-09-15 | Dalli Werke Gmbh & Co Kg | ALPHA OLEFIN AND ALPHA OLEFIN CELLULOSE GRANULES AS EXPLOSIVES |
| WO2005089103A2 (en) | 2004-02-17 | 2005-09-29 | Therasense, Inc. | Method and system for providing data communication in continuous glucose monitoring and management system |
| DE102004051552A1 (en) * | 2004-10-22 | 2006-04-27 | Henkel Kgaa | Machine dishwashing agent, useful in machine dishwashing procedures, comprises wash powder pack and instruction to guide the user for using the pack in pre-washing step of machine dishwashing procedure |
| DE102004051560A1 (en) * | 2004-10-22 | 2006-04-27 | Henkel Kgaa | Combination product, useful for dish washing machine, comprises compartments containing wash pack and main cleaning agent; and instructions for using wash pack and cleaning agent in the pre-washing and main washing cycle |
| DE102004055077A1 (en) * | 2004-10-22 | 2006-07-06 | Henkel Kgaa | Detergent or detergent dosing unit 2 |
| ITMI20050364A1 (en) * | 2005-03-08 | 2006-09-09 | Truffini & Regge Farmaceutici | DETERGENT TABLETS WITH CONTROLLED RELEASE |
| DE102005025690B4 (en) * | 2005-04-27 | 2007-02-01 | Henkel Kgaa | Packaging system for detergents or cleaners |
| US8112240B2 (en) | 2005-04-29 | 2012-02-07 | Abbott Diabetes Care Inc. | Method and apparatus for providing leak detection in data monitoring and management systems |
| BRPI0613471A2 (en) * | 2005-07-11 | 2011-01-11 | Genencor Int | enzyme tablets for consumer and process tissue care |
| US7766829B2 (en) | 2005-11-04 | 2010-08-03 | Abbott Diabetes Care Inc. | Method and system for providing basal profile modification in analyte monitoring and management systems |
| US7620438B2 (en) | 2006-03-31 | 2009-11-17 | Abbott Diabetes Care Inc. | Method and system for powering an electronic device |
| US8226891B2 (en) | 2006-03-31 | 2012-07-24 | Abbott Diabetes Care Inc. | Analyte monitoring devices and methods therefor |
| EP2021110A4 (en) * | 2006-04-26 | 2012-05-09 | Bromine Compounds Ltd | Multifunctional solid formulations for water conditioning |
| US20080071158A1 (en) | 2006-06-07 | 2008-03-20 | Abbott Diabetes Care, Inc. | Analyte monitoring system and method |
| US8732188B2 (en) | 2007-02-18 | 2014-05-20 | Abbott Diabetes Care Inc. | Method and system for providing contextual based medication dosage determination |
| US8930203B2 (en) | 2007-02-18 | 2015-01-06 | Abbott Diabetes Care Inc. | Multi-function analyte test device and methods therefor |
| US8123686B2 (en) | 2007-03-01 | 2012-02-28 | Abbott Diabetes Care Inc. | Method and apparatus for providing rolling data in communication systems |
| US7928850B2 (en) | 2007-05-08 | 2011-04-19 | Abbott Diabetes Care Inc. | Analyte monitoring system and methods |
| US8665091B2 (en) | 2007-05-08 | 2014-03-04 | Abbott Diabetes Care Inc. | Method and device for determining elapsed sensor life |
| US8456301B2 (en) | 2007-05-08 | 2013-06-04 | Abbott Diabetes Care Inc. | Analyte monitoring system and methods |
| US8461985B2 (en) | 2007-05-08 | 2013-06-11 | Abbott Diabetes Care Inc. | Analyte monitoring system and methods |
| US8103456B2 (en) | 2009-01-29 | 2012-01-24 | Abbott Diabetes Care Inc. | Method and device for early signal attenuation detection using blood glucose measurements |
| WO2010127050A1 (en) | 2009-04-28 | 2010-11-04 | Abbott Diabetes Care Inc. | Error detection in critical repeating data in a wireless sensor system |
| WO2010138856A1 (en) | 2009-05-29 | 2010-12-02 | Abbott Diabetes Care Inc. | Medical device antenna systems having external antenna configurations |
| EP2473099A4 (en) | 2009-08-31 | 2015-01-14 | Abbott Diabetes Care Inc | Analyte monitoring system and methods for managing power and noise |
| US9314195B2 (en) | 2009-08-31 | 2016-04-19 | Abbott Diabetes Care Inc. | Analyte signal processing device and methods |
| WO2011041469A1 (en) | 2009-09-29 | 2011-04-07 | Abbott Diabetes Care Inc. | Method and apparatus for providing notification function in analyte monitoring systems |
| WO2013070794A2 (en) | 2011-11-07 | 2013-05-16 | Abbott Diabetes Care Inc. | Analyte monitoring device and methods |
| US9968306B2 (en) | 2012-09-17 | 2018-05-15 | Abbott Diabetes Care Inc. | Methods and apparatuses for providing adverse condition notification with enhanced wireless communication range in analyte monitoring systems |
| WO2018005341A1 (en) | 2016-06-28 | 2018-01-04 | Ecolab USA, Inc. | Composition, method and use for enhanced oil recovery |
| EP3710569A1 (en) | 2017-11-14 | 2020-09-23 | Ecolab USA Inc. | Solid controlled release caustic detergent compositions |
| EP4007803A1 (en) | 2019-09-27 | 2022-06-08 | Ecolab USA Inc. | Concentrated 2 in 1 dishmachine detergent and rinse aid |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3318817A (en) * | 1965-07-16 | 1967-05-09 | Procter & Gamble | Process for preparing detergent tablets |
| US4219436A (en) * | 1977-06-01 | 1980-08-26 | The Procter & Gamble Company | High density, high alkalinity dishwashing detergent tablet |
| DE3104371A1 (en) * | 1981-02-07 | 1982-11-11 | Henkel KGaA, 4000 Düsseldorf | Cleaning composition tablet |
| DE3321082C2 (en) * | 1982-06-10 | 1996-08-22 | Kao Corp | Bleach Cleaner |
| JPS58217599A (en) * | 1982-06-10 | 1983-12-17 | 花王株式会社 | Bleaching detergent composition |
| DE3315950A1 (en) * | 1983-05-02 | 1984-11-15 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING DETERGENT TABLETS |
| DE3541145A1 (en) * | 1985-11-21 | 1987-05-27 | Henkel Kgaa | UNIFORMED DETERGENT TABLETS FOR MACHINE DISHWASHER |
| GB8804138D0 (en) * | 1988-02-23 | 1988-03-23 | Constantine & Weir Ltd | Solid shampoo composition |
| DE4010533A1 (en) * | 1990-04-02 | 1991-10-10 | Henkel Kgaa | Prodn. of high-density detergent granules |
| DE3937469A1 (en) * | 1989-11-10 | 1991-05-16 | Henkel Kgaa | GRANULAR, ALKALINE, PHOSPHATE-FREE CLEANING ADDITIVE |
| DE4121307A1 (en) * | 1991-06-27 | 1993-01-07 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF STABLE, BIFUNCTIONAL, PHOSPHATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER |
| US5205955A (en) * | 1991-07-03 | 1993-04-27 | Kiwi Brands, Inc. | Lavatory cleansing and sanitizing blocks containing a halogen release bleach and a mineral oil stabilizer |
| DE4228786A1 (en) * | 1992-08-29 | 1994-03-03 | Henkel Kgaa | Dishwashing liquid with selected builder system |
| DE4315048A1 (en) * | 1993-04-01 | 1994-10-06 | Henkel Kgaa | Process for the production of stable, bifunctional, phosphate, metasilicate and polymer-free, low-alkaline detergent tablets for automatic dishwashing |
| DE19502774A1 (en) * | 1995-01-27 | 1996-08-01 | Henkel Kgaa | Process for the manufacture of break-resistant cleaning tablets |
| DK0737738T3 (en) * | 1995-04-12 | 2003-10-20 | Cleantabs As | Bleach Tablet |
-
1994
- 1994-03-15 DE DE4408718A patent/DE4408718A1/en not_active Withdrawn
-
1995
- 1995-03-06 DK DK95910557T patent/DK0750662T3/en active
- 1995-03-06 ES ES95910557T patent/ES2121352T3/en not_active Expired - Lifetime
- 1995-03-06 JP JP7523810A patent/JPH09510252A/en active Pending
- 1995-03-06 CA CA002185723A patent/CA2185723A1/en not_active Abandoned
- 1995-03-06 WO PCT/EP1995/000821 patent/WO1995025161A1/en not_active Application Discontinuation
- 1995-03-06 US US08/716,220 patent/US5854189A/en not_active Expired - Fee Related
- 1995-03-06 AT AT95910557T patent/ATE170216T1/en not_active IP Right Cessation
- 1995-03-06 DE DE59503343T patent/DE59503343D1/en not_active Expired - Fee Related
- 1995-03-06 EP EP95910557A patent/EP0750662B1/en not_active Revoked
Also Published As
| Publication number | Publication date |
|---|---|
| EP0750662A1 (en) | 1997-01-02 |
| WO1995025161A1 (en) | 1995-09-21 |
| DK0750662T3 (en) | 1999-05-25 |
| DE59503343D1 (en) | 1998-10-01 |
| EP0750662B1 (en) | 1998-08-26 |
| US5854189A (en) | 1998-12-29 |
| JPH09510252A (en) | 1997-10-14 |
| ATE170216T1 (en) | 1998-09-15 |
| ES2121352T3 (en) | 1998-11-16 |
| DE4408718A1 (en) | 1995-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5854189A (en) | Process for the production of break-resistant, storable multifunctional detergent tablets | |
| US5898025A (en) | Mildly alkaline dishwashing detergents | |
| US5358655A (en) | Process for the production of detergent tablets for dishwashing machines | |
| JP2628812B2 (en) | Detergent composition | |
| EP2245129B1 (en) | Machine dishwash detergent compositions | |
| US6506720B1 (en) | Process for preparing household detergent or cleaner shapes | |
| CA2162459A1 (en) | Corrosion inhibitors for silver (ii) | |
| CA2145663A1 (en) | Mildly alkaline dishwashing detergents | |
| JP2003521553A (en) | Phosphate and crystalline layered silicate based solid dishwashing detergents | |
| US5888954A (en) | Corrosion inhibitors for silver | |
| EP0838519A1 (en) | Water-softening and detergent compositions | |
| JP2611071B2 (en) | Detergent composition | |
| CA1153162A (en) | Particulate bleach compositions | |
| CA2290014A1 (en) | Additive granules for moulded bodies having a detergent and cleaning action | |
| EP3947622B1 (en) | Process for making a granule or powder | |
| JP2016525153A (en) | Hygroscopic detergent formulation comprising water, aminocarboxylate chelating agent and water sensitive ingredient | |
| EP0839906B1 (en) | Detergent composition | |
| JPH11505290A (en) | Acidic granules containing redox active substance | |
| EP1556471B1 (en) | Tablet of compacted particulate cleaning composition | |
| CA2166277A1 (en) | Dishwashing detergents containing a biologically degradable builder component | |
| CA2299831A1 (en) | Dishwasher detergent shaped bodies with specific geometry | |
| CA2302141A1 (en) | A builder-containing tablet | |
| CA2166186A1 (en) | Dishwashing detergents containing a biologically degradable builder component | |
| CA2318000A1 (en) | Detergent component with finely divided solids | |
| CA2306383A1 (en) | Performance-enhanced dishwasher tablets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |