DE69730599T2 - detergent tablet - Google Patents

Description

The The present invention relates to detergent tablets, especially those intended for use in washing.

Even though Cleaning compositions in tablet form have often been proposed have these (with the exception of soap bars to Body wash) none achieved significant success, despite the various benefits of Products in a single unit. One of the reasons therefor may be that detergent tablets are usually slower dissolve as the ingredient powders from which they are made, simple in that the constituent powders are tightly compressed in the tablet and water has relatively few opportunities to penetrate them. Hence the problem that slowly dissolving tablets Cause residues, the while the washing process through the window of the washing machine are visible or clinging to textiles or causing both.

EP-A-0 716 144, published on June 12, 1996, discloses detergent tablets with water-soluble Coatings containing organic polymers including acrylic / maleic copolymers, Polyethylene glycol, PVPVA and sugar can be. It is stated that the tablets according to the invention preferably a diametral breaking stress of at least 5 kPa exhibit. The dissolution rate The tablets will pass through an exam measured using a metal mesh.

EP-A-0 522 766, published on January 13, 1933, discloses a tablet of compacted particulate cleaning composition, in essence, the tablet or a discrete area thereof a matrix of particles substantially free of Particles of less than 200 microns in size are. Particles of cleaning active Composition and Reinigungsbuilder are individually coated with binder / disintegrating agent with the ability to dive in Tablet in water to break up the structure of the tablet. A comparative Example in this application shows that the same material at of the tablet after compression of the binderless composition can be applied. From the document, however, can doctrine be drawn that it is better to use the material as a binder to use in the tablet.

Indeed are at certain front-loading washing machines problems through the window the washing machine visible tablet residues have been detected.

Of the Purpose of the present invention consists in the provision of Tablets having a core obtained by compressing particulate matter wherein the particulate material is surfactant and detergent builder includes and the tablet for Storage, shipping and handling is suitable without breakage.

One Another purpose of the invention is to provide a tablet, which includes a soft core that breaks up easily and quickly and releases the active ingredients into the wash solution and completely decomposes and in alkaline or surfactant-rich solutions such as the washing liquid dissolves.

SUMMARY THE INVENTION

The present invention relates to detergent tablets comprising a core and a coating wherein the core is produced by a densification process in which the compaction pressure does not exceed 5000 kN / m ² so that the diametral fracture stress of the core is less than 15 kPa Core comprises a gelling binder. The coating comprises from 1% to 10% by weight of the detergent tablet. The coated detergent tablet comprises a coating material which is insoluble in water, the coated detergent tablet having a diametral fracture stress of at least 20 kPa.

Of the Detergent core has a diametral fracture stress of less as 10 kPa and preferably less than 5 kPa.

The present invention also relates to a method for dissolving the coated detergent tablet as defined above in water to provide an aqueous solution of a laundry detergent for use in a front loading washing machine, the front loading washing machine having a dispenser drawer and a washing drum. According to this method, the cleaning agent isab The dispenser is introduced into the dispenser drawer and water is passed through the dispenser drawer so that the tablet is dispensed as an aqueous solution of a laundry detergent and the aqueous solution is subsequently passed into the wash drum.

DETAILED DESCRIPTION OF THE INVENTION

Detergent tablets of the present invention simply by mixing the solid ingredients and compressing the mixture in a conventional Tablet press, as used in the pharmaceutical industry is used to be produced. Preferably, the main ingredients, especially gelling surfactants, used in particulate form. Everyone any liquid Constituent, e.g. As the surfactant or the foam inhibitor may be conventional Into the solid particulate ingredients be incorporated.

Especially for detergent tablets can the ingredients, such as builder and surfactant, to conventional Way spray-dried and then compressed at a suitable pressure.

The Detergent tablets can in any size or Form and, if necessary, before coating according to the present Invention of a surface treatment be subjected. Included in the core of the tablet are one Surfactant and a builder, which is usually an essential part provide the cleaning performance of the tablet. The term "builder" here means all materials, which indicates elimination of calcium ions from the solution, either by ion exchange, complexation, deposition or precipitation.

The particulate material used to make the tablet of the present invention can be prepared by any dispersion or granulation method. An example of such a process is spray-drying (in a DC or countercurrent spray-drying tower) which typically gives low bulk densities of 600 g / L or less. Particulate materials of higher density can be prepared by granulation and densification in a batch mixer / granulator having a high shearing force or by a continuous granulation and densification process (eg. As by using Lodige ^® CB and / or Lodige ^® KM mixers). Other suitable processes include fluidized bed processes, densification processes (eg, roller compaction), extrusion, as well as any particulate material made in any chemical process such as flocculation or crystallization sintering. Individual particles can also be any other particles, granules, beads or grains.

The particulate Materials can be mixed together by any means. The Charge is suitable for example in a concrete mixer, Nauta mixer, Ribbon mixer or any other. Alternatively, the mixing process continuously take place by dosing each ingredient Weight on a conveyor belt and mixing the ingredients in one or more drum mixers. The non-gelling binder can be applied to the mixture of individual particulate Materials or sprayed on all particulate materials. Other liquid Ingredients can also separately or premixed to the mixture of particulate materials sprayed become. For example, you can Perfumes and muds be sprayed by optical brighteners. A finely divided superplasticizer (Dusting agent such as zeolites, carbonates, silicates) may be added to the particulate materials after spraying of the binder, preferably added towards the end of the process to make the mixture less heavy-flowing.

The tablets can be made by any compression method, such as tableting, briquetting or extruding, preferably tableting. Suitable equipment includes a standard single stroke or a rotary press (such as Courtoy ^®, Korch ^®, Manesty ^®, or Bonals ^®). The tablets prepared according to this invention have a diameter of between 40 mm and 60 mm and a weight of between 25 g and 100 g. The ratio between height and diameter (or width) of the tablets is preferably greater than 1: 3, more preferably greater than 1: 2. The compaction pressure used for the preparation of these tablets need not exceed 5000 kN / m, preferably not 3000 kN / m - not exceeding and most preferably not exceeding 1000 kN / m.

Suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates, and water-soluble acrylate copolymers. In the Handbook of Pharmaceutical Excipients, Second Edition, the following binder classifications are listed: acacia, alginic acid, carbomer, carboxymethylcellulose sodium, dextrin, ethylcellulose, gelatin, guar gum, type I hydrogenated vegetable oil, hydroxyethylcellulose, hydroxypropylmethylcellulose, liquid glucose, magne sium-aluminum silicate, maltodextrin, methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein. The most preferred binders also have an active laundry cleaning function, such as cationic polymers, ie, ethoxylated quaternary hexamethylenediamine compounds, bishexamethylenetriamines, or others such as pentaamines, ethoxylated polyethyleneamines, maleinacrylic polymers.

The non-gelling binder materials are preferably sprayed on and have thus a corresponding melting point temperature of below 70 ° C and preferably below 50 ° C, so that no other active ingredients in the matrix are damaged or damaged impaired become. Most preferred are non-aqueous liquid Binders (i.e., not in aqueous Solution), which sprayed in molten form become. It can However, also be solid binder by dry addition in the Matrix are incorporated, but the binding properties within the tablet.

The non-gelling binders are preferably present in an amount within the range of 0.1 to 15% of the composition, more preferably less than 5% and especially a non-washing active material below 2% of the tablet weight.

Preferably are gelling binders, such as nonionic surfactants, in their liquid or molten form avoided. Nonionic surfactants and others gelling binders are not excluded from the compositions, but it is preferred that they be considered as constituents of particulate material and not as liquids be incorporated into the detergent tablets.

According to the present Invention, the tablets are coated so that the tablet no Moisture absorbs or moisture only with a very low Speed absorbed. Furthermore the coating is strong, allowing slight mechanical shock to those the tablets during handling, packaging and transport, cause very little breakage or abrasion. Finally is the coating is so brittle that the tablet breaks up when subjected to a heavier mechanical Exposed to shock becomes. Furthermore it is advantageous if the coating material under alkaline conditions disbanded is fast or by surfactants is emulsified. This carries This helps to eliminate the problem of visible residue in the window of a front-loading washing machine during the Wash cycle is avoided, and also prevents the deposition from unresolved Particles or pieces of coating material on the laundry load.

Water is measured as described in Test Protocol ASTM E1146-87 entitled "Standard Test Method for Measurements of Aqueous Solubility ".

suitable Coating materials are dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and Mixtures thereof.

The Coating material has a melting point of preferably 40 ° C to 200 ° C.

The Coating can be applied in different ways. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of Material.

In a) the coating material is at a temperature above its Melting point is applied and solidifies on the tablet. In b) the coating becomes a solution applied and the solvent dried, a coherent one Leave a coating. The essentially insoluble material For example, by spraying or dipping on the tablet. When the melted Material is sprayed on the tablet, it solidifies usually fast and forms a coherent coating. If tablets immersed in the molten material and taken out subsequently be leads turn the fast cooling to a rapid solidification of the coating material. Clearly essentially insoluble Materials with a melting point below 40 ° C are at ambient temperatures not firm enough, and it was found to be with materials a melting point above about 200 ° C not practical are usable. Preferably, the materials melt in the area from 60 ° C up to 160 ° C, more preferably from 70 ° C up to 120 ° C.

With "melting point" is the temperature meant at which the material slow heating, for example in a capillary tube, turns into a clear liquid.

According to the invention, a Coating any desired Thickness can be applied. The coating forms from 1% to 10%, preferably from 1.5% to 5% of the weight of the tablet.

The Tablet coatings of the present invention are very hard and give the tablet extra Strength.

In a preferred embodiment The present invention is the breaking of the coating in Wash by adding a decomposing agent to the coating improved. This decomposing agent swells as soon as it comes in contact with water, and breaks up the coating into small pieces. This improves the resolution of the Coating in the wash solution. The decomposing agent is in a concentration of up to 30 wt%, preferably between 5 wt% and 20 wt%, most preferably distributed between 5 and 10 wt .-% in the coating melt. Possible Disintegrating agents are in the Handbook of Pharmaceutical Excipients (1986). Examples of suitable decomposing agents include strength: natural, modified or pregelatinized starch, Natriumstärkegluconat; Gum: agar-agar gum, guar gum, locust bean gum, karaya gum, Pectin gum, gum tragacanth; Croscarmylose sodium, crospovidone, cellulose, Carboxymethylcellulose, alginic acid and their salts, including sodium alginate, Silicon dioxide, clay, polyvinylpyrrolidone, soy polysaccharides, ion exchange resins and mixtures thereof.

Depending on the composition of the starting material and the shape of the tablet the applied compaction force is adjusted so that they not the strength (diametral breaking stress) and the decomposition time in the washing machine affected. This process can be used to produce homogeneous or layered Tablets of any size or Form to be used.

wobei F die Höchstkraft (Newton) bezeichnet, die ein Zugversagen (Bruch) verursacht und mit einem Tabletten-Härtemessgerät VK 200, lieferbar durch Van Kell Industries, Inc., gemessen wird. D bezeichnet den Durchmesser der Tablette und t die Dicke der Tablette.The diametral fracture stress is a term for the thickness of a tablet and is determined by the following equation:

where F denotes the maximum force (Newton) causing tensile failure (breakage) and measured with a tablet hardness tester VK 200, available from Van Kell Industries, Inc. D denotes the diameter of the tablet and t the thickness of the tablet.

(Method Pharmaceutical Dosage Forms: Tablets, Volume 2, pages 213 to 217). A tablet with a diametral fracture stress of less than 20 kPa is considered brittle viewed and leads probably with it, that the consumer some broken Receives tablets. A diametral fracture stress of at least 25 kPa is preferred.

• a) In einem "VAN KEL" Friabilator mit Trommeln vom Typ „Vankel".
• – 2 Tabletten, deren Gewicht und diametrale Bruchspannung bekannt sind, in die Friabilatortrommel geben.
• – Die Trommel 20 Umdrehungen drehen.
• – Das gesamte Produkt und die restlichen Tablettenstücke aus der Friabilatortrommel auffangen und auf einem Sieb mit 5 mm und durch 1,7 mm Maschenweite sieben.
• – Den Messwert in % Rest auf 5 mm und durch 1,7 mm angeben.
• – Je höher der %-Wert Material durch 1,7 mm, desto besser ist die Zersetzung.
• b) In einer Waschmaschine nach folgendem Verfahren

The rate of decomposition of a detergent tablet can be determined in two ways:

• a) In a "VAN KEL" Friabilator with drums of the type "Vankel".
• - Place 2 tablets, whose weight and diametral breaking stress are known, in the friabilator drum.
• - Turn the drum 20 turns.
• - Collect all product and remaining pieces of tablet from the friabilator drum and sieve on a sieve of 5 mm and 1.7 mm sieve.
• - Specify the measured value in% residual to 5 mm and 1.7 mm.
• - The higher the% value of material by 1.7 mm, the better the decomposition.
• b) In a washing machine according to the following procedure

Three tablets, nominal weight 60 g each, are weighed, and then introduced to the bottom of the wash drum of a front loading laundry washing machine Miele ^® W831. Then fill the machine with a 2.5 kg clean ballast consisting of 8 terry towels, 5 T-shirts and 5 kitchen towels. Set the washing machine washing temperature to 30 ° C, set the water hardness to 21 grains per gram, and set the washing cycle to the "White / Colorful, Short program" washing program.

At the end of the wash cycle, the debris is thrown out of the laundry load and the debris adhered to the front window input port is collected and weighed as a whole. The quantity of the arrears becomes by ten-fold repetition of the procedure and calculation one average residue quantity determined from the ten individual measurements. In this accentuated test, an amount of residue of 18 g (ie corresponding to 10% of the tablet starting weight) is considered acceptable. A residue of less than 10 g is preferred, less than 5 g is more preferred.

at one stronger stressed exam If the washing machine is stopped 10 minutes after the start of the washing cycle, and the arrears become collected and weighed.

In another preferred embodiment In addition, in the present invention, the tablets include bubbling agent.

Bubbling, as defined herein, means the evolution of gas bubbles from a liquid as a result of a chemical reaction between a soluble acid source and an alkali metal carbonate to produce carbon dioxide gas, ie C ₆ H ₈ O ₇ + 3NaHCO ₃ → Na ₃ C ₆ H ₅ O ₇ + 3CO ₂ ↑ + 3H ₂ O

Further Examples of acid and carbonate sources and other bubbling systems can be found in: (Pharmaceutical Dosage Forms: Tablets, Volume 1, pages 287 to 291).

One bubbling agent may additionally be added to the detergent ingredients to the tablet mixture. The addition of this bubbling agent to the detergent tablet leads to a better disintegration time of the tablet. The amount is preferably between 5 and 20% by weight, and most preferably between 10 and 20% by weight of the tablet. Preferably, the bubbling agent should be added as an agglomerate of different particles or compacted, and not as separate particles.

by virtue of of the gas produced by bubbling in the tablet, the Tablet a higher diametral fracture stress and yet have the same decomposition time have like a tablet without bubbling. If the diametral breaking stress the tablet with bubbly is maintained as well as the tablet without, runs the decomposition of the tablet with effervescence faster.

detergent surfactants

Non-limiting examples of surfactants useful herein at typical levels of from 1% to 55% by weight include the conventional C ₁₁ -C ₁₈ alkyl benzene sulfonates ("LAS") and primary, branched chain and random C ₁₀ -C ₂₀ alkyl sulfates ("AS"), the C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates of the structure CH ₃ (CH ₂ ) _x (CHOSO ₃ -M ⁺ ) CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ -M ⁺ ) CH ₂ CH ₃ , where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C ₁₀ -C ₁₈ - Alkylalkoxysulphates ("AE _x S", in particular EO 1-7 ethoxysulphates), C ₁₀ -C ₁₈ -alkyl alkoxycarboxylates (in particular the EO 1-5-ethoxycarboxylates), the C _10-18 -glycerol ethers, the C ₁₀ -C ₁₈ - Alkylpolyglycosides and their corresponding sulfated polyglycosides and C ₁₂ -C ₁₈ -alpha-sulphonated fatty acid esters. Optionally, the conventional nonionic and amphoteric Surfactants such as the C ₁₂ -C ₁₈ alkyl ethoxylates ("AE"), including narrow peaked alkyl ethoxylates and C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C ₁₂ -C ₁₈ betaines and sulfobetaines ( "Sultaines"), and C ₁₀ -C ₁₈ amine oxides are also included in the overall compositions. The C ₁₀ -C ₁₈ n-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ₁₂ -C ₁₈ n-methylglucamides. See WO 9,206,14. Other sugar-derived surfactants include the n-alkoxy polyhydroxy fatty acid amides, such as C ₁₀ -C ₁₈ n- (3-methoxypropyl) glucamide. The n-propyl to n-hexyl C ₁₂ -C ₁₈ glucamides can be used for low foaming. Conventional C ₁₀ -C ₂₀ soaps can also be used. If high lathering is desired, the branched chain C ₁₀ -C ₁₆ soaps can be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventional, useful surfactants are listed in standard texts.

Builder

Detergent builder can optionally included in the present compositions, to control the mineral hardness to support. Inorganic and organic builders can be used. Builder are typically used in fabric laundering compositions for removal of particulate To support dirt.

The builder concentration may be very high depending on the purpose of use of the composition vary.

inorganic or P-containing detergent builders include the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates), Phosphonates, phytic acid, Silicates, carbonates (including bicarbonates and sesquicarbonates), Sulfates and aluminosilicates, but are not limited to these. In some regions, however, builders that are not phosphates are required. Importantly, the compositions even in the presence the so-called "weak" builder (in comparison to phosphate), such as citrate, or in the so-called "inadequate set "situation, which can occur with zeolite or phyllosilicate builders, surprisingly are very effective.

Examples of silicate builders are the alkali metal silicates, especially those having a SiO ₂ : Na ₂ O ratio in the range of 1.6: 1 to 32: 1, and phyllosilicates, such as the layered sodium silicates disclosed in U.S. Patent 4,664,839, issued 12 May 1987 to HP Rieck. NaSKS-6 is the trademark of a crystalline layered silicate marketed by Hoechst (commonly abbreviated as "SKS-6") Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum, NaSKS-6 has the morphological delta-Na ₂ SiO ₅ form of a layered silicate. It can be prepared by methods described in DE-a-37,42,043, such as described in German DE-a-34,17,649 and. SKS-6 is a particularly preferred layered silicate for use herein, other such Phyllosilicates, such as those having the general formula NaMSi _x O _{2x + 1} · yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably However, they may also be used here Several other phyllosilicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma forms As noted above, the delta Na is ₂ SiO ₅ (NaSKS-6 form) for use most prefers. Other silicates may also be useful, such as: For example, magnesium silicate, which may serve as a solidifying agent in granular formulations, as an oxygen bleach stabilizing agent, and as an ingredient in foam control systems.

Examples for carbonate builders are the alkaline earth and alkali metal carbonates, as in the German Patent Application No. 23,21,001, published November 15 1973, revealed.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently available heavy duty granular detergent compositions and may also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: M _z (zAlO _{2) y]} .xH ₂ O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to about 0.5, and x is an integer of about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may have a crystalline or amorphous structure and may be naturally occurring aluminosilicates or synthetically derived. A method of making aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the structure: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .xH ₂ O where x is from about 20 to about 30, especially about 27. This material is known as zeolite A. Dewatered zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3. Carboxylates Polycarboxylate builder may generally be added to the composition in acid form, but may also be added in the form of a neutralized salt Alkali metals such as sodium, potassium and lithium, or alkanolammonium salts before Trains t.

polycarboxylate shut down a variety of categories more useful Materials. An important category of polycarboxylate builders includes the ether polycarboxylates, including oxydisuccinate, as in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972. Please refer also "TMS / TDS" builder in US Patent 4,663,071, issued to Bush et al. on May 5, 1987. Suitable Etherpolycar boxylate shut down also cyclic compounds, in particular alicyclic compounds such as those described in U.S. Patents 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903.

Other useful Close detergent builder the ether hydroxypolycarboxylates, the copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid and polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble Salts thereof, a.

Citrate builders, for example, citric acid and soluble Salts thereof (especially the sodium salt) are due to their Availability from renewable resources and their biodegradability especially important polycarboxylate builders for heavy duty liquid detergent formulations. Citrate can also in grainy Compositions, especially in combination with zeolite and / or Phyllosilicate builders, to be used. Oxydisuccinates are in such Compositions and combinations are also particularly useful.

Also useful in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanediates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic builders include the C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include laurylsuccinates, myristylsuccinates, palmitylsuccinates, 2-dodecenyl succinates (preferred), 2-pentadecenylsuccinates. Lauryl succinates are the preferred builders of this group and are described in European Patent Application 0,200,263, published November 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued Mar. 13, 1979, and U.S. Patent 3,308,067, Diehl, issued Mar. 7, 1967, described. See also Diehl, U.S. Patent 3,723,322.

Fatty acids, for example C ₁₂ -C ₁₈ monocarboxylic acids, may also be included in the compositions, either alone or in combination with the above-mentioned builders, especially citrate and / or succinate builders, to provide additional builder activity. Such use of fatty acids generally results in a reduction in foaming, which should be considered by the manufacturer.

In Situations in which phosphorus-based builders can be used, and especially in the formulation of piece molds used for hand washing procedures can be used the various alkali metal phosphates, such as the well-known Sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate, to be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patent 3,19,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137) may also be used.

bleach

The Cleaning compositions herein may optionally include bleaches or bleaching compositions containing a bleaching agent and comprise one or more bleach activators. If available lie Bleach typically at levels between 1% and 30%, more typically between 5% and 20% of the detergent composition in particular for textile washing. If the amount of bleach activators is typically between 0.1% and 50%, more typically between 0.5% and 40% of the bleach and bleach activator Bleaching composition.

The bleaching agents used herein may be any of the bleaching agents that are required for detergent compositions compositions for textile cleaning, hard surface cleaning or other cleaning purposes now known or known. These include oxygen bleaching and other bleaching agents. Perborate bleaches, for example, sodium perborate (for example, mono- or tetrahydrate) can be used here.

A other category of bleaching agents used without restriction includes percarboxylic acid bleach and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioc one. Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, Hartman, issued November 20, 1984, US Patent Application 740,446, Burns et al., filed June 3, 1985, European Patent Application 0,133,354, Banks et al., Published on February 20, 1985, and in U.S. Patent No. 4,412,934, Chung et al., issued on November 1, 1983, disclosed. Most preferred bleaching agent shut down also 6 nonylamino-6-oxoperoxycaproic acid, which are described in US Pat. 4,634,551 issued January 6, 1987 to Burns et al is.

peroxygen can also be used. Suitable peroxygen bleach compounds shut down Sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, Urea peroxyhydrate and sodium peroxide. persulfate (for example OXONE, manufactured by DuPont) can also to be used.

One preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 Microns to about 1,000 microns, with no more than about 10 wt .-% of the particles are smaller than about 200 microns and not more than about 10% by weight of the particles are greater than about 1250 microns. The percarbonate may optionally be silicate, borate or water soluble Surfactants coated be. Percarbonate is available from various sources, like FMC, Solvay and Tokai Denka.

mixtures of bleaching agents also be used.

peroxygen the perborates, the percarbonates are preferably combined with bleach activators, resulting in in situ production in aqueous solution (ie during the washing process) of the peroxyacid and the corresponding bleach activator. Various non-limiting examples for Activators are disclosed in U.S. Patent No. 4,915,854, issued April 10 1990 to Mao et al., And U.S. Patent No. 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) - and the tetraacetylethylenediamine (TAED) activator are typical, and mixtures thereof can also be used. For further typical bleaches and activators that are useful here See also U.S. Patent No. 4,634,551.

Especially preferred amido-derived bleach activators are those having the structures: R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L wherein R ^{1 is} an alkyl group containing from 6 to 12 carbon atoms, R ^{2 is} an alkylene containing from 1 to 6 carbon atoms, R ^{5 is} H or alkyl containing 1 to 10 carbon atoms, aryl or alkaryl, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator by the perhydrolysis anion due to nucleophilic attack on the bleach activator. A preferred leaving group is phenylsulfonate.

preferred examples for Bleach activators of the above formulas include (6-octanamido-caproyl) -oxybenzenesulfonate, (6-nonanamidocaproyl) -oxybenzenesulfonate, (6-decanamido-caproyl) -oxybenzenesulfonate and mixtures thereof, as in U.S. Patent No. 4,634,551, which is incorporated by reference herein.

A another class of bleach activators includes the activators of Benzoxazine type described by Hodge et al. in U.S. Patent No. 4,966,723, issued on October 30, 1990, are disclosed. A much more preferred Activator of benzoxazine type is:

wobei R⁶ H eine von 1 bis 10 Kohlenatome enthaltende Alkyl-, Aryl-, Alkoxyaryl- oder Alkarylgruppe ist. Besonders bevorzugte Lactam-Aktivatoren schließen Benzoylcaprolactam, Octanoylcaprolactam, 3,5,5-Trimethylhexanoylcaprolactam, Nonanoylcaprolactam, Decanoylcaprolactam, Undecenoylcaprolactam, Benzoylvalerolactam, Octanoylvalerolactam, Decanoylvalerolactam, Undecenoylvalerolactam, Nonanoylvalerolactam, 3,5,5-Trimethylhexanoylvalerolactam und Mischungen davon ein. Siehe auch US-Patent Nr. 4,545,784, erteilt an Sanderson, 8. Oktober 1985, das Acylcaprolactame, einschließlich Benzoylcaprolactam, adsorbiert in Natriumperborat offenbart.Another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams having the formulas:

wherein R ⁶ H is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 10 carbon atoms. Particularly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, and mixtures thereof. See also U.S. Patent No. 4,545,784, issued to Sanderson, Oct. 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed in sodium perborate.

Bleach, that are different from oxygen bleaches are in the art also known and can used here. A type of non-oxygen bleach of particular interest photoactivated bleaches, such as the sulfonated zinc and / or Aluminum phthalocyanines, a. See U.S. Patent No. 4,033,718 issued on July 5, 1977 to Holcombe et al. Optionally, cleaning compositions contain typically from 0.025% to 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanine.

Optionally, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent No. 5,246,621, U.S. Patent No. 5,244,594, U.S. Patent No. 5,194,416, U.S. Patent No. 5,114,606, and U.S. Patent Nos. 5,194,616; European patent applications Publication no. 549,271A1, 549,272A1, 544,440A2, and 544,490A1. Preferred examples of these catalysts include Mn ^IV ₂ (μ-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (μO) ₁ (μ-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO ₄ ) ₂ , Mn ^IV ₄ (μ-O) ₆ (1,4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (μ-O) ₁ (μ-OAc) ₂ - (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4, 7-trimethyl-1,4,7-triazacyclononane) - (OCH ₃ ) ₃ (PF ₆ ), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Patent No. 4,430,243 and U.S. Patent No. 5,114,611. The use of manganese with various complexing ligands to enhance bleaching is also described in the following U.S. patents: 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161 and 5,227,084.

Out practical reasons and by no means limiting the compositions and processes herein to be of the order of at least 1 ppm of the active bleach catalyst species in the aqueous washing liquid and they are preferably from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm of the catalyst species in the wash liquor beistellen.

enzymes

enzymes can in the present formulations for a wide variety of textile washing purposes, including Removal of proteinaceous, carbohydrate-containing or triglyceride-containing Stains for example, and for the prevention of transmission volatile Dyes and used for tissue care. The to be integrated Enzymes include proteases, amylases, lipases, cellulases and peroxidases and mixtures thereof. It can also other types of enzymes are included. You can do any have suitable origin, such as plants, animals, bacteria, fungi and yeasts. However, are for the choice of different factors such as pH-activity and / or stability optima, Thermal stability, resistance relevant to active cleaning agents and builders. In this regard Be bacterial or fungal enzymes, such as bacterial amylases and proteases and fungal cellulases are preferred.

enzymes are usually trapped in sufficient quantity to at about 5 mg by weight, more typically 0.01 mg to 3 mg of the active To provide enzyme per gram of the composition. In other words, include the compositions typically 0.001 wt% to 5 wt%, preferably 0.01% to 1% by weight of a commercially available Enzyme preparation. Protease enzymes are available in such commercially available Preparations usually in sufficient proportions to 0.005 to 0.1 Anson units (AU) of activity per gram of composition.

suitable examples for Proteases are the subtilisins that are derived from certain strains of the B. subtilis and B. licheniformis. Another suitable Protease with maximum activity in the pH range 8 to 12 is obtained from a Bacillus strain, developed and from Novo Industries A / S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is in the British Patent No. 1,243,784 to Novo. For the distance proteinaceous stains, suitable proteolytic enzymes which are used in the Trade available include, those under the trade names ALCALASE and SAVINASE from Novo Industries A / S (Denmark) and MAXATASE from International Bio-Synthetics, Inc. (Netherlands). Other proteases include protease A (see European Patent Application 130,756, published on January 9, 1985) and Protease B (see European Patent Application 251 446, filed on 28 April 1987 and European patent application 130,756, Bott et al., Published on January 9, 1985).

amylases include, for example, α-amylases, described in British Patent No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.

The cellulase usable according to the invention comprises cellulase from bacteria or fungi. Preferably, they have a pH optimum of 5 to 9.5. Suitable cellulases are disclosed in US Pat. No. 4,435,307, Barbesgoard et al., Issued Mar. 6, 1984, which discloses fungal cellulase prepared from Humicola insolens and Humicola strain DSM1800 or a cellulase 212 producing fungus of the Aeromonas group, and cellulase from the midgut gland of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275 and DE-OS-22.47.832. CAREZYME ^® (Novo) is especially useful.

Suitable lipase enzymes for use as laundry detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154 as disclosed in British Patent 1,372,034. See also Lipases in Japanese Patent Application 53,20487, published February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd. of Nagoya, Japan, under the trade name Lipase P " Amano", hereinafter referred to as "Amano-P". designated. Other commercially available lipases include Amano-CES, Chromobacter viscosum lipases, for example Chromobacter viscosum var. Lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan, and further Chromobacter viscosum lipases from US Biochemical Corp. , USA, and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli. The enzyme LIPOLASE derived from Humicola lanuginosa and commercially available from Novo (see also US Pat EP 0 341947 ) is a preferred lipase for use herein.

peroxidase be used in combination with oxygen sources such as percarbonate, perborate, Persulfate and hydrogen peroxide used They become "bleaching the solution ", that is to the transfer of Dyes or pigments that are used during the washing process Substrates were added to other substrates in the wash solution prevent. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase, like chlorine and bromine peroxidase. Peroxidase-containing cleaning compositions are, for example, in PCT International Application WO 89/099813, released on October 19, 1989, by O. Kirk, transferred to Novo Industries A / S, revealed.

A wide range of enzyme materials and means for their incorporation into synthetic Cleaning compositions are also disclosed in U.S. Patent No. 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are in U.S. Patent No. 4,101,457, Place et al. In U.S. Patent No. 4,507,219, Hughes, issued on May 26, 1978; March 1985, both, revealed. For liquid Detergent formulations useful Enzyme materials and their incorporation into such formulations are disclosed in U.S. Patent No. 4,261,868, Hora et al., issued April 14 1981, disclosed. Enzymes for The use in detergents can be done by various methods be stabilized. Techniques for stabilizing enzymes are disclosed and exemplified in U.S. Patent 3,600,319 issued to August 17, 1971 to Gedge, et al., And European Patent Publication No. 0 199 405, published on October 29, 1986, Venegas. Systems for enzyme stabilization are also for example in US patent No. 3,519,570.

Other Ingredients that usually be used in cleaning compositions and in the detergent tablets according to the invention can be included include complexing agents, soil solubilizers, agents that have a wicking deposit prevent dirt, dispersants, whiteners, foam inhibitors, Fabric softening agents, color transfer inhibitors and perfumes.

The Procedure, detergent tablets together with the laundry in to enter the washing drum is known. However, this procedure results easily to unsightly residues that visible on the window, especially in certain types of Washing machines for the operation was designed with a lower water consumption. In extreme cases can visible residues at the end of the wash cycle also on the garments deposit.

The The present invention also relates to a washing method in which this problem is largely avoided. The new method includes the preparation of an aqueous solution a laundry detergent for use in a front-loading washing machine, with the front-loading washing machine a Dispensiereinzug and a washing drum, wherein the aqueous solution of the laundry detergent by dissolving a detergent tablet is formed in water, and is characterized in that the detergent tablet in the Dispenser drawer is inserted and water through the dispenser drawer is passed, leaving the tablet as an aqueous solution of a laundry detergent is dispensed and the watery solution is therefore passed into the washing drum.

Although any detergent tablet may be used in the method of the present invention, it has been found that the tablets described herein are most readily dispensed from the dispensing drawer without leaving residue in the dispensing drawer. Further, it is preferable that the density of the tablet is between 0.9 and 1.1 g / cm ^3, and more preferably between 0.95 and 1.05 g / cm ³ .

EXAMPLES

anionic Agglomerates include 18% anionic surfactant, 22% zeolite and 40% Carbonate.

nonionic Agglomerates include 26% nonionic surfactant, 48% zeolite and 26% carbonate.

cationic Agglomerates comprise 24% cationic surfactant (alkylhydroxyethyldimethylammonium chloride), 64% zeolite, and 12% sulphate.

Bleichmittelaktivatoragglomerate include 81% TAED, 17% acrylic / maleic copolymers (acid form) and 2% water.

Zinc phthalocyanine sulphonate encapsulates 10% are active.

defoamers include 11.5% silicone oil (eg Dow Corning) and 88.5% starch.

phyllosilicates comprise 78% SKS-6 (eg Hoechst) and 22% citric acid.

Farbübertragungsinhibitoragglomerate include 21% PVNO / PVPVI, 61% zeolite and 18% carbonate.

Perfume capsules include 50% perfume and 50% starch.

AE7 / PEG4000 Aufsprühmittel includes 83% C12-C15 AE7 (alcohol with an average of 7 ethoxy groups per molecule), 17% Polyethylene glycol with an average molecular weight from 4000.

PEG200 is polyethylene glycol with an average molecular weight from 200.

diamine Quat is an ethoxylated hexamethylenediamine quaternary compound.

example 1

A detergent base powder of composition 1 is prepared in the following steps:
Nonionic AE7 / PEG4000 mixture is sprayed onto the sodium perborate in a mixing drum. After spraying, zeolite is used to dust the perborate for impregnation with the nonionic mixture to eliminate its ability to bind the other powders;
ethoxylated hexamethylene-diamine Quat (the non-gelling binder) is sprayed onto the layered silicate, bleach activator agglomerates and carbonate;
The contents of these two mixing drums are then mixed with the remaining particulate materials of composition to form a homogeneous particle mixture.

80 Parts of composition 1 are then in a mixing drum with 15 parts of sodium acetate and 5 parts of a 54.5% sodium bicarbonate and 45.5% citric acid existing, bubbling agent mixed.

The tablets are then prepared by feeding 55 g of the mixture into a round die (54 mm diameter) and compressing to obtain tablets having a height of 21 minutes and a density of 1.1 g / cm ³ . The diametral fracture stress is 6 kPa.

The Tablets are then immersed in a coating bath, the 90 parts of dodecanedioic acid mixed with 10 parts of Nymcel z6b16, heated to 140 ° C. The Tablets are left in the bath just long enough for a 5 g coating is applied, after which the tablets are taken out and while 24 hours at 25 ° C cooling down. The diametral breaking stress is increased by the coating increased as 20 kPa.

Example 2

A detergent base powder of composition 2 is prepared in the following steps:
Nonionic AE7 / PEG4000 mixture is sprayed onto the sodium perborate in a mixing drum. After spraying, zeolite is used to dust the perborate for impregnation with the nonionic mixture to eliminate its ability to bind the other powders;
PEG200 (the non-gelling binder) is sprayed onto the layered silicate, bleach activator agglomerates and carbonate;
and then the rest of the procedure of Example 1 is repeated except that 45 g of the composition is compressed to a 45 mm diameter tablet, 23 mm high, and 1.1 g / cm ³ density.

The uncoated tablet has a diametral breaking stress of 10.2 kPa.

It detergent tablets are manufactured with the following characteristics:

In Examples 1 and 2 the tablets are used to wash a laundry load, by three tablets are input together with the laundry in the drum of a washing machine Miele ^® W831.

Example 3

• i) The detergent composition 3 becomes prepared as follows: all particulate materials of the basic composition 3, except for diamine quat and perfume, were mixed in a drum mixed into a homogeneous particle mixture. During this mixing process found the spraying of diamine quat and perfume instead.
• ii) The tablets were then prepared as follows: 45 g of the mixture were compacted into a round die of 4.5 cm diameter until tablets of 2.3 cm height and a density of 1.0 g / cm ^{3 were} obtained. The breaking strength (diametral breaking stress) of the tablet was 10.2 kPa.

In Examples 4, 5 and 6, the same tablets were prepared as in Examples 1, 2 and 3 except that in Examples 4, 5 and 6 the density of the tablet was 1 g / cm ³ . The tablets are fed into the dispensing drawer of a washing machine Miele ^® W831, the laundry is introduced into the drum and the washing machine cycle takes place.

Claims (8)

A detergent tablet comprising a core and a coating, wherein the core is made by a densification process wherein the compaction pressure does not exceed 5000 KN / m ² so that the diametral stress at break of the core is less than 15 kPa, the core comprising a non-gelling binder and wherein the coating comprises from 1% to 10% by weight of the detergent tablet, characterized in that the coated detergent tablet comprises a coating material that is insoluble in water, and wherein the coated detergent tablet has a diametral fracture stress of at least 20 kPa having. A detergent tablet according to claim 1, wherein the Detergent core a diametral fracture stress of less than 10 kPa and preferably less than 5 kPa. A detergent tablet according to claim 1, wherein the coated detergent tablet comprises a coating, the dicarboxylic acid includes. Detergent tablet according to claim 3, wherein dicarboxylic acid the group consisting of oxalic acid, malonic, Succinic acid, glutaric, adipic acid, pimelic, suberic, azelaic acid, sebacic, undecanoic, dodecanedioic, tridecanedioic and mixtures thereof becomes. A detergent tablet according to any one of claims 1 to 4, wherein the tablet has a density of 0.9 g / cm ³ to 1.1 g / cm ³ . Method for dissolving in water of a coated Detergent tablet according to claim 1 and / or 2 to an aqueous solution of a laundry detergent for use in a front loading washing machine, wherein the Front loading washing machine comprises a Dispensiereinzug and a washing drum, characterized in that the detergent tablet in the Dispenser drawer is inserted and water through the dispenser drawer is passed, leaving the tablet as an aqueous solution of a laundry detergent is dispensed, the aqueous solution subsequently passed into the washing drum. The method of claim 6, wherein the coated Detergent tablet comprises a coating and wherein the Coating a dicarboxylic acid includes. The method of claim 6 or 7, wherein the tablet has a density of 0.9 g / cm ³ to 1.1 g / cm ³ .