DE69637030T2 - Coated cleaning agent in tablet form and manufacturing method therefor - Google Patents

Description

The present invention relates to coated detergent tablets, especially those designed for use in washing machines, and method of making the coated detergent tablets.

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 for that can be that the detergent tablets a relatively complex manufacturing process require. In particular, it is often desirable to use the tablet coating and this adds to the manufacturing difficulties.

Even though Tablets without coating are completely effective in use, is absent they usually the necessary Surface hardness, um To withstand attrition, which is part of normal manufacturing, Packaging and handling is. The result is that uncoated Tablets while These methods undergo attrition, resulting in chipped tablets and loss of active substance.

Ultimately The coating of tablets is often desired for aesthetic reasons The external appearance to improve the tablet or to achieve a special aesthetic effect.

It Numerous methods for coating tablets have been proposed, and many of these were for Detergent tablets proposed. However, all of these have Process certain disadvantages, as explained below.

GB-A-0 989 683, published on April 22, 1965, discloses a method of manufacturing a particulate Detergent of surfactants and inorganic salts; Spraying on water-soluble Silicate; and pressing the detergent particles into a solid tablet, that preserves its form. Ultimately, one readily provides water-soluble organic film-forming polymer (for example polyvinyl alcohol) a coating to the detergent tablet against abrasion and to prevent accidental breakage.

EP-A-0 002 293, published on June 13, 1979, discloses a tablet coating which is hydrated Salt, such as acetate, metaborate, orthophosphate, tartrate and sulfate, includes.

EP-A-0 716 144, published on June 12, 1996, also discloses detergent tablets with water-soluble Coatings containing organic polymers including acrylic / maleic copolymers, Polyethylene glycol, PVPVA and sugar can be.

WO9518215, released on July 6, 1995, presents water-insoluble coatings for solid Pouring pills ready. The tablets are made with hydrophobic coatings, including Paraffin, fatty acid, fatty acid amides and polyethylene glycol.

One Disadvantage of the disclosures of the prior art is that a coating that is thick enough and strong enough to wear to withstand, also tends to break open or dissolve in use to be slow.

The The present invention provides a means by which tablets with a core obtained by densification of a particulate material wherein the particulate material is surfactant and detergency builder includes, with a hard, thin Coating can be provided so they can be stored, transported and handled, however the coating is broken when the tablet is in the washing machine is and the soft core is exposed, which breaks easily and quickly, whereby the active ingredients are released into the wash solution.

The The aim of the present invention is to provide a tablet, especially in alkaline or surfactant-rich solutions such as the wash liquor completely decomposed and distributed.

SUMMARY OF THE INVENTION

The object of the present invention is achieved by providing a tablet comprising a core and a coating, wherein the core is made by densification of a particulate material, the particulate material comprising surfactant and detergency builder, characterized in that the coating material has a water solubility at 25 ° C of less than 20 g / l and of C ₂ -C _13- dicarboxylic acids and the coating comprises a decomposer which swells upon contact with water in a concentration to break the coating of up to 30% by weight of the coating. It is preferred that the tablet further comprises an effervescent, for example, a soluble acid source and an alkali metal carbonate.

• (a) Bilden eines Kerns durch Verdichtung eines teilchenförmigen Materials, wobei das teilchenförmige Material Tensid und Reinigungsmittelbuilder umfasst;
• (b) Auftragen eines Beschichtungsmaterials auf den Kern, wobei das Beschichtungsmaterial die Form einer Schmelze aufweist;
• (c) Verfestigenlassen des geschmolzenen Beschichtungsmaterials; dadurch gekennzeichnet, dass das Beschichtungsmaterial ein Zersetzungsmittel, das bei Kontakt mit Wasser aufquillt, in einer Konzentration, um die Beschichtung zu brechen, von bis zu 30 Gew.-% umfasst, und wobei das Beschichtungsmaterial eine Wasserlöslichkeit bei 25 °C von weniger als 20 g/l aufweist und aus C₂-C₁₃-Dicarbonsäuren ausgewählt ist.

In another aspect of the invention, there is provided a method of making a tablet comprising the steps of:

• (a) forming a core by densification of a particulate material, wherein the particulate material comprises surfactant and detergency builder;
• (b) applying a coating material to the core, wherein the coating material is in the form of a melt;
• (c) allowing the molten coating material to solidify; characterized in that the coating material comprises a disintegrant that swells upon contact with water at a concentration to break the coating of up to 30% by weight, and wherein the coating material has a water solubility at 25 ° C of less than 20 g / l and of C ₂ -C ₁₃ dicarboxylic acids is selected.

Preferably the coating materials have a melting point in the range from 40 ° C up to 200 ° C.

DETAILED DESCRIPTION OF THE INVENTION

In The tablets to be coated according to the present invention can be simple 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. Any liquid ingredients, eg. B. the surfactant or suds suppressor may be in a conventional manner in the solid particulate Components are incorporated. Preferably, the main components used in particulate form.

Especially for laundry 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 the cleaning performance of the tablet is provided. With the term "builder" here are all materials meant, on a removal 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 methods include fluidized bed processes, densification processes (eg, roller compaction), extrusion, and any particulate material made by any chemical process such as flocculation, crystallization, sintering, etc. Individual particles can also be any other particles, granules, spheres or grains.

The particulate materials can be mixed together by any means. The batch is, for example, suitable in a concrete mixer, nauta mixer, belt mixer or any other. Alternatively, the mixing process may be carried out continuously by measuring all ingredients by weight and placing them on a conveyor belt and mixing them in one or more drums or mixers. Spraying of liquid onto the mixture of particulate materials (eg, nonionic surfactants) may be performed. Other liquid ingredients may also be sprayed separately or premixed onto the mixture of particulate materials. For example, perfumes and slurries can be sprayed on optical brighteners. A fine distribution Resin (dusting agents such as zeolites, carbonates, silicates) can be added to the particulate materials after spraying the nonionic surfactant, preferably towards the end of the process to make the mixture less tacky.

The tablets can be made by any compression method, such as tableting, briquetting or extruding, preferably tableting. Suitable devices include a standard single stroke or a rotary press (such as Courtoy ^®, Korch ^®, Manesty ^®, or Bonals ^®). The tablets prepared according to this invention preferably have a diameter between 40 mm and 50 mm and a weight between 25 and 60 g. The compaction pressure used to make these tablets need not be greater than 5 MPa (5000 kN / m ² ), preferably not greater than 3 MPa (3000 kN / m ² ), and most preferably not greater than 1 MPa (1000 kN / m ² ).

According to the invention the tablets afterwards with a coating coated so that the tablet does not absorb moisture or Absorbs moisture only very slowly. In addition, the coating strong, so that moderate mechanical Shocks, those the tablets during handling, packaging and transport, cause very little breakage or abrasion. Ultimately is the coating is preferably brittle, so that the tablet breaks, if they are stronger exposed to mechanical shocks is. Furthermore it is advantageous if the coating material under alkaline Conditions resolved or simply emulsified by surfactants. This will be the Deposition of undissolved particles or lumps of the coating material on the laundry load avoided. This can be important if the coating material in water completely insoluble is (for example less than 1 g / l).

As as defined herein means "im Essentially insoluble "a very small one solubility in water. Below that should be a solubility in water at 25 ° C from below 20 g / l, preferably less than 5 g / l, and more preferably less than 1 g / l be understood. Water is measured as described in Test Protocol ASTM E1148-87 entitled "Standard Test Method for Measurements of Aqueous Solubility ".

The Coating materials are C2-C13 dicarboxylic acids. Preferred dicarboxylic acids are oxalic acid (C2), malonic acid (C3), succinic acid (C4), glutaric acid (C5), adipic acid (C6), pimelic acid (C7), suberic acid (C8), azelaic acid (C9), sebacic acid (C10), undecanedioic acid (C11), dodecanedioic acid (C12) and tridecanedioic acid (C13).

however if the detergent tablets are made, then they will, which form they also have, according to the invention with a coating material coated with a melting point preferably from 40 ° C to 200 ° C.

The Coating is done by coating with a molten material applied. The coating material is at a temperature above its Melting point is applied and solidifies on the tablet. The Coating material can be, for example, by spraying or Dip on the tablet. When the melted Material is sprayed on the tablet, it usually solidifies fast, to get a coherent To form coating. When tablets in the molten material dipped and then taken out, causes the fast cooling down again rapid solidification of the coating material. Clearly are essentially insoluble Materials with a melting point below 40 ° C at ambient temperatures not tight enough, and it has been shown that materials with a melting point over approximately 200 ° C practically are not usable. Preferably, the materials melt in the Range of 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. For For most purposes, the coating forms 1% to 10%, preferably 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 the present invention, the breaking of the coating during the washing process is improved by the addition of a disintegrating agent to the coating. This disintegrating agent swells as soon as it comes in contact with water and breaks the coating into small pieces. This improves the dissolution of the coating in the wash solution. The decomposing agent is in a concentration Ration of up to 30 wt .-%, preferably between 5 wt .-% and 20 wt .-% and most preferably between 5 and 10 wt .-% suspended in the coating melt.

Possible decomposing Drugs are in the Handbook of Pharmaceutical Excipients (1986) described. Examples of suitable decomposing agents include Strength: natural, modified or pregelatinized starch, sodium starch gluconate; 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, silica, clay, polyvinyl pyrrolidone, soy polysaccharides, Ion exchange resins and mixtures thereof.

Depending on the composition of the starting material and the shape of the tablets the applied compaction force is set to the strenght (diametrical breaking stress) and the decomposition time in the washing machine unaffected. This process can be used to produce homogeneous or coated tablets of any size or shape.

worin 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.
(Method Pharmaceutical Dosage Forms: Tablets, Band 2, Seiten 213 bis 217) The diametrical fracture stress is a term for the thickness of a tablet and is determined by the following equation:

where F is the maximum force (Newton) causing tensile failure (fracture) and measured with a VK 200 Tablet Hardness Tester, 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) In einem „VAN KEL" Friabilator mit Trommeln vom Typ „Vankel". – 2 Tabletten, deren Gewicht und diametrische 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 – Zwei Tabletten mit einem bekannten Gewicht und einer bekannten Bruchspannung auf den Boden einer Waschmaschine (d. h. einer Bauknecht WA 950) geben. – Eine gemischte 3-kg-Waschladung auf die Tabletten geben. – Einen Kurzwaschgang bei 30 °C (Programm 4) mit Wasser aus dem städtischen Wassernetz laufen lassen. – Den Waschgang nach 5 min anhalten und die Waschmaschinenladung nach nicht aufgelösten Tablettenteilchen untersuchen, diese auffangen und abwiegen und den verbliebenen Rest in Prozent erfassen.

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 diametric 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 - Place two tablets with a known weight and a known breaking stress on the floor of a washing machine (ie a Bauknecht WA 950). - Apply a mixed 3 kg load to the tablets. - Run a short cycle at 30 ° C (program 4) with water from the municipal water network. - Stop the wash after 5 minutes and inspect the washing machine load for unresolved tablet particles, collect and weigh them, and record the remainder in percent.

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).

A bubbling agent may be added to the tablet mixture in addition to the detergent ingredients. The addition of this bubbling agent to the detergent tablet results in 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 the various particles or compacted rather than as a separate part chen.

by virtue of of the gas produced by bubbling in the tablet, the Tablet a higher diametrical fracture stress and yet the same decomposition time have like a tablet without bubbling. If the diametric Breaking tension of the tablet with bubbling is maintained exactly the same like a tablet without, runs the decomposition of the tablet with effervescence faster.

detergent surfactants

Non-limiting examples of surfactants typically useful herein at levels of from about 1% to about 55% by weight include the conventional C ₁₁ -C ₁₈ alkyl benzene sulfonates ("LAS") and primary, branched chain and random C's C ₁₀ -C ₂₀ alkyl sulfates ("AS"), the secondary C ₁₀ -C ₁₈ (2,3) alkyl sulfates of the formula CH ₃ (CH ₂ ) _x (CHOSO ₃ -M ⁺ ) CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ -M ⁺ ) CH ₂ CH ₃ , wherein x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfates, the C ₁₀ -C ₁₈ alkyl alkoxy sulfates ("AE _x S"; especially EO 1-7 ethoxy sulfates), C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C ₁₀ - ₁₈ glycerol ethers, the C ₁₀ -C ₁₈ alkyl and their corresponding sulfated polyglycosides, and alpha-sulfonated fatty acid esters, C ₁₂ -C ₁₈ gewünsc case. Likewise, the conventional nonionic and amphoteric surfactants such as the C ₁₂ -C ₁₈ alkyl ethoxylates ("AE") including the so-called narrowly distributed alkyl ethoxylates and C ₆ -C ₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C ₁₂ -C ₁₈ betaines and sulfobetaines ("sultaines"), C ₁₀ -C ₁₈ amine oxides and the like are 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 Patent No. 9,206,154. 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 through 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 foaming 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. It can inorganic and organic builders are used. Builder are typically used in fabric laundering compositions for removal of particulate To support dirt.

The Builder concentration may vary depending on the purpose the composition is very variable.

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, are, however not limited to this. In some regions, however, builders that are not phosphates are required. Importantly, the present compositions even in the presence of so-called "weak" builders (compared to phosphates), like citrate, or in the so-called "inadequately adjusted" situation at Zeolite or layered silicate builders can occur, 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 3.2: 1, and phyllosilicates, such as the layered sodium silicates disclosed in U.S. Patent 4,664,839 issued to May 12, 1987 to HP Rieck. NaSKS-6 is the trade name of a crystalline layered silicate marketed by Hoechst (commonly abbreviated as "SKS-6" herein). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum morphological delta-Na ₂ SiO ₅ form of a layered silicate. It can be prepared by methods such as are described in German patents DE-a-3,417,649 and DE-a-3,742,043. SKS-6 is a highly for use herein preferred sheet silicate, but also other sheet silicates such as those of 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 of 0 However, they can also be used here, as are 20, preferably 0. 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 ₂ SiO ₅ (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful, such as. For example, magnesium silicate, which may serve as a solidifying agent in granular formulations, as a stabilizer for oxygen bleach 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. 2,321,001, 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 following 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 formula: 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. Dehydrated zeolites (x = 0-10) can also be used herein. The aluminosilicate preferably has a particle size of about 0.1 to 10 microns in diameter.

organic Detergent builders for the purposes of the invention are suitable, include one size Variety of polycarboxylate compounds, but is not limited thereto. As used herein, "polycarboxylate" refers to compounds with several carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be used in the composition acid form However, it can also be added in the form of a neutralized Salt are added. When used in salt form, alkali metals, such as sodium, potassium and lithium, or alkanolammonium salts.

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. See also "TMS / TDS" builder of the US patent 4,663,071, issued to Bush et al. on May 5, 1987. Suitable ether polycarboxylates shut down also cyclic compounds, especially 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 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. Oxydisuccinates are in such compositions and combinations also particularly useful.

Also useful in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is Dodece nylbernsteinsäure. Specific examples of succinate builders include laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group and are described in European Patent Application 86200690.5 / 0,200,263, published November 5, 1986.

Further 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, disclosed. 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 are used can and especially in the formulation of piece molds suitable for hand washing procedures can be used the various alkali metal phosphates, such as the well-known Sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate, be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137) may also be used 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. Bleach are, if present, usually in concentrations of about 1% to about 30%, more typically from about 5% to about 20% of the detergent composition before, especially for washing clothes. The amount of bleach activators, if present, is typically from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the Bleaching composition containing bleach plus bleach activator includes.

The bleaches used here can any of the bleaches necessary for detergent compositions for textile cleaning, for cleaning hard surfaces or other cleaning purposes, which are now known or will become known in the future, are useful. Close this Oxygen bleach and other bleaches. perborate, z. For example, sodium perborate (eg, mono- or tetrahydrate) may be used herein become.

A other bleach category that can be 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. Patent 4,483,781, Hartman on November 20, 1984, in U.S. Patent Application 740,446, Burns et al., filed June 3, 1985, in European Patent Application 0,133,354, Banks et al., Published on February 20, 1985, and in U.S. Patent 4,412,934, Chung et al on November 1, 1983, disclosed. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as disclosed in U.S. Patent 4,634,551 issued January 6, 1987 to Burns et al., described.

peroxide bleaching agent can also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, Urea peroxyhydrate and sodium peroxide. persulfate (eg OXONE, manufactured by DuPont) may also be used 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 Be coated surfactants. Percarbonate is from various trade sources available, like FMC, Solvay and Tokai Denka.

mixtures of bleaching agents also be used.

Peroxygen bleaches, perborates, percarbonates, etc. are preferably combined with bleach activators which, in aqueous solution (for example during the washing process), result in the in situ production of the peroxy acid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al., And U.S. Patent 4,412,934. The nonanoylbenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical and mixtures thereof can also be used. For other typical bleaches and activators that are useful here, see also US 4,634,551 ,

Especially preferred amido-derived bleach activators are those having the formulas: 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 of from about 6 to about 12 carbon atoms, R ^{2 is} an alkylene of from 1 to about 6 carbon atoms, R ^{5 is} H or alkyl, aryl or alkaryl of from about 1 to about 10 carbon atoms, and L is a suitable leaving group. A leaving group is any group which is displaced from the bleach activator due to nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylsulfonate.

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

Another class of bleach activators includes the benzoxazine-type activators described by Hodge et al. in U.S. Patent 4,966,723, issued October 30, 1990, which is incorporated herein by reference. A particularly preferred benzoxazine-type activator is:

worin R⁶ H oder eine Alkyl-, Aryl-, Alkoxyaryl- oder Alkarylgruppe mit 1 bis etwa 12 Kohlenstoffatomen ist. Besonders bevorzugte Lactamaktivatoren 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 4,545,784, erteilt an Sanderson, 8. Oktober 1985, welches durch Bezugnahme hierin eingeschlossen ist und Acylcaprolactame, einschließlich Benzoylcaprolactam, das in Natriumperborat adsorbiert ist, offenbart.Another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams having the formulas:

wherein R ^{6 is} H or an alkyl, aryl, alkoxyaryl or alkaryl group having from 1 to about 12 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 4,545,784, issued to Sanderson, October 8, 1985, which is incorporated herein by reference and discloses acyl caprolactams, including benzoyl caprolactam, which is adsorbed in sodium perborate.

Other Bleaching agents as oxygen bleaching agents also correspond to the State of the art and can used here. A type of non-oxygen bleach Of particular interest includes photoactivated Bleaching agents, such as the sulfonated zinc and / or aluminum phthalocyanines, one. See U.S. Patent No. 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions contain typically from about 0.025% to about 1.25% by weight of such Bleaching agents, especially sulfonate zinc phthalocyanine.

If desired, 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 described in U.S. Patent 5,246,621, U.S. Patent 5,244,594; U.S. Patent 5,194,416; U.S. Patent 5,114,606; the European Patentanm. Pub. 549.271 A1, 549.272 A1, 544.440 A2 and 544.490 A1. Preferred examples of these catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triaza cyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) _2- (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-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 described in U.S. Pat. 4,430,243 and in U.S. Pat. 5,114,611 are disclosed. 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 not for limitation can the present compositions and methods are adapted by an order of magnitude at least one part per ten million active bleach catalyst species in the aqueous Provide wash liquor, and preferably make about 0.1 ppm to about 700 ppm, more preferably about 1 ppm to about 500 ppm of Catalyst species in the wash liquor ready.

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 Close enzymes Proteases, amylases, lipases, cellulases and peroxidases and mixtures one of them. It can other types of enzymes are also included. You can anyone of any suitable origin, such as plants, animals, bacteria, Mushrooms and yeasts. However, your choice is determined by various factors like pH activity and / or stability optima, Thermostability and stability across from active detergents, builders and so on. In this Regard bacterial or fungal enzymes, such as bacterial Amylases and proteases and fungal cellulases, preferred.

The Integration of enzymes is usually sufficient Concentrations up to about 5 mg, more typical 0.01 mg to about 3 mg of effective enzyme per gram of composition. In other words For example, the compositions herein typically comprise about 0.001 Wt% to about 5 wt .-%, preferably from 0.01 wt .-% to 1 wt .-% one commercially available Enzyme preparation. Protease enzymes are available in such commercially available Preparations usually in sufficient concentrations to 0.005 to 0.1 Anson units (AU) of activity to provide per gram of the 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 No. 87303761.8, filed on April 28, 1987 and European Patent Application 130,756, Bott et al., published on January 9, 1985). Amylases include, for example, α-amylases, those disclosed in British Patent No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc., and TERMAMYL, Novo Industries, are described.

The Cellulase useful in the present invention includes cellulase from bacteria or fungi. Preferably, they have a pH optimum between 5 and 9.5. Suitable cellulases are described in U.S. Patent 4,435,307, Barbesgoard et al., Issued Mar. 6, 1984, discloses which Mushroom cellulase disclosed by Humicola insolens and the Humicola strain DSM1800 or a cellulase 212 producing Fungus belonging to the genus Aeromonas, and cellulase, those from the midgut gland of a marine mollusk (Dolabella auricula Solander) becomes. Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2095275 and DE-OS-2,247,832. CAREZYME (Novo) is especially good suitable.

Suitable lipase enzymes for use in 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., Nagoya, Ja pan, under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other commercially available lipases include Amano-CES, lipases from Chromobacter viscosum, e.g. B 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 EPO 341,947) is a preferred lipase for use herein.

peroxidase be in combination with oxygen sources, eg. B. percarbonate, Perborate, persulfate, hydrogen peroxide, etc. used. you will be to "bleaching the solution "used d. H. to the transfer of dyes or pigments during the washing process of 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, disclosed. Enzyme materials useful for liquid detergent formulations are suitable, and their inclusion in such formulations are in U.S. Patent 4,261,868, Hora et al., Issued April 14, 1981. Enzymes for use in detergents can be prepared by various methods be stabilized. Methods for enzyme stabilization are disclosed in U.S. Patent No. 3,600,319, issued August 17, 1971 to Gedge et al., And in U.S. Pat the European Patent application, publication no. 0 199 405, registration no. 86200586.5, published October 29, 1986, Venegas, revealed and illustrated. Systems for enzyme stabilization are also described, for example, in U.S. 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 shut down Complexing agents, soil release agents, anti-redeposition agents, Dispersants, brighteners, suds suppressors, fabric softeners, dye transfer inhibitors and fragrances.

Examples

anionic Agglomerates include 38% anionic surfactant, 22% zeolite and 40% % Carbonate.

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

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.

The nonionic pasty spray comprises 67% C12-C15 AE5 (alcohol with an average of 5 ethoxy groups per molecule), 24% N-methylglucoseamide and 9% water.

The Sparkling agent, compact, includes 54.5% sodium bicarbonate and 45.5% citric acid.

All the particulate Materials of Example 1, except the dried zeolite were mixed together in a mixing drum, around a homogeneous particulate To form a mixture while The sprays were made in this mixing. After this spray on was dusts carried out with dried zeolite.

A first series of tablets was prepared as follows, approximately 37.5 g of the mixture was placed in a 4.5 cm diameter round mold and compacted with a force of 0.5 kN or about 30 Newton / cm ² to form tablets of about 2.2 cm height and a density of about 1.1 g / cm ³ . The tensile strength of the tablet was 3.5 kPa.

Adipic acid was heated in a thermostatic bath to 170 ° C with gentle stirring until it melted. The disintegrant, Nymcel ZSB-16 ^®, was then added under continuous stirring to the adipic acid to form a suspension. The tablets, prepared as above, were then dipped in a liquid to produce the finished coated tablet, this tablet had a total weight of 41.1 g and a tensile strength of 12.6 kPa.

A second series of tablets was made with a compaction force of 1 kN or about 65 N / cm ² to form tablets of about 2.0 cm in height, a density of about 1.2 g / cm ³ and a tensile strength of 9.0 kPa to create.

To the coating with adipic acid the tablets had a weight of 41.2 g, and the tensile strength was 21.2 kPa.

A third series of tablets was made with a compaction force of 1.5 kN or about 95 N / cm ² to give tablets of about 1.9 cm in height, a density of about 1.3 g / cm ³ and a tensile strength of 12, 9 kPa to produce. After coating with adipic acid, the tablets had a weight of 41.1 g, and the tensile strength was 31.5 kPa.

Example 2

Mix according to the in Example 1, after dewing were the Sprudel granules was added to the mixing drum and a final mixture was prepared.

The Tableting and coating was carried out according to the procedure described in Example 1 Procedure performed.

A first series of tablets was made with a compaction force of 1 kN or about 63 Newton / cm ² to form tablets of about 2.2 cm in height, a density of about 1.1 g / cm ³ and a tensile strength of 4.5 kPa to create.

To the coating with adipic acid the tablets had a weight of 41.1 g, and the tensile strength was 14.4 kPa.

A second series of tablets was made with a compaction force of 1.5 kN or about 95 N / cm ² to form tablets of about 2.2 cm height, a density of about 1.2 g / cm ³ and a tensile strength of 8, 5 kPa to produce.

After coating with adipic acid, the tablets had a weight of 41.1 g, and the drafts activity was 22.2 kPa.

A third series of tablets was made with a compaction force of 2.5 kN or about 160 N / cm ² to form tablets of about 2.0 cm in height, a density of about 1.2 g / cm ³ and a tensile strength of 15, 7 kPa to produce.

To the coating with adipic acid the tablets had a weight of 41.1 g, and the tensile strength rose to 31 kPa.

In Comparative Example 3, the procedure of Example 1 was repeated, but without the decomposer. The ultimate tensile strength of the three rows of tablets was 6.5 kPa, 15.5 kPa and 19.5 kPa, respectively.

In Comparative Example 4, the procedure of Example 4 was repeated, but without the decomposer. The ultimate tensile strength The three rows of tablets were 10.4 kPa, 14.5 kPa and 21.3 kPa, respectively.

Claims (6)

A tablet comprising a core and a coating, wherein the core is made by densification of a particulate material, wherein the particulate material comprises surfactant and detergency builder, characterized in that the coating material has a water solubility at 25 ° C of less than 20 g / l and is selected from C ₂ -C ₁₃ dicarboxylic acids and the coating comprises a disintegrant which swells on contact with water in a concentration to break the coating of up to 30% by weight of the coating. A tablet according to claim 1 comprising a decomposer, selected from the group consisting of natural starch, modified starch, pregelatinized Strength, Natriumstärkegluconat, Croscarmellose sodium, crospovidone, cellulose, carboxymethyl cellulose, alginic acid, Sodium alginate, silica, clay, agar-agar gum, guar gum, Locust bean gum, karaya gum, pectin gum, gum tragacanth, polyvinylpyrrolidone, Soy polysaccharides, ion exchange resins and mixtures thereof. A tablet according to either claim 1 or claim 2, further comprising an effervescent agent. A tablet according to claim 3, wherein the effervescent agent a soluble one acid source and an alkali metal carbonate. A method of making a tablet, comprising the steps of: (a) forming a core by densifying a particulate material, the particulate material comprising surfactant and detergency builder; (b) applying a coating material to the core, wherein the coating material is in the form of a melt; (c) allowing the molten coating material to solidify; characterized in that the coating material comprises a disintegrant that swells upon contact with water at a concentration to break the coating of up to 30% by weight, and wherein the coating material has a water solubility at 25 ° C of less than 20 g / l and is selected from C ₂ -C ₁₃ dicarboxylic acids. Method according to claim 5, wherein the coating material, or the mixture of materials having a melting point of 40 ° C to 200 ° C.