DE69938228T2 - Perfumed detergent tablet - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION

The The present invention relates to perfumed detergent tablets, especially those designed for use in washing machines, and methods of making such detergent tablets.

BACKGROUND OF THE INVENTION

Perfumed products are known in the art. Consumer acceptance of such perfumed products However, as washing and cleaning products is not only from the determined by these products, but also by the associated aesthetics. The perfume ingredients are therefore an important consideration the successful formulation of such commercial products.

Besides that is a clay mineral compound is more desirable Component of such a detergent and cleaning product, in particular those products that are in tablet form. In fact, the clay may have a softening benefit However, it can also be used as a decomposing agent Detergent tablets serve.

however is a problem associated with perfumed detergent tablets, that contain a clay mineral compound, that the clay is a detrimental Affect the performance of the fragrance contained therein can. Without being bound to a theory, it is therefore assumed that due to physical proximity, which is given by the tablet which absorbs perfume in the clay is where he deals with heavy metal ions and acid or base sites within of the clay can interact, resulting in a discoloration of the Sounds can cause. Also, the interaction between the Perfume and cause the sound that the tablet has a less attractive color.

It is accordingly an object the invention, a perfumed To provide detergent tablet containing a clay mineral compound includes the good perfume performance with reduced discoloration of the Has clay.

Further cleaning compositions in tablet form have been proposed many times However, these have (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 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 April 22, 1965, discloses a process for producing a particulate detergent from surfactants and inorganic salts; Spraying on water-soluble silicate; and pressing the detergent particles into a tablet which retains its solid form. Finally, a readily water-soluble organic film-forming polymer (e.g., polyvinyl alcohol) provides a coating to render the detergent tablet resistant to attrition and accidental breakage.

EP-A-0 002 293 , published June 13, 1979, discloses a tablet coating comprising hydrated salt such as acetate, metaborate, orthophosphate, tartrate and sulfate.

EP-A-0 716 144 , published June 12, 1996, also discloses detergent tablets having water-soluble coatings, which may be organic polymers including acrylic / maleic copolymers, polyethylene glycol, PVPVA, and sugars.

WO9518215 , published July 6, 1995, provides water-insoluble coatings for solid cast pills. The tablets are provided with hydrophobic coatings, including paraffin, fatty acid, fatty acid amides and polyethylene glycol.

EP-A-0 846 754 , published June 10, 1998, provides a tablet having a coating comprising a dicarboxylic acid, the coating material typically having a melting point of from 40 ° C to 200 ° C.

EP-A-0 846 755 , published June 10, 1998, provides a tablet having a coating comprising a material which is insoluble in water at 25 ° C, such as C12-C22 fatty acids, adipic acid or C8-C13 dicarboxylic acids.

EP-A-0 846 756 , published June 10, 1998, provides a tablet having a coating comprising a disintegrating agent, and preferably an effervescent.

Recently, agents have been found by which coated tablets can be provided with a coating so that they can be stored, transported and handled without being damaged, with the coating being easily broken when the tablet is in the washing machine, the Active ingredients are released into the wash solution. Typical of such disclosure is in the pending European patent applications EP 99870017.3 . EP 99870018.1 and EP 99870019.9 to find.

Even though However, satisfactory results have now been achieved also shown that when a clay mineral compound in the coating the detergent tablet is present, the clay from the same above assumed reasons an adverse effect on the performance of the contained therein Perfume and the appearance of the coating, d. H. Discoloration of the Coating, has.

It has been shown to be more acute over time, and more specifically, if the coating also has an acid with a melting point of at least 40 ° C, more specifically comprising a melting point of at least 145 ° C.

Accordingly is the detergent manufacturer also facing the problems to provide a coated tablet that has a coating that has a satisfactory appearance is tough enough to prevent the tablet from mechanical forces during storage, transportation and to protect handling and easily in an aqueous solution distributed while still satisfactory perfume performance is offered.

Further is perfuming The detergent tablet is an issue for the detergent manufacturer. Thus, the presence of the coating on the tablet can cause diffusion reduce the fragrance from the tablet, resulting in a less attractive smell leads.

It has now become surprising shown that the addition of a heavy metal ion sequestrant to the perfumed Detergent tablet overcomes these problems.

SUMMARY OF THE INVENTION

The present invention is a coated perfumed detergent tablet, wherein the tablet is a clay mineral compound and a heavy metal ion sequestrant wherein the coating is the heavy metal ion sequestering agent includes.

With "perfumed Detergent tablet "is meant that the perfume in the coating or in the detergent composition or may be present in both.

DETAILED DESCRIPTION OF THE INVENTION

volume

An essential ingredient of the detergent tablet is a clay. The clay can be added in the detergent composition, the coating or be present in both.

With Clay mineral compound (or abbreviation "clay") herein is a hydrous phyllosilicate meant, usually with a two- or three-layered crystal structure. For reasons For the sake of clarity, the term clay mineral compound, as used herein, sodium aluminosilicate zeolite builder compounds excludes however, as an optional ingredient in the compositions of the invention can be included. Another description of clays is in Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Edition, Volume 6, page 381, as published by John Wiley and Sons, to find.

The clay mineral compound is preferably a smectite clay compound. Smectite clays are in the U.S. Patent Nos. 3,862,058 . 3,948,790 . 3,954,632 and 4,062,647 and European patents no. EP-A-299,575 and EP-A-313,146 , all in the name of The Procter and Gamble Company.

As used herein, the term smectite clay includes both the clays in which alumina is present in a silicate lattice and the clays in which magnesia is present in a silicate lattice. Typical smectite clay compounds include the compounds having the general formula Al ₂ (Si ₂ O ₅ ) ₂ (OH) ₂ .nH ₂ O and the compounds having the general formula Mg ₃ (Si ₂ O ₅ ) ₂ (OH) ₂ .nH ₂ o one. Smectite clays usually assume an expandable three-layer structure.

specific Examples of suitable smectite clays include those that are selected from the classes of Montmorillonite, Hectorite, Volchonskoite, Nontronite, Saponites and sauconites, especially those containing an alkali or Have alkaline earth metal ion within the crystalline lattice structure. Sodium or calcium montmorillonite are particularly preferred.

suitable Smectite clays, especially montmorillonites, are of various types Suppliers, including English China Clays, Laviosa, Fordamine, Georgia Kaolin and Colin Stewart Minerals (CSM).

preferred Smectite clays are sold under the trade name White Bentonite STP from Fordamin and Detercal P7 from Laviosa Chemical Mineria SPA.

aluminas for this purpose Can use an acid wash treatment subjected to a suitable mineral or organic acid become. Such clays result in dissolution in distilled water an acid pH. A commercially available "sour tone" of this kind is sold under the trade name Tonsil P by Süd-Chemie AG.

Within the crystalline lattice structure of the smectite clays, there may typically be substitution of small cations, such as protons, sodium ions, potassium ions, magnesium ions and calcium ions, and certain organic molecules, including those having positively charged functional groups. A clay can be selected for its ability to preferentially adsorb a cation type, such ability being determined by measuring the relative ion exchange capacity. The smectite clays useful herein typically have a cation exchange capacity of at least 50 meq / 100g. U.S. Patent No. 3,954,632 describes a method for measuring cation exchange capacity.

The crystalline lattice structure of the clay mineral compounds may, in a preferred embodiment, contain a substituted cationic fabric softener. Such substituted clays are called 'hydrophobically activated' clays. The cationic fabric softeners are typically present in a weight ratio of cationic fabric softener to clay of from 1: 200 to 1:10, preferably from 1: 100 to 1:20. Suitable cationic fabric softening agents include the water-insoluble tertiary amines or amide materials having two long chains as in GB A 1 514 276 and EP B 0 011 340 disclosed.

One more preferred "commercially available" hydrophobic activated "sound is a bentonite clay that is about 40% by weight of quaternary Dimethylditalgammonium salt, distributed by English China Clays International under the brand name Claytone EM.

Preferably, the clay present in the detergent composition is present in an intimate mixture or in a particle with a humectant and a hydrophobic compound, preferably a wax or oil, such as paraffin oil. Preferred humectants are organic compounds including propylene glycol, ethylene glycol, dimers or trimers of glycol, most preferably glycerol. The particle is preferably an agglomerate. Alternatively, the particle may be such that the wax or oil and optionally the humectant form an encapsulation of the clay, or alternatively, the clay may be an encapsulant for the wax or oil and humectant. It may be preferred that the particle comprises an organic salt or silica or silicate.

In another embodiment For example, the clay is preferably included in the detergent composition one or more surfactants and optionally builders and optionally Mixed water, the mixture preferably dried below becomes. Preferably, such a mixture is in a spray-drying process further processed to a spray-dried To obtain particles containing the clay.

It It may also be preferred that the intimate mixture be a sequestering agent includes.

Depending on its end use, the clay is preferably in different Particle sizes available. If softening desired Thus, it is preferred that at least 50% by weight, preferably essentially the entire (eg, at least 90% by weight or 95%) Wt .-%) of the clay are present as granules. With granules is meant that the particles of the clay mineral compound used in the Detergent composition is present, as constituents of agglomerate particles, optionally containing other detergent compounds, included are. Where they exist as such components, the Term "largest particle dimension" of the clay mineral compound to the largest dimension of the clay mineral component as such, and not on the agglomerated Total particles. As a rule, the granules have a particle size of at least 100 microns, generally 100-1700 Micrometers.

It is often desired to have a clay as a decomposer in the coating. In In this case, the clay is preferably present in the coating and has a particle size of less than 75 μm, more preferably less than 53 microns.

Preferably the tablet is a softening tablet. With softening Tablet is meant that the concentration of clay is usually at least 5% by weight, preferably at least 8% by weight and most preferably at least 10 wt .-% of the tablet. The amount can be less as 25% by weight, usually less than 20% by weight and preferably at most 15% by weight of the tablet be.

Heavy metal ion sequestrant

The Detergent composition tablet of the invention also contains a heavy metal ion sequestering agent contained in the coating is available. The heavy metal ion sequestrant can be used both in the coating as well as the detergent composition be. With heavy metal ion sequestrants herein are ingredients meant to act to mask (chelate) heavy metal ions. These ingredients can also the ability to the formation of calcium and magnesium complexes possess show but preferably selectivity across from the binding of heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrant are generally in a concentration of 0.005 wt .-% to 20 wt .-%, preferably from 0.1% to 10% by weight, more preferably from 0.25 Wt% to 7.5 wt% and most preferably from 0.5 wt% to 5 wt .-% of the tablet present.

Heavy metal ion sequestrant are acidic in nature, for example, have phosphonic acid or carboxylic acid functionalities, can either in their acid form or as a complex / salt with a suitable counter cation, such as Alkali or alkali metal ion, ammonium or substituted ammonium ion or any mixtures thereof are present. Preferably, any Salts / complexes soluble in water. The molar ratio from counter cation to heavy metal ion sequestrant is preferably at least 1: 1.

suitable Heavy metal ion sequestrants for use herein include organic ones Phosphonates such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates and nitrilotrimethylene phosphonates.

Prefers among the above species are diethylene triamine penta (methylene phosphonate), Ethylenediaminetri (methylenephosphonate), hexamethylenediamine tetra (methylenephosphonate) and hydroxyethylene-1,1-diphosphonate.

Other suitable heavy metal ion sequestrants for this purpose Use include nitrilotriacetic acid and polyaminocarboxylic, such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic, ethylenediamine, ethylenediaminediglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof, one.

Particularly preferred are ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or the sodium or magnesium complex thereof. Examples of such preferred EDDS sodium salts include Na ₂ EDDS and Na ₃ EDDS. Examples of such preferred magnesium complexes of EDDS include MgEDDS and Mg ₂ EDDS.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives, such as 2-hydroxyethyl diacetic acid or glyceryliminodiacetic acid, described in EP-A-0 470 047 EP-A-317.542 and EP-A-399,133 ,

Iminodiacetic acid N-2-hydroxypropylsulfonic acid masking agents and aspartic acid-N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid described in EP-A-0 403 878 EP-A-516,102 , are also suitable for this. The masking agents of β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid, described in EP-A-509,382 , are also suitable.

EP-A-476,257 describes suitable amino-based sequestering agents. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528.859 describes a suitable masking agent of alkyliminodiacetic acid. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

At the most preferred heavy metal ions for use herein are alkali metal ethane 1-hydroxy diphosphonates, especially when combined with diethylenetriamine-penta (methylenephosphonate) be used.

perfume

The Optionally, tablets of the present invention may also comprise a perfume composition, either in the coating, if any, or in the detergent composition or even in both the coating and the detergent composition is available. Suitable perfumes herein include materials, the one odorous aesthetic Provide advantage, for. B. to such tablets for the consumer aesthetically make it pleasant to treat the treated fabrics with a pleasant To give fragrance and / or "chemical" smell, that the Product may have to cover.

As used here, concludes Perfume scented substances or mixtures of substances, including natural (ie by extraction of flowers, herbs, leaves, roots, bark, wood, flowers or Preserved plants), artificial (i.e., a mixture of different natural oils or oil components) and synthetic ones (i.e., synthetically produced) fragrant substances. Such Materials become common accompanied by auxiliary materials, such as fixatives, extenders, Stabilizers and solvents. These adjuvants are also in the meaning of "fragrance" as used herein locked in. As a rule, fragrances are complex mixtures from several organic compounds.

Suitable fragrances are in U.S. Patent No. 5,500,138 which patent is incorporated herein by reference.

Examples of perfume ingredients that are useful in the perfume compositions include, but are not limited to, hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octene-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl-trans-2,6-octadiene-1-ol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde; tricyclodecenyl; tricyclodecenyl; anisaldehyde; 2-methyl-2- (para-iso-propylphenyl) propionaldehyde; Ethyl-3-methyl-3-phenylglycidate; 4- (parahydroxyphenyl) -butan-2-one; 1- (2,6,6-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one; Paramethoxyacetophenon; Paramethoxy-alpha-phenylpropene; Methyl-2-n-he xyl-3-oxocyclopentanecarboxylate; gamma-undecalactone.

Additional examples of perfume materials include, but are not limited to, orange oil; Lemon oil; Grapefruit oil; bergamot; Clove oil; gamma-dodecalactone; Methyl-2- (2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methyl ether; Methyl-beta-naphthyl ketone; coumarin; decyl; benzaldehyde; 4-Tertbutylcyclohexylacetate; alpha, alpha-dimethylphenethyl acetate; methyl phenyl; cyclic ethylene glycol diester of tridecanedioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; gamma-methyl; alpha-ionone; beta-ionone; Bitter Orange; methyl cedrylone; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene; Methyl; Methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone; 6-acetyl-1,1,2,3,3,5-hexamethylindane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal; 7-hydroxy-3,7-dimethyloctanal; 10-undecen-1-al; isohexenyl cyclohexyl; formyl tricyclodecan; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; AMBROXAN.RTM; Dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b] furan; cedrol; 5- (2,2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol; caryophyllene alcohol; cedryl acetate; Paratertbutylcyclohexylacetat; patchouli; Weihrauchresinoid; labdanum; vetiver; Copaibabalsam; Spruce Balsam; Hydroxycitronellal and indole; Phenylacetaldehyde and indole;
More examples of perfume ingredients are geraniol; Geranylacetat; linalool; Linalylacetat; tetrahydrolinalool; citronellol; citronellyl; dihydromyrcenol; dihydromyrcenyl; tetrahydromyrcenol; terpinyl; monopoly; nopyl acetate; 2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl acetate; benzyl; benzyl benzoate; Styrallyl acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl methylphenylcarbinyl; isononylacetate; vetiveryl; Vetyverol; 2-methyl-3- (p-tert-butylphenyl) -propanal; 2-methyl-3- (p-isopropylphenyl) -propanal; 3- (p-tert-butylphenyl) -propanal; 4- (4-methyl-3-pentenyl) -3-cyclohexene carbaldehyde; 4-acetoxy-3-pentyltetrahydropyran; methyldihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentylcyclopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethylisobutyrate; phenylacetaldehyde; phenylacetaldehyde; geranonitrile; citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedryl methyl ether; isolongifolanone; Anisaldehydnitril; anisaldehyde; heliotropin; eugenol; vanillin; diphenyl oxide; hydroxycitronellal; methyl ionones; isomethyl ionomes; Irone; cis-3-hexenol and esters thereof; Moschusindan-fragrances; Moschustetralin-fragrances; Moschusisochroman-fragrances; macrocyclic ketones; Moschusmakrolacton-fragrances; Ethylene.

The Perfumes used in the compositions of the present invention are substantially free of halogenated materials and nitro-musk compounds.

Preferably contains the perfume composition to less than 0.6% by weight of the perfume composition Ship's base. The perfume for use herein is in concentrations used up to 5 grams per tablet and is preferably in the Essentially free of Schiff's base.

With "essentially free "is meant that the fragrance composition to less than 0.4% by weight Schiffs Base and more preferably is free of Schiff base.

Schiff bases are the condensation of an aldehyde perfume ingredient with an anthranilate. A typical description is in US 4853369 to find. The Schiff's bases may be added directly to the perfume composition or may be formed in situ in the perfume composition by adding thereto an anthranilate, such as methyl or ethyl anthranilate, together with an aldehyde which can react with the anthranilate to form the Schiff's base , is given.

Without being bound to a theory, it is believed that if this Contact with the sound, it undergoes reactions, the most likely are catalyzed by the metal ions present in the clay, and that these reactions are stronger colored Form by-products.

typical Ship bases are selected from Schiff's base of 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde and methyl anthranilate; Condensation products of: hydroxycitronellal and methyl anthranilate; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde and methyl anthranilate; Methyl anthranilate and hydroxycitronellal, available in the stores under the trade name Aurantiol; Methyl anthranilate and methyl nonyl acetaldehyde, available in the stores under the trade name Agrumea; Methyl anthranilate and PT Bucinal, available in the stores under the trade name Verdantiol; Methyl anthranilate and lyral, available in the stores under the trade name Lyrame; Methyl anthranilate and Ligustral, available in the stores under the trade name Ligantral; and mixtures thereof.

Preferably the fragrance composition is fragrance-free, the selected are from methylanthranilate and hydroxycitronellal, available commercially under the trade name Aurantiol; Methyl anthranilate and methyl nonyl acetaldehyde, available in the stores under the trade name Agrumea; Methyl anthranilate and PT Bucinal, available in the stores under the trade name Verdantiol; Methyl anthranilate and lyral, available in the stores under the trade name Lyrame; Methyl anthranilate and Ligustral, available in the stores under the trade name Ligantral; and mixtures thereof.

suitable Solvent, thinner or carrier for the above-mentioned perfume ingredients are, for example, ethanol, Isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, Diethyl phthalate, triethyl citrate, etc. The amount of these solvents, thinner or carrier, which are included in the fragrances is preferably on the minimum is limited, which is necessary to obtain a homogeneous perfume solution.

tablets of the present invention as well as coated tablets according to the invention improved perfume attachment to fabric ready.

Preferably is the perfume composition in an amount of 0.001% by weight to 10 wt .-%, preferably from 0.005 wt .-% to 5 wt .-%, more preferably from 0.01% to 3% by weight and more preferably from 0.02 wt .-% to 2 wt .-% of the tablet present.

Of the Perfume can be used with any conventional, the agent known in the art are included in the tablet. A preferred agent is the spraying of the perfume composition on the tablet.

Detergent ingredients

The tablets may include ingredients such as surfactants, enzymes, detergents, etc. Typical tablet compositions for the preferred embodiment of the present invention are described in the attached European applications of the applicant No. 96203471.6 . 96203462.5 . 96203473.2 and 96203464.1 for example disclosed. Elements which are typically included in the composition of detergent tablets or other forms of detergents, such as liquids or granules, are described in detail in the following paragraphs.

Cleaning surfactants

surfactants are usually included in a detergent composition. The resolution of surfactants is favored by the addition of the highly soluble compound.

Non-limiting examples of surfactants useful herein, typically 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 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 sulfate, 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 polyglycosides and their corresponding sulfated polyglycosides and alpha-sulfonated C ₁₂ -C ₁₈ fatty acid esters. If desired, conventional nonionic and amphoteric surfactants may also be used, such as the C ₁₂ -C ₁₈ alkyl ethoxylates ("AE") including the so-called narrow 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. Please refer 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 sudsing is desired, the branched chain C ₁₀ -C ₁₆ soaps can be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventional suitable surfactants are listed in standard texts. In a preferred embodiment, the tablet comprises at least 5 wt% surfactant, more preferably at least 15 wt%, even more preferably at least 25 wt%, and most preferably between 35 wt% and 45 wt% surfactant ,

Non-gelling binders

Non-gelling Binders can be integrated into detergent compositions to further dissolve to facilitate.

If non-gelling binders are used, include suitable ones non-gelling binders synthetic organic polymers such as Polyethylene glycols, polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers. In the Handbook of Pharmaceutical Excipients, second edition, are the the following binder classifications: acacia, alginic acid, carbomer, Carboxymethylcellulose sodium, dextrin, ethylcellulose, gelatin, Guar gum, hardened vegetable oil Type I, hydroxyethylcellulose, hydroxypropylmethylcellulose, liquid glucose, Magnesium aluminum silicate, maltodextrin, methylcellulose, polymethacrylates, Povidone, sodium alginate, starch and zein. The most preferred binders also have one active cleaning function during laundry, such as cationic polymers, d. H. ethoxylated quaternary hexamethylenediamine compounds, Bishexamethylenetriamines, or others such as pentaamines, ethoxylated Polyethylene amines, maleic acrylic polymers.

Non-gelling Binders are preferably sprayed on and therefore have a corresponding Melting temperature of below 90 ° C, preferably below 70 ° C and even more preferably below 50 ° C, not to damage the other active ingredients in the matrix or to decompose. Most preferred are nonaqueous liquid binders (i.e., not in water Solution), which are sprayed in molten form can. You can However, also be solid binder by dry addition in the Matrix are included, however, binding properties within own the tablet.

Non-gelling Binders are preferably used in an amount in the range of 0.1 up to 15% by weight of the composition, more preferably below 5% by weight and, especially if it is not an active detergent substance, under 2 wt .-% of the tablet used.

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, however, it is preferred that they be considered as constituents of particulate material and not as liquids be incorporated into the detergent tablets.

builders

detergent builder can optionally contained in the present compositions, to the regulation of mineral hardness to support. It can inorganic and organic builders are used. Builder are typically used in fabric washing compositions used to assist in the removal of particulate soil.

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

inorganic or P-containing builders 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 do not contain 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 from 1.6: 1 to 3.2: 1, and phyllosilicates, such as the sodium phyllosilicates, which are known in U.S. Patent 4,664,839 issued May 12, 1987 to HP Reck. NaSKS-6 is the trade name of a crystalline layered silicate marketed by Hoechst (commonly abbreviated to "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, which can be prepared by methods such as described in German patents DE-A-3,417,649 and DE-A-3,742,043 are described. SKS-6 is a highly preferred phyllosilicate for use herein, but other phyllosilicates such as those of the general formula NaMSi _x O _{2x + 1} x yH ₂ O, where M is sodium or hydrogen, x may have a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, are used herein. 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 can be used in granular formulations as an extender, as a stabilizer for oxygen bleach and as an ingredient in foam control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates, as in the German Patent Application No. 2,321,001 , published November 15, 1973, discloses.

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 process for the preparation of aluminosilicate ion exchange materials is 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 Builder for the purposes of the invention are suitable, close a big 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 builders include a variety of categories of 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, discloses. See also "TMS / TDS" images of the U.S. Patents 4,663,071 issued to Bush et al. on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds such as those described in U.S. Pat U.S. Patents 3,923,679 . 3,835,163, 4,158,635 . 4,120,874 and 4,102,903 are described.

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 particularly important polycarboxylate builders for liquid heavy duty detergent formulations because of their availability from renewable sources and their biodegradability. Citrates may also be used in granular compositions, especially in combination with zeolite and / or layered silicate builders be used. Oxydisuccinates are also particularly useful in such compositions and combinations.

Also useful in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in U.S. Pat U.S. Patent 4,566,984 Bush, issued January 28, 1986, are disclosed. 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 dodecenylsuccinic acid. Specific examples of succinate builders include laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group and are in the European Patent Application 86200690.5 / 0,200,263 , published November 5, 1986.

Other suitable polycarboxylates are in U.S. Patent 4,144,226 , Crutchfield et al., Issued Mar. 13, 1979, and in US Pat U.S. Patent 3,308,067 , Diehl, issued March 7, 1967, discloses. 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 aforementioned builders, particularly 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 where phosphorus-based builders can be used, and particularly in the formulation of bar molds used for hand washing processes, the various alkali metal phosphates, such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate, can 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 ) can also be used.

bleach

The Cleaning compositions herein may optionally include bleaches or bleach compositions containing a bleaching agent and one or more bleach activators. Bleach, 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, which comprises the bleach plus bleach activator.

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.

Another category of bleach that can be used without limitation includes percarboxylic acid bleaches 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 diperoxydodecanedioic acid. Such bleaches are in the U.S. Patent 4,483,781 Hartman, issued November 20, 1984, in the U.S. Patent Application 740,446 , Burns et al., Filed June 3, 1985, in the European patent application 0,133,354 , Banks et al., Published February 20, 1985, and in the U.S. Patent 4,412,934 , Chung et al., Issued November 1, 1983. Highly preferred bleaches also include 6-nonylamino-6-oxoperoxycaproic acid, as described in U.S. Pat U.S. Patent 4,634,551 , issued January 6, 1987 to Burns et al.

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.

A preferred percarbonate bleaching agent comprises dry particles having an average portion The particle size range is from about 500 microns to about 1000 microns, with no more than about 10 wt% of the particles being smaller than about 200 microns and no more than about 10 wt% of the particles larger than about 1250 microns. The percarbonate may optionally be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from several sources, including FMC, Solvay and Tokai Denka.

mixtures of bleaching agents also be used.

Peroxygen bleaches, the perborates, the percarbonates, etc., are preferably combined with bleach activators which, in aqueous solution (ie, during the washing process), result in the in situ generation of the peroxyacid corresponding to the bleach activator. Various non-limiting examples of activators are in the U.S. Patent 4,915,854 , issued April 10, 1990 to Mao et al., and im U.S. Patent 4,412,934 disclosed. 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 ,

Highly 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 by the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylsulfonate.

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

Another class of bleach activators includes the benzoxazine-type activators described by Hodge et al. in the 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 , granted Sanderson, 8 October 1985, which is incorporated herein by reference and discloses acylcaprolactams, including benzoyl-caprolactam, which is adsorbed in sodium perborate.

Bleaching agents other than oxygen bleach are also known in the art and may be used herein. One type of non-oxygen bleach of particular interest includes photoactivated bleaches, such as the sulfonated zinc and / or aluminum phthalocyanines. Please refer U.S. Patent No. 4,033,718 issued July 5, 1977 to Holcombe et al. When used, detergent compositions typically contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially sulfonate 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, manganese-based catalysts useful in the art 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. Veröffentlichungsar. 549.271 A1 . 549,272 A1 . 544,440 A2 and 544,490 A1 one. Preferred examples of these catalysts include Mn ^IV ₂ (uO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 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 known in the art US Pat. 4,430,243 and in US Pat. 5,114,611 of fenbart are. 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, for example, proteinaceous, carbohydrate-containing or triglyceride-containing stains and to prevent transmission volatile Dyes and be included for replenishment. The to be integrated Close enzymes Proteases, amylases, lipases, cellulases and peroxidases and mixtures one of them. It can also other types of enzymes are included. They can be any of suitable origin, such as plants, animals, bacteria, fungi and yeasts. However, your choice is determined by various factors like pH activity and / or stability optima, thermal stability 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 of proteases are the subtilisins obtained from certain strains of B. subtilis and B. licheniformis. Another suitable protease with a maximum activity in the pH range of 8 to 12 is obtained from a Bacillus strain, developed and marketed by 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 described by Novo. Commercially available proteolytic enzymes suitable for the removal of proteinaceous stains include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A / S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (Netherlands). Other proteases include Protease A (see European Patent Application 130,756 , published 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 January 9, 1985).

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

The cellulase useful in the present invention comprises cellulase from bacteria or fungi. Preferably, they have a pH optimum between 5 and 9.5. Suitable cellulases are in U.S. Patent 4,435,307 , Barbesgoard et al., Issued Mar. 6, 1984, which discloses fungal cellulase produced by Humicola insolens and the Humicola strain DSM1800 or a cellulase 212 producing fungus belonging to the genus Aeromonas, and cellulase, extracted from the midgut gland of a marine mollusk (Dolabella auricula solander). Suitable cellulases are also in GB-A-2075028 ; GB-A-2095275 and DE-OS 2,247,832 disclosed. CAREZYME (Novo) is particularly well suited.

Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as described in U.S. Pat British Patent 1,372,034 disclosed. See also Lipases in the 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". 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 also 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 enzymes are used in combination with oxygen sources, e.g. As percarbonate, perborate, persulfate, hydrogen peroxide, etc. used. They are used to "bleach the solution", ie to prevent the transfer of dyes or pigments removed from substrates during the washing process to other substrates in the wash solution Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and Haloperoxidase such as chloro and bromo peroxidase, peroxidase-containing cleaning compositions are disclosed, for example, in the PCT International Application WO 89/099813 , published October 19, 1989, by O. Kirk, assigned to Novo Industries A / S.

A wide range of enzyme materials and agents for their incorporation into synthetic cleaning compositions are also known in the art U.S. Patent No. 3,553,139 issued January 5, 1971 to McCarty et al. Enzymes are still in the U.S. Patent No. 4,101,457 , Place et al., Issued July 18, 1978, and in U.S. Patent No. 4,507,219 , Hughes, issued March 26, 1985, discloses. Enzyme materials suitable for liquid detergent formulations and their incorporation into such formulations are disclosed in U.S.Pat U.S. Patent 4,261,868 , Hora et al., Issued April 14, 1981. Enzymes for use in detergents can be stabilized by various methods. Methods for enzyme stabilization are in the U.S. Patent No. 3,600,319 issued to Gedge et al. on August 17, 1971, and in the European patent application, publication no. 0 199 405 . Ser. 86200586.5 , published October 29, 1986, Venegas, discloses and illustrates. Systems for enzyme stabilization are also for example in U.S. Patent No. 3,519,570 described.

flocculants

The Detergent composition may contain a clay flocculating agent preferably in a concentration of 0.005 wt .-% to 10 Wt .-%, more preferably from 0.05 wt .-% to 5 wt .-%, most preferably from 0.1% by weight to 2 wt .-% of the composition is present.

The Tonflockungsmittel has the function, the particles of the clay compound in the washing solution bring together and so their attachment to the surface of the Tissue during to assist the washing. This functional requirement therefore differs from that clay dispersant compounds commonly used in detergent compositions added to increase the removal of clay contaminants from tissues support and to allow their dispersion in the wash solution.

When Clay flocculating agents are preferred herein as organic polymeric materials with an average weight of 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000.

Suitable organic polymeric materials include homopolymers or copolymers which are monomials purity selected from alkylene oxide, in particular ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinylpyrrolidone and ethyleneimine. Homopolymers, in particular of ethylene oxide, but also of acrylamide and acrylic acid, are preferred.

European patents no. EP-A-299 575 and EP-A-313 146 on behalf of the Procter and Gamble Company describe preferred organic polymeric clay flocculating agents for use herein.

inorganic Clay flocculating agents are also suitable herein, typical examples for that include lime and alum.

The Flocculant is preferably in a detergent base grain such as a detergent agglomerate, extrudate or spray dried particle, the generally comprises one or more surfactants and builders, available.

It may be preferred that the flocculant also in the Particles or the granule, which includes the clay, is included.

If present, amounts to the weight ratio from clay to flocculation polymer, preferably from 1000: 1 to 1: 1, more preferably from 500: 1 to 1: 1, most preferably from 300: 1 to 1: 1 or even more preferably from 80: 1 to 10: 1 or in certain Applications even from 60: 1 to 20: 1.

To other ingredients commonly used in detergent compositions and that can be included in detergent tablets, include complexing agents, Soil release agents, anti-redeposition agents, dispersants, Suds suppressors, Fabric softener, dye transfer inhibitor and mixtures thereof.

Strongly soluble compounds

• 1 20 g der speziellen Verbindung werden in ein Sotax-Becherglas gegeben. Dieses Becherglas wird in ein Bad mit einer auf 10°C eingestellten konstanten Temperatur gestellt. Ein Schraubenrührer, der eine axiale Strömung erzeugt, wird so in dem Becherglas platziert, dass sich das untere Ende des Rührers 5 mm über dem Boden des Sotax-Becherglases befindet. Der Mischer wird auf eine Drehgeschwindigkeit von 20,9 rad/s (200 U/min) eingestellt.
• 2 980 g des deionisierten Wassers werden in das Sotax-Becherglas eingeleitet.
• 3 10 s nach der Einleitung des Wassers wird die Leitfähigkeit der Lösung mithilfe eines Leitfähigkeitsmessers gemessen.
• 4 Schritt 3 wird nach 20, 30, 40, 50, 1 min, 2 min, 5 min und 10 min nach Schritt 2 wiederholt.
• 5 Der nach 10 min erhaltene Messwert wird als der Plateauwert oder Höchstwert verwendet.

The tablet may comprise a highly soluble compound. Such a compound may be formed from a mixture or from a single compound. A highly soluble compound is defined as follows:
A solution is prepared as follows, comprising deionized water and 20 grams per liter of a specific compound:

• 1 20 g of the specific compound are placed in a Sotax beaker. This beaker is placed in a bath with a constant temperature set at 10 ° C. A screw agitator producing an axial flow is placed in the beaker such that the bottom of the stirrer is 5 mm above the bottom of the Sotax beaker. The mixer is set to a rotational speed of 20.9 rad / s (200 rpm).
• 2 980 g of the deionized water are introduced into the Sotax beaker.
• 3 10 s after the water has been introduced, the conductivity of the solution is measured using a conductivity meter.
• 4 Step 3 is repeated after 20, 30, 40, 50, 1 min, 2 min, 5 min and 10 min after step 2.
• 5 The reading obtained after 10 minutes is used as the plateau or peak.

The specific compound is highly soluble according to the invention, if the conductivity the solution in less than 10 seconds, starting with the complete addition of the deionized water to the compound, 80% of its maximum value reached. When the conductivity is checked in such a way actually reaches them after a certain period of time a plateau, this plateau is regarded as the maximum value. For easy handling is one Such compound preferably at temperatures between 10 and 80 ° Celsius in the form of a flowable material before, which consists of solid particles, but other forms, such as a paste or a liquid, be used.

To Examples of highly soluble Belong to connections Sodium diisoalkylbenzenesulfonate (DIBS) or sodium toluenesulfonate.

cohesive effect

The tablet may comprise a compound which exerts a cohesive effect on the particulate material of a detergent matrix forming the tablet. The cohesive effect on the particulate material of a detergent matrix forming the tablet or a layer of the tablet is by the force which is required to break a tablet or layer based on the tested detergent matrix pressed under controlled compression conditions. For a given compressive force, high tablet or layer strength indicates that the granules strongly adhered to each other when compressed so that a strong cohesive effect occurs. Agents for evaluating tablet or sheet strength (also referred to as diametrical fracture stress) are listed in Pharmaceutical Dosage Forms: Tablets, Volume 1, Ed. HA Lieberman et al., Published in 1989.

The cohesive effect is measured by the tablet or layer strength of the original base powder without association with cohesive action with the tablet or layer strength of a powder mixture, the 97 parts of the original Base powder and 3 parts of the compound having cohesive effect, compared becomes. The compound with cohesive action is preferably added in a mold to the matrix in which it is is substantially free of water (water content less than 10% (vorzugsw. below 5%)). The temperature of the addition is between 10 and 80 ° C, more preferably. between 10 and 40 ° C.

A By definition, compound has a cohesive effect on the particulate material of the invention, if at a given compaction force of 3000 N the tablet tensile strength of tablets weighing 50 g of particulate detergent material and a diameter of 55 mm by the presence of 3% of the compound with cohesion effect in the particulate Base material by more than 30% (preferably 60 and more preferred 100%) increases.

One example for a compound with cohesive action is sodium diisoalkylbenzenesulfonate.

At the Incorporation of a highly soluble Compound, which also has a cohesive effect on the particulate Material has that for a tablet or a layer is used that by compaction a particulate one Material, which comprises a surfactant, is the resolution of the Tablet or layer significantly increased in an aqueous solution.

In a preferred embodiment is at least 1 wt .-% of a tablet or layer of the strong soluble Compound formed, more preferably at least 2 wt .-%, even more preferably at least 3% by weight, and most preferably at least 5% by weight of the tablet or layer consisting of the highly soluble Compound having a cohesive effect on the particulate material Has.

It should be noted that a composition comprising a highly soluble compound as well as a surfactant, in EP-A-0 524 075 is disclosed, wherein this composition is a liquid composition.

A highly soluble Compound that has a cohesive effect on the particulate Material has enabled the preparation of a tablet compared to conventional Tablets a higher Tensile strength at constant compressive force or the same Has tensile strength at lower compression force. In the Usually a whole tablet has a tensile strength of more than 5 kPa, preferably greater than 10 kPa, more preferably, in particular for use in laundry applications, of more than 15 kPa, more preferably more than 30 kPa and most preferably greater than 50 kPa, especially for use in dishwashing or machine dishwashing applications; and a tensile strength of less than 300 kPa, preferably from less than 200 kPa, more preferably less than 100 kPa, still more preferably less than 80 kPa, and most preferably from less than 60 kPa. Indeed should the tablets, in the case of laundry application, less compressed than, for example, in the case of dishwashing applications, being the resolution is achieved faster, so that the tensile strength in a laundry application preferably less than 30 kPa.

This allows the production of tablets or layers, their strength and mechanical resistance with the strength and mechanical Resistance of conventional Tablets is comparable while you get a tablet or layer that less densifies is and dissolves faster. Because the connection is strong soluble is, will as well the resolution the tablet or layer further simplified, resulting in a synergy results in the simplified dissolution of a tablet according to the invention leads.

Preparation of the tablets

The Tablet can comprise several layers. For the purpose of manufacturing For a single layer, the layer itself can be considered as a tablet become.

Detergent tablets can simply by mixing together 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. Liquid ingredients, For example, surfactant or suds suppressor may be conventional Way into the solid particulate Components are included.

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. Preferably become the tablets of the invention compressed with a force of less than 100,000 N, more preferably less than 50,000 N, even more preferably less than 5,000 N and most preferably less than 3000 N. In fact, the most preferred embodiment one for washing clothes suitable tablet, which is compressed with a force of less than 2500 N. was, but tablets for dishwashers can for example, also considered be such tablets for dishwashers stronger be pressed together as detergent tablets.

The particulate material used to make a tablet may be prepared by any dispersion or granulation process. 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 Ingredients of the particulate Materials can by any conventional Mixtures are mixed. The batch is, for example, suitable in a concrete mixer, nauta mixer, belt mixer or any others. Alternatively, the mixing process may be carried out continuously, by measuring all ingredients by weight and placing on a conveyor belt given and mixed in one or more drums or mixers become. Non-gelling binder can affect the mixture of some, or all components of the particulate matter. Other liquid Ingredients can also, either separately or premixed, on the ingredient mixture be sprayed on. For example, you can Perfumes and muds be sprayed by optical brighteners. So the mixture becomes less sticky, after spraying the binder, preferably towards the end of the process, a finely divided solvent (Dusts such as zeolites, carbonates, silicas) to the particulate material added become.

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 produced according to this invention preferably have a diameter between 20 mm and 60 mm, preferably at least 35 and up to 55 mm, and a weight between 25 and 100 g. The ratio of height to diameter (or width) of the tablets is preferably greater than 1: 3, more preferably greater than 1: 2. The compaction pressure used to make these tablets may not exceed 100,000 kN / m ² , preferably not exceeding 30000 kN / m ² , more preferably not exceeding 5000 kN / m ² , even more preferably 3000 kN / m ² and most preferably it must not exceed 1000 kN / m ² . In a preferred embodiment of the invention, the tablet has a density of at least 0.9 g / cm ^3, more preferably at least 1.0 g / cm ³ and preferably less than 2.0 g / cm ^3, more preferably less than 1.5 g / cm ³ , more preferably less than 1.25 g / cm ^3, and most preferably less than 1.1 g / cm ³ .

multilayer Tablets are usually formed in rotary presses by the matrices of each layer in succession in matrix Kraftfüllkolben are given. As the process progresses, the matrix layers become then in the stations of precompression and compression stages pressed together to form the multilayer tablet. For some rotary presses, it is also possible to use the first fed layer to compress before the whole tablet is compressed.

Hydrotrope compound

• 1. Es wird eine Lösung hergestellt, die 25 Gew.-% der speziellen Verbindung und 75 Gew.-% Wasser umfasst.
• 2. Danach wird Octansäure in einem Verhältnis von 1,6 Mal das Gewicht der speziellen Verbindung in der Lösung zu der Lösung gegeben, wobei die Lösung bei einer Temperatur von 20°Celsius vorliegt. Die Lösung wird in einem Sotax-Becherglas mit einem Rührer mit einem Unterwasserpropeller gemischt, wobei sich der Propeller ungefähr 5 mm über dem Boden des Bechers befindet, wobei der Mischer auf eine Drehgeschwindigkeit von 20,9 rad/s (200 U/min) eingestellt ist.
• 3. Die spezielle Verbindung ist hydrotrop, wenn die Octansäure vollständig löslich gemacht ist, d. h. wenn die Lösung nur eine Phase umfasst, wobei die Phase eine flüssige Phase ist.

A highly soluble compound having a cohesive effect may be included in a detergent tablet, which compound is also a hydrotrope. Such a hydrotrope can generally be used to promote surfactant dissolution by avoiding gelation. A specific compound is defined as hydrotrope as follows (see SE Friberg and M. Chiu, J. Dispersion Science and Technology, 9 (5 & 6), pages 443-457, (1988-1989)):

• 1. A solution is prepared comprising 25% by weight of the specific compound and 75% by weight of water.
• 2. Thereafter, octanoic acid in a ratio of 1.6 times the weight of the specific compound in the solution is added to the solution, the solution being at a temperature of 20 ° Celsius. The solution is mixed in a Sotax beaker with a stirrer with an underwater propeller with the propeller about 5 mm above the bottom of the beaker with the mixer set at a rotational speed of 20.9 rad / s (200 rpm) is.
• 3. The particular compound is hydrotrope when the octanoic acid is completely solubilized, ie when the solution comprises only one phase, the phase being a liquid phase.

It It should be noted that in a preferred embodiment the invention, the hydrotrope compound under operating conditions between 15 and 60 ° Celsius a flowable material is particulate matter.

Hydrotropic compounds include the following compounds:
A list of commercially available hydrotrope compounds can be found in McCutcheon's Emulsifiers and Detergents, published by the McCutcheon division of Manufacturing Confectioners Company.

• 1. Nichtionische hydrotrope Verbindungen mit der folgenden Struktur:
  
  worin R eine C8-C10-Alkylkette ist, x im Bereich von 1 bis 15, y von 3 bis 10 ist.
• 2. Anionische hydrotrope Verbindungen, wie Alkalimetallarylsulfonate. Dazu gehören Alkalimetallsalze von Benzoesäure, Salicylsäure, Benzolsulfonsäure und ihre vielen Derivate, Naphthoesäure und verschiedene hydroaromatische Säuren. Beispiele dafür sind Natrium-, Kalium- und Ammoniumbenzolsulfonatsalze, die abgeleitet sind von Toluolsulfonsäure, Xylolsulfonsäure, Cumolsulfonsäure, Tetralinsulfonsäure, Naphthalinsulfonsäure, Methylnaphthalinsulfonsäure, Dimethylnaphthalinsulfonsäure, Trimethylnaphthalinsulfonsäure= Zu anderen Beispielen gehören Salze von Dialkylbenzolsulfonsäure, wie Salze von Diisopropylbenzolsulfonsäure, Ethylmethylbenzolsulfonsäure, Alkylbenzolsulfonsäure mit einer Alkylkettenlänge mit 3 bis 10, (bev. 4 bis 9), lineare oder verzweigte Alkylsulfonate mit einer Alkylkette mit 1 bis 18 Kohlenstoffen.
• 3. Lösungsmittelhydrotropika, wie alkoxylierte Glycerine und alkoxylierte Glyceride, Ester von alkoxylierten Glycerinen, alkoxylierte Fettsäuren, Ester von Glycerin, Polyglycerinester. Bevorzugte alkoxylierte Glycerine haben die folgende Struktur:
  
  worin l, m und n jeweils eine Zahl von 0 bis ungefähr 20 sind, wobei l + m + n = von ungefähr 2 bis ungefähr 60, vorzugsweise von ungefähr 10 bis ungefähr 45, und R für H, CH₃ oder C₂H₅ steht Bevorzugte alkoxylierte Glyceride haben die folgende Struktur:
  
  worin R1 und R2 jeweils C_nCOO oder -(CH2CHR₃-O)₁-H sind, worin R₃ = H, CH₃ oder C₂H₅ und 1 eine Zahl von 1 bis ungefähr 60 ist, n eine Zahl von ungefähr 6 bis ungefähr 24 ist.
• 4. Polymere hydrotrope Verbindungen, wie die in EP636687 beschriebenen:
  
  worin E eine hydrophile funktionelle Gruppe ist, R H oder eine C1-C10-Alkylgruppe ist oder eine hydrophile funktionelle Gruppe ist; R1 H, eine Niederalkylgruppe oder eine aromatische Gruppe ist, R2 H oder eine cyclische Alkyl- oder eine aromatische Gruppe ist. Das Polymer hat in der Regel ein Molekulargewicht zwischen ungefähr 1000 und 1.000.000.
• 5. Hydrotrope Verbindungen ungewöhnlicher Struktur, wie 5-Carboxy-4-hexyl-2-cyclohexen-1-yloctansäure (Diacid^®)

Suitable connections also include:

• 1. Nonionic hydrotropes having the structure:
  
  wherein R is a C8-C10 alkyl chain, x is in the range of 1 to 15, y is 3 to 10.
• 2. Anionic hydrotrope compounds, such as alkali metal aryl sulphonates. These include alkali metal salts of benzoic acid, salicylic acid, benzenesulfonic acid and its many derivatives, naphthoic acid and various hydroaromatic acids. Examples thereof include sodium, potassium and ammonium benzenesulfonate salts derived from toluenesulfonic acid, xylenesulfonic acid, cumene sulfonic acid, tetralinsulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, trimethylnaphthalenesulfonic acid. Other examples include salts of dialkylbenzenesulfonic acid such as salts of diisopropylbenzenesulfonic acid, ethylmethylbenzenesulfonic acid, alkylbenzenesulfonic acid having an alkyl chain length from 3 to 10 (Examples 4 to 9), linear or branched alkyl sulfonates having an alkyl chain of 1 to 18 carbons.
• 3. Solvent hydrotropics, such as alkoxylated glycerols and alkoxylated glycerides, esters of alkoxylated glycerols, alkoxylated fatty acids, esters of glycerol, polyglycerol esters. Preferred alkoxylated glycerols have the following structure:
  
  wherein each of l, m and n is a number from 0 to about 20, where l + m + n = from about 2 to about 60, preferably from about 10 to about 45, and R is H, CH ₃ or C ₂ H ₅ Preferred alkoxylated glycerides have the following structure:
  
  wherein R ₁ and R ₂ are each C _n COO or - (CH 2 CHR ₃ -O) ₁ -H, wherein R ₃ = H, CH ₃ or C ₂ H ₅ and 1 is a number from 1 to about 60, n is a number from about 6 to about 24.
• 4. Polymers hydrotropic compounds, such as those in EP636687 described:
  
  wherein E is a hydrophilic functional group, R is H or a C 1 -C 10 alkyl group or is a hydrophilic functional group; R1 is H, a lower alkyl group or an aromatic group, R2 is H or a cyclic alkyl or an aromatic group. The polymer typically has a molecular weight of between about 1,000 and 1,000,000.
• 5. Hydrotrope of unusual structure such as 5-carboxy-4-hexyl-2-cyclohexen-1-yloctansäure (Diacid ^®)

The Use of such a compound in the invention would be dissolution rate continue to increase the tablet, because a hydrotrope compound, for example, the dissolution of Surfactants relieved. Such a compound can be made from a mixture or formed from a single compound.

tensile strenght

For the purpose the measurement of the tensile strength of a layer, the layer as Tablet itself to be considered.

Depending on the composition of the starting material and the shape of the tablets the compression force used can be adjusted so that the tensile strength and the decomposition time in the washing machine is not impaired become. This method can be used to prepare homogeneous or layered tablets any size or Form to be used.

In a cylindrical tablet, the tensile strength corresponds to the diametric breaking stress (DFS), which is one way of expressing the strength of a tablet or layer, and is determined by the following equation: Tensile strength = 2 F / πDt 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 is the diameter of the tablet or layer and t is the thickness of the tablet or layer. For a non-round tablet, πD can be easily replaced by the perimeter of the tablet.

(Method Pharmaceutical Dosage Forms: Tablets, Volume 2, pages 213 to 217). A tablet with a diametrical fracture stress of less than 20 kPa is considered brittle viewed and leads likely to cause the consumer some broken tablets receives. A diametric breaking stress of at least 25 kPa is preferred.

This applies equally for not cylindrical tablets for determining the tensile strength, wherein the height of Tablet vertical cross-section is not round and where the force in a direction perpendicular to the direction of the height of the tablet and perpendicular to the tablet side, the side being vertical to not round cross-section.

tablet dispensing

The release rate of a detergent tablet can be determined as follows:
Two tablets, each 50 g denomination, are weighed and then placed in the dispenser of a Bauknecht ^® WA9850 (Baucknecht ^® WA9850) washing machine. The water supply of the washing machine is set to a temperature of 20 ° C and a hardness of 21 grains per gallon, the flow rate for the water inlet of the dispenser set to 8 l / min. The concentration of tablet residues in the dispenser is checked by turning on the washing machine and setting the wash cycle to wash program 4 (white / color wash, short program). The percentage of the delivery back status is determined as follows: % Dispensing = residue weight × 100 / original tablet weight

The Amount of residues will by tenfold repetition of the process and calculating an average amount of residue determined from the ten individual measurements. In this stress test becomes a backlog from 40% of the initial one Tablet weight considered acceptable. A residue less than 30% is preferred and less than 25% becomes more prefers.

It should be noted that the measurement of water hardness is given in the traditional unit "grain per 3.8 l (gallon)", with 0.001 mol per liter = 7.0 grain per 3.8 l (gallon), the concentration of Represents Ca ²⁺ ions in the solution.

effervescent

detergent tablets can further comprising an effervescent 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 the various particles or compacted and not as separate particles.

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.

One further aid for the decomposition could through the use of compounds such as sodium acetate or urea to be provided. A list of suitable tools for decomposition can also be found in Pharmaceutical Dosage Forms: Tablets, Volume 1, second Edition, edited by H.A. Lieberman et al., ISBN 0-8247-8044-2, to find.

coating

The Strength of a tablet can be achieved by producing a coated Tablet be improved, wherein the coating is an uncoated Tablet surrounds the mechanical properties of the tablet further improved while the resolution maintained or further improved.

This applies advantageously for multilayer tablets, the mechanical properties of a more elastic Layer over the coating can be transferred to the rest of the tablet, causing the Advantage of the coating with the advantage of the more elastic layer combined. Indeed become mechanical constraints transmitted through the coating, whereby the mechanical integrity the tablet is improved.

In one embodiment of the present invention, the tablets may then be coated so that the tablet does not absorb moisture or absorb moisture only very slowly. In addition, the coating is strong, so that moderate mechanical shock to which the tablets are exposed during handling, packaging and transport will cause very little breakage or abrasion. Finally, the coating is preferably brittle so that the tablet breaks up quickly when thicker is exposed to mechanical shocks. In addition, it is advantageous if the coating material is dissolved under alkaline conditions or simply emulsified by surfactants. This helps to avoid the problem of visible residue in the window of a front loading washing machine during the washing cycle and also prevents the deposition of undissolved particles or pieces of coating material on the laundry load.

Water is measured as described in Test Protocol ASTM E1148-87 entitled "Standard Test Method for Measurements of Aqueous Solubility ".

The Breaking the coating during washing is done by adding a decomposer improved to the coating. This decomposing active ingredient swells as soon as he comes in contact with water comes and breaks the coating into small pieces. This improves the resolution the coating in the wash solution. In general, the decomposer is in a concentration of up to 30% by weight, preferably between 5% and 20% by weight, most preferably between 5 and 10% by weight in the coating melt suspended.

A Clay mineral compound as described above is a decomposer for this purpose Use.

Other possible Decomposers, in addition to the clay decomposers can be used in the Handbook of Pharmaceutical Excipients (1986). Examples Suitable disintegrating agents include starch: natural, modified or pre-gelled Strength, Natriumstärkegluconat; Rubber: Agar-agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; Croscarmylose sodium, crospovidone, cellulose, carboxymethyl cellulose, alginic acid and their salts, including Sodium alginate, silicon dioxide, clay, polyvinylpyrrolidone, soy polysaccharide, Ion exchange resins, polymers containing cationic groups (e.g. quaternary Ammonium groups), amine-substituted polyacrylates, polymerized cationic amino acids, like poly-L-lysine, Polyallylamine hydrochloride) and mixtures thereof.

Preferably the coating material has a melting point of at least 40 ° C, preferably from 40 ° C up to 200 ° 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.

Preferably is the coating material that has a melting point of at least Has 40 ° C, an acid. acids with a melting temperature of at least 40 ° C, for example, dicarboxylic acids. Especially 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. Most preferred is adipic acid.

More Preferably, the coating comprises a crystallized structure. Under crystallized is to be understood that the coating a Includes material that is solid at ambient temperature (25 ° C) and has a structure that has a certain order. These is usually by ordinary Crystallography techniques, e.g. B. X-ray analysis, on the material to recognize yourself. In a more preferred embodiment the material that forms the crystallized structure, not or only partially with the above-mentioned optional ingredient, at 25 ° C liquid is crystallized. Indeed it is preferred that the optional ingredient at 25 ° C in the crystalline structure of the coating remains liquid to the structure flexibility and durability to confer against mechanical stress. Most preferably the aforementioned acid with a melting temperature of at least 40 ° C a crystallized structure.

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 are practically usable. Preferably an acid with a melting point of more than 90 ° C, like azelaic acid, sebacic, Dodecanedioic acid. For the However, the purpose of the present invention is the use of sebacic acid less preferred because they are detrimental to the resulting product Gives off smell. It has according to the invention it turned out that an acid having a melting point of more than 145 ° C, such as adipic acid, especially was found suitable.

The coating can be applied in various ways. Two preferred Beschich ting methods are a) coating with a molten material and b) coating with a solution of the 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 is applied as a solution and the solvent dried to a coherent Leave a coating. The essentially insoluble material can for example by spraying or dipping on the tablet. When the melted Material is sprayed on the tablet, it solidifies usually fast to form a coherent coating. When tablets are immersed in the molten material and then taken out be leads turn the fast cooling to a rapid solidification of the coating material. During the Solidification phase experiences the coating has some internal stress (eg shrinkage when cooling down) and external voltage (eg tablet relaxation). This causes probably some cracks in the structure, like edge splintering, if the coating material is too brittle to this mechanical To withstand tension, as is the case when using a coating consists only of components that are solid at 25 ° C. It is because of that preferred that the coating comprises a component which at 25 ° C liquid is. Thus, it is believed that this liquid component of the coating allows better withstand and absorb mechanical stress, by making the coating structure more flexible. The part, at 25 ° C liquid is preferably in proportions of less than 10 wt .-% of Coating, more preferably less than 5% by weight and most preferably less than 3% by weight to the coating materials added. The ingredient, which is at 25 ° C liquid is preferably in proportions of more than 0.1% by weight of the coating, more preferably more than 0.3% by weight and most preferably from more than 0.5 wt .-% added to the coating materials.

To Examples of optional ingredients that are liquid at 25 ° C include polyethylene glycols, Thermal oil, silicon oil, ester of dicarboxylic acids, Monocarboxylic acids, Paraffin, triacetin, perfumes or alkaline solutions. For example, particularly good results were obtained using NaOH solution as an alkaline solution achieved.

It it is preferred that the structure of the ingredients which are liquid at 25 ° C, close to the material that forms the crystallized structure, so that the structure is not overly interrupted becomes.

In another embodiment For example, the optional ingredient that is liquid at 25 ° C can be beneficial a functionality washing clothes have, for example silicone oil, the foam suppression benefits or perfume oil. If present, the perfume oil may be the perfume composition be as described herein or another fragrance composition than those already in the tablet, provided that it contains less than 0.6% by weight of Schiff's bases.

The Coating may also contain other materials than the optional ingredient, at 25 ° C is liquid, include. Thus, it is further preferred to add reinforcing Fibers to the coating to further strengthen the structure.

In a most preferred embodiment, the crystallized structure is made from adipic acid, wherein the component which is liquid at 25 ° C is available under the designation Coasol ^™ from Chemoxy International and is a mixture of the diisobutyl esters of glutaric, succinic and adipic acid , The advantage of using this ingredient is the good dispersion in adipic acid to provide flexibility. It should be noted that decomposition of adipic acid is further enhanced by the adipate content of Coasol ^™ .

According to a preferred embodiment of the invention, the coating comprises an acid having a melting temperature of at least 145 ° C, such as adipic acid, and a clay, such as bentonite clay, which clay is used as a disintegrating agent and, moreover, more advantageous to the structure of adipic acid for water penetration and thus to improve the dispersion of adipic acid in an aqueous medium. Preferred are clays that are present in the coating and have a particle size of less than 75 microns, more preferably less than 53 microns, to achieve the desired effect on the structure of the acid. Preferred clays are bentonite clays. In fact, the acid has such a melting point that conventional cellulosic disintegrants undergo thermal degradation during the coating process, while such clays are found to be more heat stable. Further, conventional cellulosic disintegrants, such as Nymcel ^™ , show a brown coloration at these temperatures.

In another preferred embodiment, the coating further comprises reinforcing fibers. It has been found that such fibers further improve the resistance of the coating to stress and minimize the occurrence of chipping defects. Such fibers preferably have a length of at least 100 microns, more preferably at least 200 microns, and most preferably at least 250 microns to allow structural reinforcement. Such fibers preferably have a length of less than 500 microns, more preferably less than 400 microns, and most preferably less than 350 microns, so as not to interfere with dispersion of the coating in an aqueous medium. Materials which can be used for these fibers include viscose rayon, natural nylon, synthetic nylon (type 6 and 6,6 polyamides), acrylic acid, polyester, cotton and derivatives of cellulose such as CMC. Most preferred is a cellulosic material available under the trademark Solka-Floc ^™ from Fibers Sales & Development. It should be noted that such fibers do not normally require pre-compression to enhance the coating structure. Such fibers are preferably added in a concentration of less than 5% by weight of the coating, more preferably less than 3% by weight. Such fibers are preferably added in a concentration greater than 0.5% by weight of the coating, more preferably greater than 1% by weight.

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.

tablet coatings are very hard and give the tablet extra strength.

method

• (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 in Form einer Schmelze vorliegt;
• (c) Verfestigenlassen des geschmolzenen Beschichtungsmaterials;

dadurch gekennzeichnet, dass die Beschichtung einen Ton umfasst.A preferred method for producing a tablet according to the invention comprises the following steps:

• (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 comprises a clay.

• (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 in einem Lösungsmittel oder Wasser gelöst ist;
• (c) Verdampfenlassen des Lösungsmittels oder des Wassers;

dadurch gekennzeichnet, dass die Beschichtung einen Ton umfasst.Another preferred method for producing a tablet according to the invention comprises the following steps:

• (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 dissolved in a solvent or water;
• (c) allowing the solvent or water to evaporate;

characterized in that the coating comprises a clay.

The Compounds mentioned above for a product are disclosed are advantageously in a packaging system packed up.

A packaging system can be formed from a layer of flexible material. Materials suitable for use as an elastic layer include single layer, coextruded or layer pressed films. Such films may include various ingredients such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate. Preferably, the packaging system made of a film made of coextruded polyethylene and bi-oriented polypropylene having a MVTR of less than 5 g / day / m ² is composed. The MVTR of the packaging system is preferably less than 10 g / day / m ² , more preferably less than 5 g / day / m ² . The film (2) can have different thicknesses. The thickness should generally be between 10 and 150 μm, preferably between 15 and 120 μm, more preferably between 20 and 100 μm, even more preferably between 25 and 80 μm and most preferably between 30 and 40 μm.

A packaging material preferably comprises a barrier layer normally found in low oxygen transmission rate packaging materials, typically less than 300 cm ³ / m ² / day, preferably less than 150 cm ³ / m ² / day, more preferably from less than 100 cm ³ / m ² / day, even more preferably less than 50 cm ³ / m ² / day, and most preferably less than 10 cm ³ / m ² / day. Typical materials having such barrier properties include bioriented polypropylene, polyethylene terephthalate, nylon, poly (ethylene vinyl alcohol), or laminated materials comprising any of these, as well as SiOx (silicon oxides), or metal foils such as aluminum foils. Such a packaging material can have a favorable influence on the stability of the product, for example during storage.

The packaging methods used usually include the packaging methods used in WO92 / 20593 including horizontal packaging or full wrap. Using such methods, a longitudinal seal is provided, which may be a rib seal or an overlapping seal, after which a first end of the packaging system is closed with a first end seal, followed by sealing the second end with a second end seal. The packaging system may be a reclosing agent, as in WO92 / 20593 described include. In particular, a twist, a cold seal or an adhesive are particularly suitable. Indeed, in a position adjacent to the second end of the packaging system, a cold seal strip or strip of adhesive may be applied to the surface of the packaging system so that this strip can provide both the initial sealing and resealing of the packaging system. In such a case, the adhesive or cold seal may correspond to a region having a cohesive surface, ie, a surface that adheres only to another cohesive surface. Such reclosing devices may also include intermediate pieces that prevent unwanted sticking. Such spacers are in WO 95/13225 , published May 18, 1995. There may also be several intermediate pieces and a plurality of adhesive strips. The main requirement is that the transfer between the exterior and the interior of the package should be minimal, even after the first opening of the packaging system. A cold seal may be used, particularly a cold seal grid pattern, where the cold seal is designed to facilitate opening of the package.

Examples

The following is a non-limiting example of a suitable perfume composition A used in the following nonlimiting detergent tablets Examples 1 and 2 according to the present invention: Perfume ingredient % in fragrance composition geraniol 5.0 Citronellol 5.0 4-t-butylcyclohexyl acetate 5.0 phenylethyl 10.0 Hexahydro-4,7-methanoinden-5-yl acetate, commercially available under the 6.0 Trade name Cyclacet citronellyl 2.5 Geranylacetat 2.5 hexyl cinnamic aldehyde 4.5 Parahydroxyphenylbutanon 3.0 PT Bucinal 24.0 Methyl 10.0 Rosalva 2.0 methyldihydrojasmonate 7.0 undecylenic 0.5 methyl isobutenyl 1.0 Ortho-t-butylcyclohexyl 6.0 hexyl salicylate 6.0 All in all 100.0

In the following detergent examples 1-6 used Abbreviations

• Anionische Agglomerate 1 umfassen 40% anionisches Tensid, 27% Zeolith und 33% Carbonat.
• Anionische Agglomerate 2 umfassen 40% anionisches Tensid, 28% Zeolith und 32% Carbonat.
• Nichtionisches Agglomerat umfasst 26% nichtionisches Tensid, 6% Lutensit K-HD 96, 40% Natriumacetat wasserfrei, 20% Carbonat und 8% Zeolith.
• Kationische Agglomerate umfassen 20% kationisches Tensid, 56% Zeolith und 24% Sulfat.
• Schichtsilikat umfasst 95% SKS 6 und 5% Silikat.
• Bleichaktivatoragglomerate umfassen 81% TAED, 17% Acryl/Malein-Copolymer (Säureform) und 2% Wasser.
• Ethylendiamin-N,N-dibernsteinsäure-Natriumsalz-/Sulfatteilchen umfassen 58% Ethylendiamin-N,N-dibernsteinsäure-Natriumsalz, 23% Sulfat und 19% Wasser.
• Schaumunterdrücker umfasst 11,5% Silikonöl (von Dow Corning); 59% Zeolith und 29,5% Wasser.
• Bindemittel-Aufsprühsystem umfasst 16 Gew.-% Polymer der folgenden Art:
  
  68 Gew.-%: PEG4000 und 16 Gew.-%: DIES (Natriumdiisoalkylbenzolsulfonat oder Natriumtoluolsulfonat).

In the detergent compositions, the abbreviated component designations have the following meanings:

• Anionic agglomerates 1 include 40% anionic surfactant, 27% zeolite and 33% carbonate.
• Anionic agglomerates 2 include 40% anionic surfactant, 28% zeolite and 32% carbonate.
• Nonionic agglomerate comprises 26% nonionic surfactant, 6% Lutensit K-HD 96, 40% sodium acetate anhydrous, 20% carbonate and 8% zeolite.
• Cationic agglomerates include 20% cationic surfactant, 56% zeolite, and 24% sulfate.
• Phyllosilicate comprises 95% SKS 6 and 5% silicate.
• Bleach activator agglomerates include 81% TAED, 17% acrylic / maleic copolymer (acid form) and 2% water.
• Ethylenediamine N, N-disuccinic acid sodium salt / sulfate particles include 58% ethylenediamine-N, N-disuccinic acid sodium salt, 23% sulfate, and 19% water.
• Suds suppressor comprises 11.5% silicone oil (ex Dow Corning); 59% zeolite and 29.5% water.
• Binder spray system comprises 16% by weight of polymer of the following type:
  
  68% by weight: PEG4000 and 16% by weight: DIES (sodium diisoalkylbenzenesulfonate or sodium toluenesulfonate).

In the following detergent example 7 used abbreviations

In the detergent compositions, the abbreviated component designations have the following meanings: READ: Linear C _11-13 sodium alkylbenzenesulfonate TAS: Natriumtalgalkylsulfat CxyAS: C ₁ -C _{1 -alkylsulfate} C46SAS: Secondary C ₁₄ -C ₁₆ sodium (2,3) alkyl sulfate CxyEzS: C ₁ -C _{1 -alkylsulfate} condensed with z moles of ethylene oxide CxyEz: Predominantly linear primary C _1x -C _{1 -ycohol} condensed with an average of z moles of ethylene oxide QAS: R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) with R ₂ = C ₁₂ -C ₁₄ QAS 1: R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) with R ₂ = C ₈ -C ₁₁ SADS: C ₁₄ -C ₂₂ -sodium alkyldisulfate of the formula 2- (R) .C ₄ H _7. -1,4- (SO ₄ -) ₂ , wherein R = C ₁₀ -C ₁₈ SADE2S: C ₁₄ -C ₂₂ -sodium alkyldisulfate of the formula 2- (R) .C ₄ H _7. -1,4- (SO ₄ -) ₂ , wherein R = C ₁₀ -C ₁₈ , condensed with z moles of ethylene oxide MES: x-sulfomethyl ester of C ₁₈ fatty acid APA: C ₈ -C ₁₀ amidopropyldimethylamine Soap: Linear sodium alkyl carboxylate derived from an 80/20 blend of tallow and coconut fatty acids STS: sodium toluene CFAA: C ₁₂ -C ₁₄ (coco) alkyl-N-methylglucamide TFAA: C ₁₆ -C ₁₈ -alkyl-N-methylglucamide TPKFA: Populated C ₁₆ -C ₁₈ whole cut fatty acids STPP: Anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ 27H ₂ O having a primary particle size in the range of 0.1 to 10 microns (weight expressed on anhydrous basis) NaSKS-6: Crystalline sheet silicate of the formula δ-Na ₂ Si ₂ O ₅ citric acid: Anhydrous citric acid Borat: sodium borate carbonate: Anhydrous sodium carbonate with a particle size between 200 microns and 900 microns bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400 microns and 1200 microns Silicate: Amorphous sodium silicate (SiO ₂ : Na ₂ O = 2.0: 1) Sulfate: Anhydrous sodium sulfate Mg sulfate: Anhydrous magnesium sulfate citrate: Trisodium citrate dihydrate with an activity of 86.4% with a particle size distribution between 425 microns and 850 microns MA / AA: Copolymer of 1: 4 maleic / acrylic acid, average molecular weight about 70,000 MA / AA (1): Copolymer of 4: 6 maleic / acrylic acid, average molecular weight about 10,000 AA: Sodium polyacrylate polymer with average molecular weight of 4,500 CMC: sodium cellulose ethers: Methyl cellulose ethers having a degree of polymerization of 650 available from Shin Etsu Chemicals protease: Proteolytic enzyme having 3.3% by weight of active enzyme sold by NOVO Industries A / S under the trade name Savinase Protease I: Proteolytic enzyme having 4% by weight of active enzyme as in WO 95/10591 described by Genencor Int. Inc. Alcalase: Proteolytic enzyme having 5.3% by weight of active enzyme sold by NOVO Industries A / S cellulase Cellulytic enzyme having 0.23% by weight of active enzyme sold by NOVO Industries A / S under the trade name Carezyme amylase: Amylolytic enzyme having 1.6% by weight of active enzyme sold by NOVO Industries A / S under the trade name Termamyl 120T Amylase II: Amylolytic enzyme as in PCT / US9703635 disclosed lipase: Lipolytic enzyme having 2.0% by weight of active enzyme sold by NOVO Industries A / S under the brand name Lipolase Lipase II: Lipolytic enzyme having 2.0% by weight of active enzyme sold by NOVO Industries A / S under the brand name Lipolase Ultra Endolase®: Endoglucanase enzyme containing 1.5% by weight of active enzyme sold by NOVO Industries A / S PB4: Sodium perborate tetrahydrate of nominal formula NaBO ₂ 3H ₂ O.H ₂ O ₂ PB1: Anhydrous sodium perborate bleach of nominal formula NaBO ₂ H ₂ O ₂ percarbonate: Sodium percarbonate of nominal formula 2Na ₂ CO ₃ 3H ₂ O ₂ DOBS: Decanoyloxybenzenesulfonate in the form of the sodium salt DPDA: diperoxydodecanedioc NOBS: Nonanoyloxybenzenesulfonate in the form of the sodium salt NACA-OBS: (6-nonamidocaproyl) oxybenzene LOBS: Dodecanoyloxybenzenesulfonate in the form of the sodium salt DOBS: Decanoyloxybenzenesulfonate in the form of the sodium salt DORA: decanoyloxybenzoic TAED tetraacetylethylenediamine DTPA: Diethylenetriamine pentaacetic acid DTPMP: Diethylenetriamine penta (methylene phosphonate), marketed by Monsanto under the tradename Dequest 2060 EDDS: Ethylenediamine N, N'-disuccinic acid (S, S) isomer in the form of its sodium salt. Photo Activated: Sulfonated zinc phthalocyanine encapsulated in dextrin soluble polymer of bleach (1) Photo Activated: Sulfonated aluminophthalocyanine encapsulated in dextrin soluble polymer of bleach (2) Brightener 1: Disodium 4,4'-bis (2-sulphostyryl) biphenyl Brightener 2: Disodium 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) -amino) stilbene-2: 2'-disulfonate HEDP: 1,1-hydroxyethane PEGx: Polyethylene glycol with a molecular weight of x (typically 4,000) PEO: Polyethylene oxide with an average molecular weight of 50,000 TEPAE: Tetraethylenepentaamine ethoxylate PVI: Polyvinylimidazole with an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer with an average molecular weight of 60,000 PVNO Polyvinylpyridine N-oxide polymer with an average molecular weight of 50,000 PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole with an average molecular weight of 20,000 QEA: bis ((C ₂ H ₅ O) (C ₂ H ₄ O) _n ) (CH ₃ ) -N ⁺ C ₆ H ₁₂ -N ⁺ - (CH ₃ ) to ((C ₂ H ₅ O) - (C ₂ H ₄ O)) _n , where n = from 20 to 30 PEI: Polyethyleneimine having an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy radicals per nitrogen Sound I: bentonite clay Tone II: Smectite clay Flocculant I: Polyethylene oxide of average molecular weight between 200,000 and 400,000 Flocculant II: Polyethylene oxide of average molecular weight between 400,000 and 1,000,000 Flocculant III: Polymer of acrylamide and / or acrylic acid with average molecular weight between 200,000 and 400,000 SRP I: Anionically end-capped polyester soil release polymer SRP II: Polysaccharide soil release SRP 1: Nonionic endcapped polyester SRP 2: Diethoxylated short poly (1,2-propylene terephthalate) block polymer Silicone antifoam: Polydimethylsiloxane foam control agent with siloxane-oxyalkylene copolymer as dispersant, with a ratio of foam control agent to dispersant of 10: 1 to 100: 1. Opacifiers: Hydrous monostyrene latex blend sold by BASF Aktiengesellschaft under the trade name Lytron 621 Wax: paraffin wax Stains: Colored carbonate salt or organic carboxylic acid salt

example 1

• i) A detergent base powder of Composition A was prepared as follows: The entire particulate material of the base composition was mixed together in a mixing drum or spray drum to form a homogeneous particulate mixture, except for the binder spray system, fluorescer or brightener, and photobleach Zinc phthalocyanine sulphonate. The particulate mixture was then divided into two equal parts, one part to make a white layer, another part to make a green layer. The material of the white layer is obtained by spraying the brightener or fluorescer together with half of the binder. The material of the green layer is obtained by spraying the photobleach zinc phthalocyanine sulfonate together with the rest of the binder. The layers were then processed independently in a Lödige KM ^600® .
• ii) Using a Bonals ^® -Rotationspresse were both matrices filled in two independent Kraftfüllkolben. Both layers are compressed together in the pre-compression and compression stations to form a two-layered tablet.
• iii) In this particular example, the tablets have one square cross section of 45 mm side, a height of 24 mm and a weight of 45 g. The height of the green lower layer corresponded 50% of the total height the tablet. The tensile strength of the uncoated tablets was 13 kPa.
• iv) The tablet was then treated with 2.5 g of the coating, the from 89 wt .-% adipic acid and 10 wt .-% bentonite clay of CSM and 1 wt .-% ethane-1-hydroxydiphosphonat was formed, coated.

composition A (%) anionic Agglomerates 1 9.1 anionic Agglomerates 2 22.5 nonionic agglomerates 9.1 cationic agglomerates 4.6 phyllosilicate 9.7 sodium 12.2 Bleach 6.1 sodium 7.67 EDDS / Sulphate 0.5 Tetrasodium salt of hydroxyethanediphosphonic acid 0.6 soil release 0.3 fluorescent agents 0.2 Zinc phthalocyanine sulphonate 0.03 soap powder 1.2 Suds suppressors 2.8 citric acid 5.5 protease 1 lipase 0.35 cellulase 0.2 amylase 1.1 Binder spray- 4.75 perfume for spraying 0.5

Example 2

• i) A detergent base powder of Composition A was prepared as follows: The entire particulate material of the base composition was mixed together in a mixing drum or spray drum to form a homogeneous particulate mixture, except for the binder spray system, fluorescer or brightener, and photobleach Zinc phthalocyanine sulphonate. The particulate mixture was then divided into two equal parts, one part to make a white layer, another part to make a green layer. The material of the white layer is obtained by spraying the brightener or fluorescer together with half of the binder. The material of the green layer is obtained by spraying the photobleach zinc phthalocyanine sulfonate together with the rest of the binder. The layers were then processed independently in a Lödige KM ^600® .
• ii) Using a Bonals ^® -Rotationspresse were both matrices filled in two independent Kraftfüllkolben. Both layers are compressed together in the pre-compression and compression stations to form a two-layered tablet.
• iii) In this particular example, the tablets have one square cross section of 45 mm side, a height of 24 mm and a weight of 45 g. The height of the green lower layer corresponded 50% of the total height the tablet. The tensile strength of the uncoated tablets was 13 kPa.
• iv) The tablet was then treated with 2.5 g of the coating, the from 89% by weight of adipic acid and 10 wt .-% bentonite clay of CSM and 0.5 wt .-% ethane-1-hydroxydiphosphonat and 0.5% by weight of diethylenetriamine-penta (methylenephosphonate) was coated.

Example 3

• i) A detergent base powder of composition A was prepared as follows: the whole Particulate material of the base composition was mixed together in a mixing drum or a spray drum to form a homogeneous particulate mixture, except for the binder spray system, the fluorescer or brightener, and the photobleach zinc phthalocyanine sulfonate. The particulate mixture was then divided into two equal parts, one part to make a white layer, another part to make a green layer. The material of the white layer is obtained by spraying the brightener or fluorescer together with half of the binder. The material of the green layer is obtained by spraying the photobleach zinc phthalocyanine sulfonate together with the rest of the binder. The layers were then processed independently in a Lödige KM ^600® .
• ii) Using a Bonals ^® -Rotationspresse were both matrices filled in two independent Kraftfüllkolben. Both layers are compressed together in the pre-compression and compression stations to form a two-layered tablet.
• iii) In this particular example, the tablets have one square cross section of 45 mm side, a height of 24 mm and a weight of 45 g. The height of the green lower layer corresponded 50% of the total height the tablet. The tensile strength of the uncoated tablets was 13 kPa.
• iv) The tablet was then treated with 2.5 g of the coating, the from 89 wt .-% adipic acid and 10 wt .-% bentonite clay of CSM and 0.5 wt .-% ethane-1-hydroxydiphosphonat and 0.5% by weight of diethylenetriamine-penta (methylenephosphonate) was coated.

Example 4

• i) A detergent base powder of composition A was prepared as follows: The entire particulate material of base composition A was mixed together in a mixing drum or a spray drum to form a homogeneous particulate mixture. Then the binder system was sprayed on. The powder was then processed in a Lödige KM ^600® .
• ii) Using a Instron ^® -Labortischpresse detergent powder was filled in the nozzle. The powder was compressed with such a force that the tensile strength of the tablet was 10 kPa.
• iii) In this particular example, the tablets have one Diameter of 54 mm side, a height of 24 mm and a weight of 45 g.
• iv) The tablet was then treated with 2.5 g of the coating, the from 90 wt .-% adipic acid and 10 wt.% bentonite clay was formed by CSM.

The tablet was then treated with 2.5 grams of the coating consisting of 77 weight percent adipic acid, 18.5 weight percent bentonite clay and 1 weight percent Coasol ^™ and 2.5 weight percent NaOH (1M) and 1 wt .-% ethane-1-hydroxydiphosphonat was formed, coated.

Example 5

• i) A detergent base powder of composition A was prepared as follows: The entire particulate material of base composition A was mixed together in a mixing drum or a spray drum to form a homogeneous particulate mixture. Then the binder system was sprayed on. The powder was then processed in a Lödige KM ^600® .
• ii) Using a Instron ^® -Labortischpresse detergent powder was filled in the nozzle. The powder was compressed with such a force that the tensile strength of the tablet was 10 kPa.
• iii) In this particular example, the tablets have one Diameter of 54 mm side, a height of 24 mm and a weight of 45 g.

The tablet was then coated with 2.5 grams of the coating formed from 88 weight percent adipic acid, 10 weight percent bentonite clay and 1 weight percent Coasol ^™ and 1 weight percent ethane-1-hydroxy diphosphonate ,

Example 6

• i) A detergent base powder of composition A was prepared as follows: The entire particulate material of base composition A was mixed together in a mixing drum or a spray drum to form a homogeneous particulate mixture. Then the binder system was sprayed on. The powder was then processed in a Lödige KM ^600® .
• ii) Using a Instron ^® -Labortischpresse detergent powder was filled in the nozzle. The powder was with compressed such that the tensile strength of the tablet was 10 kPa.
• iii) In this particular example, the tablets have one Diameter of 54 mm side, a height of 24 mm and a weight of 45 g.
• iv) The tablet was then treated with 2.5 g of the coating consisting of 86% by weight of adipic acid, 10% by weight of bentonite clay and 1% by weight of Coasol ^™ and 2% by weight of Solka-Floc ^™ 1016 and 0 , 5 wt .-% ethane-1-hydroxy disphosphonate and 0.5 wt .-% diethylene triamine penta (methylene phosphonate) was formed coated.

Example 7

It follow detergent compositions according to the invention, those so or instead of composition A, described above, in each of Examples 1-6 can be used.

In the following examples, all concentrations are given in weight percent of the composition: B C D e Blown powder Sound I or II 7.0 10.0 6.0 2.0 Flocculant I or II 0.3 1.0 1.0 0.5 READ 16.0 5.0 11.0 6.0 TAS - 5.0 - 2.0 Zeolite A - 20.0 - 10.0 STPP 24.0 - 14.0 - sulfate - 2.0 - - MA / AA - 2.0 1.0 1.0 silicate 4.0 7.0 3.0 - CMC 1.0 - 0.5 0.6 brighteners 0.2 0.2 0.2 0.2 sodium 10.0 10.0 20.0 - DTPMP 0.4 0.4 0.2 - spray brighteners 0.02 - - 0.02 C45E7 or E9 - - 2.0 1.0 C45E3 or E4 - - 2.0 4.0 perfume 0.5 - 0.5 0.2 Silicone antifoam 0.3 - - - dry additives QEA - - - 1.0 HEDP / EDDS 0.3 - - - sulfate 2.0 - - - carbonate 20.0 13.0 15.0 24.0 citric acid 2.5 - - 2.0 QAS - - 0.5 0.5 SKS-6 3.5 - - 5.0 percarbonate - - - 9.0 PB4 - - 5.0 NOBS - - - 1.3 TAED - - 2.0 1.5 protease 1.0 1.0 1.0 1.0 lipase - 0.4 - 0.2 amylase 0.2 0.2 0.2 0.4 brighteners 0.05 - - 0.05 perfume 1.0 0.2 0.5 0.3 stains 1.2 0.5 2.0 - Other / minor components up to 100%

There follow compositions suitable for use herein. F G H I J K L C ₁₁ -C ₁₃ Sodium alkylbenzenesulfonate 12.0 16.0 23.0 19.0 18.0 20.0 16.0 C ₁₄ -C _{1 5} -Natriumalkoholsulfat 4.5 - - - 4.0 C ₁₄ -C ₁₅ alcohol ethoxylate (0.5) sulfate - - - - - C ₁₄ -C ₁₅ -alcohol ethoxylate (3) sulfate - - 2.0 - 1.0 1.0 1.0 C ₁₄ -C ₁₅ sodium alcohol ethoxylate 2.0 2.0 - 1.3 - - 5.0 Quaternary C ₉ -C ₁₄ -alkyldimethylhydroxyethyl ammonium salt - - 1.0 0.5 2.0 tallow - - - - 1.0 Tallow alcohol ethoxylate (50) - - - - - - - Sodium tripolyphosphate / Zeolite 23.0 25.0 14.0 22.0 20.0 10.0 20.0 sodium 25.0 22.0 35.0 20.0 28.0 41.0 30.0 Sodium polyacrylate (45%) 0.5 0.5 0.5 0.5 - - - Sodium polyacrylate / -malest polymer - - 1.0 1.0 1.0 2.0 0.5 Sodium silicate (1: 6 ratio NaO / SiO ₂ ) (46%) 3.0 6.0 9.0 8.0 9.0 6.0 8.0 sodium sulphate - - - - - 2.0 3.0 Sodium perborate / percarbonate 5.0 5.0 10.0 - 3.0 1.0 - Poly (ethylene glycol), MW 4000 (50%) 1.5 1.5 1.0 1.0 - - 0.5 sodium 1.0 1.0 1.0 - 0.5 0.5 0.5 citric acid - - - - - - - NOBS / DOBS - 1.0 - - 1.0 0.7 - TAED 1.5 1.0 2.5 - 3.0 0.7 - SRP 1.5 1.5 1.0 1.0 - 1.0 - Sound I or II 5.0 6.0 12.0 7.0 10.0 4.0 3.0 Flocculant I or III 0.2 0.2 3.0 2.0 0.1 1.0 0.5 Humectants 0.5 1.0 0.5 1.0 0.5 0.5 - wax 0.5 0.5 1.0 - - 0.5 0.5 humidity 7.5 7.5 6.0 7.0 5.0 3.0 5.0 magnesium sulfate - - - - - 0.5 1.5 complexing - - - - 0.8 0.6 1.0 Enzymes, including amylase, cellulase, protease and lipase - - - - 2.0 1.5 2.0 stains 2.5 4.1 4.2 4.4 5.6 5.0 5.2 Minor ingredients, eg. Perfume, PVP, PVPVI / PVNO, 2.0 1.0 1.0 1.0 2.5 1.5 1.0 Brightener, photobleach,

There follow detergent compositions suitable for use herein. M N O P C ₁₁ -C ₁₃ Sodium alkylbenzenesulfonate 23.0 13.0 20.0 18.0 C ₁₄ -C ₁₅ sodium alcohol sulfate - 4.0 - - Sound I or II 5.0 10.0 14.0 6.0 Flocculant I or II 0.2 0.3 0.1 0.9 wax 0.5 0.5 1.0 - Humectants (Glycerin / Silica) 0.5 2.0 1.5 - C ₁₄ -C ₁₅ alcohol ethoxylate sulfate - - 2.0 C ₁₄ -C ₁₅ sodium alcohol ethoxylate 2.5 3.5 - - Quaternary C ₉ -C ₁₄ -alkyldimethylhydroxyethyl ammonium salt - - 0.5 tallow 0.5 - - - Tallow alcohol ethoxylate (50) - - 1.3 sodium tripolyphosphate - 41.0 - 20.0 Zeolite A, Hydrate (0.1-10 μm size) 26.3 - 21.3 - sodium 24.0 22.0 35.0 27.0 Sodium polyacrylate (45%) 2.4 - 2.7 - Sodium polyacrylate / maleate polymer - - 1.0 2.5 Sodium silicate (ratio of NaO / SiO ₂ 1.6 or 2 or 2.2) (46%) 4.0 7.0 2.0 6.0 sodium sulphate - 6.0 2.0 - Sodium perborate / percarbonate 8.0 4.0 - 12.0 Poly (ethylene glycol), MW ~ 4000 (50%) 1.7 0.4 1.0 - sodium 1.0 - - 0.3 citric acid - - 3.0 - NOBS / DOBS 1.2 - - 1.0 TAED 0.6 1.5 - 3.0 perfume 0.5 1.0 0.3 0.4 Soil release polymer - 1.5 1.0 1.0 humidity 7.5 3.1 6.1 7.3 magnesium sulfate - - - 1.0 complexing - - - 0.5 granule 1.0 0.5 0.2 2.7 Enzymes, including amylase, cellulase, protease and lipase - 1.0 - 1.5 Minor ingredients, eg. B. brightener, photobleach 1.0 1.0 1.0 1.0

There follow detergent compositions suitable for use herein. Q R S T U Blown powder STPP / zeolite A 9.0 15.0 15.0 9.0 9.0 Flocculant II or III 0.5 0.2 0.9 1.5 - READ 7.5 23.0 3.0 7.5 7.5 QAS 2.5 1.5 - - - DTPMP 0.4 0.2 0.4 0.4 0.4 HEDP or EDDS - 0.4 0.2 - - CMC 0.1 0.4 0.4 0.1 0.1 sodium 5.0 20.0 20.0 10.0 - brighteners 0.05 - - 0.05 0.05 Sound I or II - 10.0 - - - STS 0.5 - - 0.5 0.5 MA / AA 1.5 2.0 2.0 1.5 1.5 agglomerates Suds suppressor (silicon) 1.0 1.0 - 2.0 0.5 agglomerate volume 9.0 - - 4.0 10.0 wax 0.5 - - 0.5 1.5 glycerin 0.5 - - 0.5 0.5 agglomerate READ - 5.0 5.0 - - TAS - 2.0 1.0 - - silicate - 3.0 4.0 - - Zeolite A - 8.0 8.0 - - carbonate - 8.0 4.0 - - spray perfume 0.3 - - 0.3 0.3 C45E7 or E9 2.0 - - 2.0 2.0 C25E3 or E4 2.0 - - 2.0 2.0 dry additives Citrate or citric acid 2.5 - 2.0 2.5 2.5 Sound I or II - 5.0 5.0 - - Flocculant I or II - - - - 0.2 bicarbonate - 3.0 - - - carbonate 15.0 - - 25.0 31.0 TAED 1.0 2.0 5.0 1.0 - Sodium perborate or percarbonate 6.0 7.0 10.0 6.0 - SRP I, II or III 0.2 0.1 0.2 0.5 0.3 CMC or nonionic cellulose ether 1.0 1.5 0.5 - - protease 0.3 1.0 1.0 0.3 0.3 lipase - 0.4 0.4 - - amylase 0.2 0.6 0.6 0.2 0.2 cellulase 0.2 0.6 0.6 0.2 0.2 Silicone antifoam - 5.0 5.0 - - Perfume (starch) 0.2 0.3 1.0 0.2 0.2 stains 0.5 0.5 0.1 - 1.0 SKS-6 (silicate 2R) 3.5 - - - 3.5 Photobleach 0.1 - - 0.1 0.1 Soap 0.5 2.5 - 0.5 0.5 sodium sulphate - 3.0 - - - Other / minor components up to 100% 100.0 100.0 100.0 100.0 100.0 Density (g / liter) 850 850 850 850 850

Claims (15)

Coated perfumed detergent tablet, wherein the tablet is a clay mineral compound and a heavy metal ion sequestrant wherein the coating is the heavy metal sequestering agent includes. A tablet according to claim 1, wherein the clay mineral compound in the coating in particles smaller than 75 μm in diameter is available. A tablet according to any one of claims 1-2, wherein the tablet is a Plasticizer tablet is. A tablet according to any one of claims 1-3, wherein the heavy metal ion sequestrant is selected from organic phosphonates, preferably from alkali metal ethane 1-hydroxydiphosphonates, Diethylene triamine penta (methylene phosphonate) and mixtures thereof. A tablet according to any one of claims 1-4, wherein the perfume composition to less than 0.4% by weight of Schiff's bases. A tablet according to any one of claims 1-5, wherein the perfume composition is free of perfume ingredients, which consists of methylanthranilate and Hydroxycitronellal; Methyl anthranilate and methylnonylacetaldehyde; Methyl anthranilate and PT Bucinal; Methyl anthranilate and lyral; methyl anthranilate and Ligustral; and mixtures thereof are selected. A tablet according to any one of claims 1-6, wherein the coating also an acid having a melting temperature of at least 40 ° C, preferably at least 145 ° C. A tablet according to claim 7, wherein the acid is with a melting temperature of at least 40 ° C a crystallized structure having. A tablet according to claim 8, wherein the acid, the forming the crystallized structure is a dicarboxylic acid, preferably Adipic acid. A tablet according to any one of claims 1-9, wherein the coating essentially adipic acid consists. A tablet according to any one of claims 1-10, wherein the coating further comprising a component which is liquid at 25 ° C. A tablet according to any one of claims 1-11, wherein the coating further reinforcing Includes fibers. A tablet according to any one of claims 1-12, wherein the detergent composition further comprises a flocculant. Method for producing a tablet after a the claims 1-13, which includes the following steps: (a) forming a nucleus by densification of a particulate material, wherein the particulate Material surfactant and detergent builder comprises; (b) Apply a coating material on the core, wherein the coating material in the form of a melt; (c) solidifying the molten coating material; characterized, that the coating comprises a clay. A method of manufacturing a tablet according to any one of claims 1 to 13, comprising the following steps comprising: (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 dissolved in a solvent or water; (c) allowing the solvent or water to evaporate; characterized in that the coating comprises a clay.