CN1350577A - Perfumed detergent tablet - Google Patents

Abstract

The present invention relates to a perfumed detergent tablet, the tablet comprising a clay mineral compound, and the perfume comprising less than 0.6% of Schiff-base by weight of the perfume composition.

Description

Perfumed detergent tablet

Field of the invention

The present invention relates to perfumed detergent tablets, especially those suitable for use in washing machines, and to a process for producing such tablets.

Background

Perfumed products are well known in the art. However, the acceptance of such perfumed products, such as laundry and cleaning products, by consumers depends not only on the properties that can be obtained with these products, but also on the aesthetic appearance associated with these products. Perfume ingredients are therefore an important aspect of the successful formulation of these commercial products.

Additionally, clay inorganic compounds are desirable ingredients for these laundry and cleaning products, especially those in tablet form. Indeed, clays can not only provide a softening effect, but also act as disintegrants for these tablets.

However, one problem encountered with perfumed tablets containing clay inorganic compounds is that the clay may have a detrimental effect on the performance of the perfume contained therein. Thus, without being bound by theory, it is believed that this is due to the close physical proximity of the tablet, the perfume being absorbed into the clay where it interacts with the heavy metal ions and acid or base sites in the clay, resulting in discoloration of the clay. Also, the interaction between the perfume and the clay may also result in a less odorous tablet product.

It is therefore an object of the present invention to provide perfumed detergent tablets containing clay mineral compounds, which detergents have excellent perfume performance while reducing discoloration of the clay.

Furthermore, cleansing compositions in tablet form have often been proposed, and although products in unit-dispensed form have some advantages, they have not been substantially successful (with the exception of soap bars for personal cleansing). One reason for this may be that tablet detergents require a relatively complicated production process. In particular, it is often necessary to provide the sheet-like product with a coating, which increases the difficulty of production.

Since uncoated sheet products function adequately in use, they often lack the necessary surface hardness to withstand the friction that is part of normal production, packaging and handling. The result is that the uncoated sheet product is subjected to friction during these processes, resulting in a broken sheet product and loss of active material.

Finally, for aesthetic reasons, it is often desirable to coat the sheet products to enhance the appearance of the sheet products or to achieve certain special aesthetic effects.

Many methods of coating tablet products have been proposed to date, many of which have been used for detergent tablets. However, all of these methods have certain disadvantages, as will be explained below.

GB-A-0989683, published 4/22/1965, discloses a process for the preparation of granular detergents from surfactants and inorganic salts; spraying onto the water-soluble silicate; the detergent particles are pressed into a tablet product which remains in solid form. Finally, an organic film-forming polymer which is readily soluble in water (e.g., polyvinyl alcohol) provides a coating to produce a detergent tablet which is resistant to abrasion and accidental breakage.

EP-A-0002293 published on 6/13 of 1979 discloses platelet-shaped coatings containing hydrated salts such as acetates, metaborates, orthophosphates, tartrates and sulfates.

EP-A-0716144 published on 12.6.1996 also describes detergent tablets having ｃA water-soluble coating which may be an organic polymer comprising acrylic acid/maleic acid copolymer, polyethylene glycol, PVPVA and ｃA sugar.

WO9518215 published 7/6 in 1995 provides a water-insoluble coating for solid cast sheet products. Sheet products are provided having a hydrophobic coating comprising a wax, a fatty acid amide, and polyethylene glycol.

EP-A-0846754 published on 10.6.1998 provides sheet-like products comprising ｃA coating of ｃA dicarboxylic acid, the coating material typically having ｃA melting point of from 40 ℃ to 200 ℃.

EP-A-0846755 published on 10.6.1998 provides tablet-like products having ｃA coating comprising ｃA material which is insoluble in water at 25 ℃, such as ｃA C12-C22 fatty acid, adipic acid or ｃA C8-C13 dicarboxylic acid.

EP-A-0846756 published on 10.6.1998 provides tablet-like products with ｃA coating comprising ｃA disintegrating material and preferably an effervescent material.

Recently it has been found that it is possible to carry out a process for coating sheet-like products with a coating which is easily broken when the sheet-like products are placed in a washing machine, releasing the active ingredients into the washing solution, so that they can be stored, transported and handled without breakage. Such disclosures may be found primarily in co-pending european patent applications EP 99870017.3, EP 99870018.1 and EP 99870019.9.

However, as a result of obtaining satisfactory results, it has been found that when a clay inorganic compound is present in the coating of a tablet detergent, the clay may adversely affect the fragrance contained therein and the appearance of the coating (i.e., discoloration of the coating) for the same reasons as described above.

It has further been found that these problems become more sensitive over time and are even more pronounced when the coating comprises an acid having a melting point of at least 40 c, more particularly at least 145 c.

Thus, detergent formulators are also faced with the problem of providing coated tablet products which have coatings with a satisfactory appearance, yet are sufficiently hard to protect the tablet product from mechanical forces during storage, transport and handling, and are readily dispersible in aqueous solutions while achieving satisfactory perfume performance.

In addition, perfuming of tablet detergents is a concern for detergent formulators. Thus, the presence of a coating on the tablet may reduce the loss of flavour due to diffusion of the perfume from the tablet.

It has now surprisingly been found that perfume compositions containing less than 0.6% of schiff base by weight of perfume in a tablet detergent overcome these problems. This finding is surprising, since it was not expected that schiff bases, which are known to impart a yellow colour to the raw material, would cause discoloration of the clay (all the more so over time).

Summary of the invention

The present invention is a perfumed detergent tablet, the tablet comprising a clay mineral compound; wherein said perfume comprises less than 0.6% by weight of said perfume composition of schiff bases.

By "perfumed detergent tablet" it is meant that the perfume may be present in the coating, if present, or in the detergent composition, or in both.

Detailed description of the invention Clay

An essential component of the detergent tablet is clay. The clay may be present in any detergent component, coating (if present), or both.

The clay inorganic compound (or abbreviated "clay") herein refers to hydrated phyllosilicate, generally having a two-or three-layer crystal structure. For the sake of clarity, it is noted that the term clay inorganic compound as used herein does not include sodium aluminosilicate zeolite builder compounds, but that said zeolite builders may be included as optional components in the compositions of the present invention. For additional description of clays, see Encyclopaedia of Chemical Technology, fourth edition, volume 6, page 381, of Kirk-Othmer, published by John Wiley and Sons.

The clay inorganic compound is preferably a smectite-type clay compound. Smectite-type clay compounds are disclosed in U.S. Pat. Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647 and European patent Nos. EP-A-299,575 and EP-A-313,146 (both from the Procter and gamble Company).

The term smectite-type clay herein includes clays with alumina present in the silicate lattice and clays with magnesia present in the silicate lattice. Typical smectite-type clay compounds include those of the formula Al₂(Si₂O₅)₂(OH)₂.nH₂O compound and general formula Mg₃(Si₂O₅)₂.nH₂A compound of O. Smectite type clays tend to form an expandable three-layer structure.

Specific examples of suitable smectite-type clays include those selected from montmorillonite, hectorite, chroimite, nontronite, saponite, and sauconite, particularly those having an alkali or alkaline earth metal ion in the crystal lattice structure. Sodium montmorillonite or calcium montmorillonite are particularly preferred.

Suitable smectite-type Clays, particularly montmorillonites, are available from various suppliers including English China Clays, Laviosa, Fordamin, Georgia Kaolin, and ColinStewart Minerals (CSM).

Preferred smectite-type clays are the commercial White Bentonite STP sold by Fordamin and the commercial Detercal P7 sold by Laviosa Chemical Mineria SPA.

The clay used herein may be acid-washed with any suitable inorganic or organic acid. These clays produce an acidic pH when dissolved in distilled water. Such a commercial "acid clay" is commercial Tonsil P available from Sud Chemie AG.

Substitution of small cations such as protons, sodium ions, potassium ions, magnesium ions, and calcium ions, as well as substitution of certain organic molecules including positively charged functional groups, can generally be performed in the crystal lattice structure of the smectite-type clay. Clays can be selected for their preferential absorption capacity for one type of cation, as assessed by measuring relative ion exchange capacity. The smectite-type clays suitable for use herein typically have a cation exchange capacity of at least 50meq/100 g. U.S. patent No. 3954632 describes a method of measuring cation exchange capacity.

The crystal lattice structure of the clay inorganic compound may have a cationic fabric softener substituted therein (preferred example). Such substituted clays are referred to as "hydrophobically activated" clays. Typically the cationic fabric softener is present in a ratio (cationic fabric softener to clay) of from 1: 200 to 1: 10, preferably from 1: 100 to 1: 20. Suitable cationic fabric softeners include the water-insoluble tertiary amine or di-long chain amide materials disclosed in GB-A-1514276 and EP-B-0011340.

A preferred "hydrophobically activated" clay is commercially available as bentonite clay containing about 40% by weight of dimethyl ditallowate quaternary ammonium salt, sold under the trade name ClaytoneEM by English China Clays International.

The clay preferably present in the detergent composition is present in an intimate mixture or in the form of particles with wetting agent and hydrophobic compound, preferably a wax or oil, such as a paraffinic oil. Preferred humectants are organic compounds including propylene glycol, ethylene glycol, dimers or trimers of glycols, and most preferably glycerol. The particles are preferably agglomerates. Alternatively, the particles may be encapsulates of wax or oil and optionally wetting agent on clay, or the clay may be encapsulates of wax or oil and wetting agent. It may be preferred that the particles comprise an organic salt or silica or silicate.

In another embodiment, the clay in the detergent composition is preferably mixed with one or more surfactants and optionally a builder and optionally water, wherein preferably the mixture is subsequently dried. Preferably, this mixture is further spray-dried to obtain spray-dried particles containing the clay.

It may also be preferred that the intimate mixture comprises a chelating agent.

Depending on the end use, it is preferred that the clay exists in different particle sizes. Thus, when softening is desired, preferably at least 50% by weight, preferably substantially all (e.g. at least 90% or 95% by weight) of the clay is present in particulate form. By particles is meant that particles of the clay inorganic compound present in the detergent composition are present as a component of the agglomerated particles, said particles optionally including other detergent compounds. The term "maximum particle size" of the clay inorganic compound, when present, refers to the maximum particle size of the clay inorganic compound, and not to the entire agglomerated particle. Typically the particles will have a particle size of at least 100 microns, typically 100-1700 microns.

When present, the coating typically requires clay as a disintegrant. In this case, it is preferred that the clay is present in the coating, the clay particle size being less than 75 microns, more preferably less than 53 microns.

Preferably the sheet product is a softened sheet product. By softening the tablet is meant that the level of clay is typically at least 5%, preferably at least 8%, most preferably at least 10% by weight of the tablet. The amount may be less than 25%, typically less than 20%, preferably not more than 15% (based on the weight of the sheet-like product). Perfume

The tablet of the present invention also includes a perfume composition, which may be present in the coating (if present) or in the detergent composition, or even in both the coating and the detergent composition. Perfumes suitable for use herein include materials which provide good olfactory impact, such as to make such sheet-like products more pleasant to the consumer, which are capable of imparting a pleasant scent to fabrics treated therewith and/or covering any "chemical" odor which the product may have.

As used herein, a fragrance includes a scented material or mixture of materials including scented materials that are natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, tree fragments, wood, flowers, or plants), artificial (i.e., a mixture of different natural oils or oil components), and synthetic (i.e., synthetically produced). These materials are usually accompanied by auxiliary materials such as fixatives, extenders, stabilizers and solvents. These auxiliary materials are also included within the meaning of "perfume" as used herein. Typically fragrances are complex mixtures of many organic compounds.

For the purposes of the present invention, the perfume composition contains less than 0.6% by weight of schiff bases. The perfumes used herein are used at levels up to 5 grams per tablet and are preferably substantially free of schiff bases.

By "substantially free" it is meant that the perfume composition contains less than 0.4% by weight of schiff bases, more preferably no schiff bases.

Schiff bases are condensation products of aldehyde fragrance components with anthranilates. For a main description see US 4853369. The schiff base may be added directly to the perfume composition or may be formed in situ therein by adding to the perfume composition an anthranilate such as methyl or ethyl anthranilate together with an aldehyde which may react with the anthranilate to form the schiff base.

Without being bound by theory, it is believed that when this compound comes into contact with clay, it is highly susceptible to reactions catalyzed by the metal ions present in the clay, which reactions produce darker colored byproducts.

Typical schiff bases are selected from the schiff bases of 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbaldehyde and methyl anthranilate, the condensation products of: hydroxycitronellal and methyl anthranilate, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbaldehyde and methyl anthranilate, methyl anthranilate and commercial hydroxycitronellal under the tradename Aurantil, methyl anthranilate and commercial methylnonyl acetaldehyde under the tradename Agrumea, methyl anthranilate and commercial PT lily lilial under the tradename Verdantiol, methyl anthranilate and commercial Lyrame, methyl anthranilate and commercial Ligustral under the tradename Ligantral, and mixtures thereof.

Preferably the perfume composition is free of perfume ingredients selected from the group consisting of: methyl anthranilate, commercially available hydroxycitronellal under the tradename Aurantil, methyl anthranilate, commercially available methylnonyl acetaldehyde under the tradename Agrumea, methyl anthranilate, commercially available PT lily-lily aldehyde under the tradename Verdantiol, methyl anthranilate, commercially available Neolilial under the tradename Lyrame, methyl anthranilate, commercially available Lignin aldehyde under the tradename Ligantral, and mixtures thereof.

Of course, the perfume composition contains one or more perfume components. Suitable perfumes are disclosed in U.S. Pat. No. 5,500,138, which is incorporated herein by reference.

Examples of perfume ingredients for use in the perfume composition include, but are not limited to, hexylcinnamaldehyde, pentylcinnamaldehyde, amyl salicylate, hexyl salicylate, terpineol, 3, 7-dimethyl-cis-2, 6-octadien-1-ol, 2, 6-dimethyl-2-octanol, 2, 6-dimethyl-7-octen-2-ol, 3, 7-dimethyl-3-octanol, 3, 7-dimethyl-trans-2, 6-octadien-1-ol, 3, 7-dimethyl-6-octen-1-ol, 3, 7-dimethyl-1-octanol, 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbaldehyde, tricyclodecenyl propionate, tricyclodecenyl acetate, anisaldehyde, 2-methyl-2- (p-isopropylphenyl) -propionaldehyde, ethyl-3-methyl-3-phenylglycidic acid ester, 4- (p-hydroxyphenyl) -butan-2-one, 1- (2, 6, 6-trimethyl-2-cyclohexenyl) -propionaldehyde, p-hexylphenyl-3-methoxyvalerolactone, p-hexylphenyl-3-methoxyvalerolactone, p-methyl-3-octylvalerolactone, and p-tert-butyl-3-methyl-2-octyl-methyl-3-.

Examples of other flavor materials include, but are not limited to, orange oil, lemon oil, grapefruit oil, bergamot oil, clove oil, γ -dodecalactone, methyl-2- (2-pentyl-3-oxo-cyclopentyl) acetate, β -naphthol methyl ether, methyl- β -naphthalenone, coumarin, decanal, benzaldehyde, 4-tert-butylcyclohexyl acetate, α -dimethylbenzyl acetate, methylbenzyl acetate, cyclic ethylene glycol diester of tridecanedioic acid, 3, 7-dimethyl-2, 6-octadiene-1-carbonitrile, methyl γ -ionone, α -ionone, β -ionone, orange leaf (petitgrain), methyl cedryl ketone, 7-acetyl-1, 2,3, 4,5, 6,7, 8-octahydro-1, 1, 6, 7-tetramethylnaphthalene, methyl ionone, methyl-1, 6, 10-trimethyl-, 2, 5, 9-cyclododecatrien-1-hydroxyindan-1, 3,6, 7, 8-octahydro-1, 1, 6, 7-tetramethylindane, 6, 7-hexahydro-1, 1, 3-1, 6-tetramethylindane, 2,3, 6-hexahydro-1, 3, 6-1, 6-hexahydro-1, 6-dihydrocinnamyl-1, 6-tetramethylindane, 7,6, 6-hexahydro-1, 6-hexahydro-1, 6, 6-1, 6-hexahydro-1, 6-dihydroindole, 1, 6-hexahydro-1, 1, 6-dihydroindole, 1, 6-dihydroindole, 2-dihydroindole, 1, 6-hexahydro-1, 6-dihydroindole, 1, 6-2-dihydroindole, 6-dihydroindole, 1, 2-dihydroindole, 6-2-dihydroindole, 1, 2-dihydroindole, 6-2-dihydroindole, 6-dihydroindole, 2-dihydroindole, 2-dihydroindole, 6-dihydroindole, 2-2;

further examples of perfume components are geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalyl, citronellol, citronellyl acetate, dihydromyrcenol acetate, tetrahydromyrcenol, terpinyl acetate, nopyl alcohol, nopyl acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, styryl acetate, dimethylbenzylcarbinyl methanol, trichloromethylphenylcarbinyl methylphenylcarbinyl acetate, isononyl acetate, citronellyl acetate, citronellol, 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde, 2-methyl-3- (p-isopropylphenyl) propionaldehyde, 3- (p-tert-butylphenyl) propionaldehyde, 4- (4-methyl-3-pentenyl) -3-cyclohexene carbaldehyde, 4-acetoxy-3-pentyltetrahydropyran, methyl dihydrojasmonate, 2-n-heptylcyclopentanone, 3-methyl-2-pentyl-cyclopentanone, n-decanal, n-dodecanal, 9-decenol-1, phenoxyethyl isobutyrate, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, geranonitrile, citronellonitrile (citronellonitril), cedryl acetal, 3-isoborneylcyclohexanol, cedryl methyl ether, isolongifalanone, anisonitrile, anisaldehyde, piperonal, eugenol, vanillin, diphenyl oxide, hydroxycitronellal ionone, methyl ionone, isomethyl ionone, irone, cis-3-hexenol and its esters, indanthrone musk fragrances, tetrahydronaphtalene musk fragrances, isochroman musk fragrances, macrocyclic ketones, macrolide musk fragrances, ethylene glycol brassylate.

The perfumes used in the compositions of the present invention are substantially free of halogenated materials and nitromusks.

Examples of solvents, diluents or carriers suitable for the above perfume ingredients include ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc. The amount of such solvents, diluents or carriers added to the perfume is preferably kept at the minimum amount necessary to provide a homogeneous perfume solution.

The tablet of the invention and the coated tablet of the invention improve fabric perfume deposition.

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

The perfume may be incorporated into the tablet by any conventional method known to those skilled in the art. One preferred method is to spray the perfume composition onto the tablet product. Heavy metal ion chelating agent

The perfumed detergent tablet according to the invention preferably further comprises as an optional component a heavy metal ion sequestrant composition, which may be present in the coating, if present, or in the detergent composition, or even in both the coating and the detergent composition. Heavy metal ion sequestrants refer to various components used to sequester heavy metal ions. These components may also have calcium-magnesium chelating capabilities, but preferably they are selective for binding heavy metal ions such as iron, manganese and copper.

Typically the heavy metal ion sequestrant is present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5%, most preferably from 0.5% to 5% by weight of the tablet.

Heavy metal ion sequestrants having acidic, e.g. phosphoric and carboxylic acid, functionalities may be present in the form of acid forms or complexes/salts with suitable counter cations, e.g. alkali or basic metal ions, ammonium or substituted ammonium ions or any mixture thereof. Preferably any salt/complex is water soluble. The molar ratio of counter cation to heavy metal ion sequestrant is preferably at least 1: 1.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates such as aminoalkylenepoly (alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates.

Among the above species, diethylenetriaminepenta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylenediamine tetra (methylene phosphonate) and hydroxy-ethylene 1, 1-diphosphonate are preferred.

Other suitable heavy metal ion sequestrants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylene diamino tetraacetic acid, ethylene triamine pentaacetic acid, ethylene diamine disuccinic acid, ethylene diamine diaminetetraglutaric acid, 2-hydroxypropanediamine disuccinic acid or any salts thereof.

Particular preference is given to ethylenediamine-N, N' -disuccinic acid (EDDS) or 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 complexes thereof. Examples of such preferred sodium salts of EDDS include Na₂EDDS and Na₃EDDS. Examples of these preferred magnesium complexes of EDDS include MgEDDS and Mg₂EDDS。

Other suitable heavy metal ion sequestrants for use herein include iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl iminodiacetic acid described in EP-A-317,542 and EP-A-399,133.

Also suitable for this are iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelants as described in EP-A-516,102 β -alanine-N, N' -diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid chelants as described in EP-A-509,382.

EP-A-476,257 describes suitable amino-based chelating agents. EP-A-510,331 describes suitable chelating agents derived from collagen, keratin or casein. EP-A-528,859 describes suitable alkyl iminodiacetic acid chelating agents. Dipicolinic acid and 2-phosphinobutane-1, 2, 4-tricarboxylic acid are also suitable. glycinamide-N, N ' -disuccinic acid (GADS), ethylenediamine-N, N ' -diaminetetraacetic acid (EDDG) and 2-hydroxypropanediamine-N, N ' -disuccinic acid (HPDDS) are also suitable.

The most preferred heavy metal ion for use herein is an alkali metal ethane 1-hydroxy diphosphonate, especially in combination with diethylene triamine penta (methylene phosphonate). Most preferably, a heavy metal ion sequestrant is present in the coating. Detergent composition

The tablet may include ingredients such as surfactants, enzymes, detergents, and the like. Typical tablet-like compositions for use in the preferred embodiments of the present invention are disclosed in co-pending european patent application nos. 96203471.6, 96203462.5, 96203473.2 and 96203464.1. Typical ingredients present in detergent compositions in tablet form or in other detergent forms such as liquid or granular form will be described in detail below. Detersive surfactant

Various surfactants are typically included in the detergent composition. The dissolution of the surfactant is aided by the addition of a highly soluble compound. Non-limiting examples of surfactants useful herein are generally present at levels of from about 1% to about 55% by weight, including conventional C₁₁-C₁₈Alkyl benzene sulfonates ("LAS") and primary, branched and random C₁₀-C₂₀Alkyl sulfates ("AS"), of the formula CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃C of (A)₁₀-C₁₈Secondary (2, 3) alkyl sulfates 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, C₁₀-C₁₈Alkyl alkoxy sulfates of (AE) ("AE)_xS "; in particular EO 1-7 ethoxysulfate), C₁₀-C₁₈Alkyl alkoxy carboxylates (especially EO 1-5 ethoxy carboxylates), C_10-18Glyceryl ether, C₁₀-C₁₈Alkyl polyglucosides and their corresponding sulfuric acid polyglucosides and C₁₂-C₁₈α -sulfonated fatty acid ester if desired, conventional nonionic and amphoteric surfactants, such as C, may also be included in the overall composition₁₂-C₁₈Alkyl ethoxylates ("AE", including so-called narrow peak alkyl ethoxylates) and C₆-C₁₂Alkylphenol alkoxylates (in particular ethoxylates and mixed ethoxy/propoxy oxides), C₁₂-C₁₈Betaines and sulfobetaines ("sulfobetaines"), C₁₀-C₁₈Amine oxides of (2), and the like. Also usable are C₁₀-C₁₈N-alkyl polyhydroxy fatty acid amides. Typical examples include C₁₂-C₁₈N-methylglucamides (see WO9,206,154). OthersSurfactants derived from sugars include N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C may be used₁₂-C₁₈The glucamide of (a) is low foaming. Conventional C may also be used₁₀-C₂₀Soap. If high foaming is desired, a branched chain C may be used₁₀-C₁₆Soap. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventionally useful surfactants are listed in standard texts. In a preferred embodiment, the tablet contains at least 5% by weight surfactant, more preferably at least 15% by weight, even more preferably at least 25% by weight and most preferably from 35% to 45% by weight surfactant.Non-gelling binders

To facilitate dissolution, a non-gelling binder may be incorporated into the detergent composition.

If a non-gelling binder is used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycol, polyvinylpyrrolidone, polyacrylates, and water-soluble acrylate copolymers. The following binder types were found in Handbook of Pharmaceutical Excipients (second edition): acacia, alginic acid, acrylic acid polymers, sodium carboxymethylcellulose, dextrin, ethylcellulose, gelatin, guar gum, hydrogenated vegetable oil type I, hydroxyethyl cellulose, hydroxypropyl methylcellulose, liquid glucose, magnesium aluminum silicate, maltodextrin, methylcellulose, polymethacrylates, polyvinylpyrrolidone, sodium alginate, starch, and zein. Most preferred binders also have an active cleaning function in laundry, such as cationic polymers, i.e. ethoxylated hexamethylene diamine quaternary ammonium compounds, bis hexamethylene triamine or others like pentylamine, ethoxylated polyvinylamine, maleic acrylic acid copolymer.

Preferably, the non-gelling binder material is sprayed, and therefore it should have a suitable melting temperature of less than 90 ℃, preferably less than 70 ℃ and even more preferably less than 50 ℃ so as not to damage or degrade the other active ingredients in the matrix. Most preferred are nonaqueous liquid binders (i.e., not in aqueous solution) that can be sprayed in molten form. However, they may also be solid binders which are incorporated into the matrix by dry addition but which have adhesive properties in the sheet-like product.

The non-gelling binder material is preferably used in an amount of 0.1 to 15% of the composition, more preferably below 5% and in particular below 2% of the weight of the sheet-like product if it is a non-detergent active material.

Gelling binders (e.g., nonionic surfactants) in liquid or molten form are preferably avoided. The compositions do not exclude nonionic surfactants and other gelling binders, but preferably they are processed into the tablet as particulate matter rather than as a liquid component. Builder

The compositions herein may optionally include builders to assist in controlling mineral hardness. Inorganic and organic builders can be used. Builders are commonly used in fabric laundry compositions to aid in the removal of particulate soils.

The level of builder may vary widely depending on the end use of the composition.

Inorganic or phosphorus-containing builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphoric acids (exemplified by triphosphates, pyrophosphates, and glassy polymer metaphosphates), phosphonic acids, phytic acids, silicic acids, carbonic acids (including bicarbonates and sesquicarbonates), sulfuric acid, and aluminosilicates. However, in some cases non-phosphate builders are required. Importantly, the compositions herein perform surprisingly even in the presence of so-called "weak" builders (as compared to phosphates), such as citrate, or in the case of so-called "under-built" (as occurs with zeolite or layered silicate builders).

Examples of silicate builders are alkali metal silicates, in particular those having SiO₂∶Na₂Alkali metal silicates and layered silicates having an O ratio of 1.6: 1 to 3.2: 1, such as the layered sodium silicate described in U.S. patent 4,664,839 issued to h.p. rieck at 12 months 5 1987. The crystalline layered silicate marketed by Hoechst is sold under the trade name NaSKS-6 (this isAbbreviated to "SKS-6" for common usage). Unlike zeolite builders, the Na SKS-6 silicate builder is free of aluminum. NaSKS-6. delta. -Na with layered silicate₂SiO₅Morphological forms. They can be prepared by processes as described in DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but those having the general formula NaMSi may also be used_xO_2x+1·yH₂(ii) layered silicates of the formula O (where M is sodium or hydrogen, x is a number from 1.9 to 4 (preferably 2) and y is a number from 0 to 20 (preferably 0 is used herein.) various other layered silicates from Hoechst include α, β and the gamma forms NaSKS-5, NaSKS-7 and NaSKS-11. As noted above, it is most preferred to use delta-Na herein₂SiO₅(NaSKS-6 form). Other silicates such as magnesium silicate may also be used, which are used in granular formulations as a profile weighting agent (crispening agent), as a stabilizer for oxygen bleaches, and as a component of a bubble control system.

Examples of carbonate builders are alkaline earth and alkali metal carbonates as disclosed in German patent application No. 2,321,001 (published on 1973, 11/15).

Aluminosilicate builders can be used in the present invention. Aluminosilicate builders are of great importance in many high performance granular detergent compositions currently on the market, as well as being a major builder component in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

[M_z(zAlO₂)_y]·xH₂wherein z and y are integers of at least 6, the molar ratio of z to y is from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure and may be derived from naturally occurring or synthetic aluminum silicates. One method of producing aluminosilicate ion exchange materials is disclosed in U.S. patent 3,985,669 issued to Krummel et al at 10/12/1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available from commercial products under the trade designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate example exchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂wherein x is about 20 to about 30, particularly about 27. This material is called Zeolite A. Dehydrated zeolites (x ═ 0 to 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1 to 10 μm in diameter.

Organic builders suitable for use in the present invention include, but are not limited to, various polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylate groups. Polycarboxylate builders can generally be added to the compositions in the acid form, but can also be added in the form of neutralized salts. When salt forms are used, alkali metal salts such as sodium, potassium and lithium or alkanolammonium salts are preferred.

The polycarboxylate builders include a variety of useful material types. One important class of polycarboxylate builders includes the ether polycarboxylates, including oxydisuccinates (oxy-disuccinates) (e.g., U.S. Pat. No. 3,128,287 issued to Berg 4/7 in 1964 and U.S. Pat. No. 3,635,830 issued to Lamberti et al 1/18 in 1972, also see the "TMS/TDS" builder in U.S. Pat. No. 4,663,071 to Bush et al 5/5 in 1987). Suitable ether polycarboxylates also include cyclic compounds, particularly cycloaliphatic compounds such as those described in U.S. Pat. Nos. 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903.

Other suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid and carboxymethyloxysuccinic acid, 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, various alkali metal, ammonium and substituted ammonium salts of carboxymethyloxybutyric acid, and soluble salts thereof.

Citrate builders, such as citric acid and soluble salts thereof (especially sodium salts), are polycarboxylate builders of particular importance for use in high performance liquid detergents because of their availability from renewable sources and their biodegradability. Citrate salts may also be used in the granular composition, particularly in combination with zeolite and/or layered silicate builders. Oxydisuccinates are particularly useful in such compositions and mixtures.

3, 3-dicarboxy-4-oxa-1, 6-adipate and related compounds disclosed in U.S. patent 4,566,984 issued to Bush on 28.1.1986 are also suitable for use in the detergent compositions of the present invention. Useful succinic acid builders include C₅-C₂₀Alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecylsuccinic acid. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, cetyl succinate, 2-dodecyl succinate (preferred), 2-pentadecyl succinate, and the like. Lauryl succinate is among the preferred builders described in European patent application 86200690.5/0,200,263, published on 5.11.1986.

Other suitable polycarboxylates are described in U.S. Pat. No. 4,144,226 to Crutchfield et al, 3/13 1979, and U.S. Pat. No. 3,308,067 to Diehl, 3/7 1967. See also U.S. patent 3,723,322 to Diehl.

Can convert fatty acids such as C₁₂-C₁₈Monocarboxylic acids are incorporated into the composition either alone or together with the aforementioned builders, especially citrate and/or the succinate builder, to provide additional building activity. Such use of fatty acids will generally result in reduced foaming, which the formulator should take into account.

Where phosphorus-based builders can be used, particularly in the formulation of bar soaps for hand-washing operations, various alkali metal phosphates can be used, such as the well-known sodium tripolyphosphates, pyrophosphates, and orthophosphates. Sodium phosphonate builders such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates may also be used (see, for example, U.S. patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137). Bleaching agent

The detergent compositions herein may optionally contain a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. When present, the detergent compositions, particularly for fabric washing, typically contain from about 1% to about 30%, more preferably from about 5% to about 20% of bleach. If present, the bleach activator is preferably present in an amount of from about 0.1% to about 60%, more preferably from about 0.5% to about 40%, of the bleaching composition (including bleach plus bleach activator).

The bleaching agent used herein may be any bleaching agent (known or to be known) used in detergent compositions for textile cleaning, hard surface cleaning or other cleaning purposes. These include oxygen bleaches and other bleaching agents. Perborate bleaching agents such as sodium perborate (e.g., monohydrate or tetrahydrate) may be used herein.

Another useful class of bleaching agents includes, without limitation, percarboxylic acid bleaching agents and salts thereof. Suitable examples of such agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaches are disclosed in U.S. Pat. No. 4,483,781 (Hartman, 11/20 1984), U.S. patent application 740,446(Burns et al, 3/6 1985), European patent application 0,133,354(Bank et al, 2/20 1985), and U.S. Pat. No. 4,412,934 (Chung et al, 11/1 1983). Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxyhexanoic acid, described in U.S. Pat. No. 4,634,551 (issued to Burns et al on 6.1.1987).

Peroxygen bleaches may also be used. Suitable peroxygen bleach compounds include sodium bicarbonate peroxygen and equivalent amounts of "percarbonate" bleaches, sodium pyrophosphate peroxygen, urea peroxygen and sodium peroxide. Persulfate bleach (e.g., OXONE, commercially produced by DuPont) may also be used.

Preferred percarbonate bleach compositions contain dry particles having an average particle size of from about 500 μm to about 1,000 μm, no more than about 10% by weight of said particles being less than about 200 μm and no more than about 10% by weight of said particles being greater than about 1,250 μm. Optionally, the percarbonate may be coated with silicates, borates or water soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents may also be used.

Preferably, peroxygen bleach, perborates, percarbonates, etc., are used in conjunction with a bleach activator, resulting in the generation of an aqueous solution of the peroxyacid corresponding to the bleach activator in situ (i.e., during the wash). Non-limiting examples of various active agents are disclosed in U.S. Pat. No. 4,915,854 (issued to Mao et al on 4.4.10.1990) and U.S. Pat. No. 4,412,934. Typically, the Nonanoyloxybenzenesulfonate (NOBS) and Tetraacetylethylenediamine (TAED) actives, and mixtures thereof, may also be used. See also U.S.4,634,551 for other typical bleaching and active agents that may be used herein.

Highly preferred amide derived bleach activators have the formula:

R¹N(R⁵)C(O)R²c (O) L or R¹C(O)N(R⁵)R²C (O) L wherein R¹Is an alkyl group containing from about 6 to about 12 carbon atoms, R²Is alkylene containing 1 to about 6 carbon atoms, R⁵Is H or an alkyl, aryl or alkaryl group containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. Leaving groups are groups that leave the bleach activator as a result of nucleophilic attack of the perhydrolysis (perhydrolysis) anion on the bleach activator. A preferred leaving group is phenyl sulfonate.

Examples of preferred bleach activators in the above formula include (6-octanoylamide-hexanoyl) oxybenzenesulfonate, (6-nonanamido-hexanoyl) oxybenzenesulfonate, (6-decanoylamide-hexanoyl) oxybenzenesulfonate, and mixtures thereof, as described in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators includes the benzoxazine-type activators disclosed in U.S. patent 4,966,723 to Hodge et al, incorporated herein by reference, at 10, 30, 1990. Highly preferredThe benzoxazine active agent is as follows:

yet another preferred class of bleach activators includes acyl lactam activators, particularly acyl caprolactams and acyl valerolactams of the formula:

in the formula R⁶Is H or an alkyl, aryl, alkoxyaryl or alkylaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam actives include benzoyl caprolactam, octanoyl caprolactam, 3,5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecanoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecanoyl valerolactam, nonanoyl valerolactam, 3,5, 5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. patent 4,545,784 to Sanderson, 10/8/1985, which is incorporated herein by reference, which discloses acetylcaprolactam (including benzoylcaprolactam) adsorbed into sodium perborate.

Bleaching agents other than oxygen bleaching agents are known in the art and may be used herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanine. See U.S. Pat. No. 4,033,718 to Holcomb et al, 1977, 7, 5. If used, the detergent compositions typically comprise from about 0.025% to about 1.25% by weight of such bleaching agents, especially zinc sulfonated phthalocyanine.

If desired, the bleaching compound may be catalysed by means of a manganese compound. Such compounds are well known in the art and include, for example, those disclosed in U.S. Pat. No. 5,246,621, U.S. Pat. No. 5,244,594, U.S. Pat. No. 5,194,416, U.S. Pat. No. 5,114,606 and European patent application publication Nos. 549,271A1, 549,272A1, 544,440A2 and 544,490A1A manganese-based catalyst of (1); preferred examples of these catalysts include Mn^IV ₂(u-O)₃(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(PF₆)₂、Mn^III ₂(u-O)₁(u-OAc)₂(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂-(ClO₄)₂、Mn^IV ₄(u-O)₆(1, 4, 7-triazacyclononane)₄(ClO₄)₄、Mn^IIIMn^IV ₄(u-O)₁(u-OAc)₂- (1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₃、Mn^IV(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane) - (OCH₃)₃(PF₆) And mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. The use of manganese with various complexing ligands to enhance bleaching is also reported 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.

As one implementation (not intended to be limiting), the compositions and methods can be modified to provide on the order of at least ten million parts of the active bleach catalyst species in the aqueous wash liquor, and preferably from about 0.1ppm to about 700ppm, more preferably from about 1ppm to about 500ppm of the catalyst species in the laundry liquor. Enzyme

Enzymes may be included in the formulations herein for various fabric laundering purposes, including, for example, removal of protein-based, carbohydrate-based, or triglyceride-based stains, and inhibition of dye transfer and fabric refreshment. Enzymes that may be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, and mixtures thereof. Other types of enzymes may also be included. They may be from any suitable source such as plants, animals, bacteria, fungi and yeasts. However, their selection is governed by several factors such as optimum pH activity and/or stability, thermal stability, stability towards various active detergents, builders, etc. Bacterial or fungal enzymes, such as bacterial amylases and proteinases and fungal cellulases are preferred in this respect.

Typically, the enzyme is incorporated in an amount sufficient to provide up to about 5mg, more typically from about 0.01mg to about 3mg, of active enzyme per gram of the composition. In other words, the compositions generally contain from about 0.001% to about 5%, preferably from 0.01% to 1%, by weight of the commercial enzyme preparation. The protease enzyme is typically present in such commercial preparations in an amount sufficient to provide an activity of 0.005 to 0.1Anson Units (AU) per gram of the composition.

Examples of suitable proteases are subtilisins obtained from specific strains of bacillus subtilis and bacillus licheniformis (b. Another suitable protease is obtained from a strain of Bacillus and has maximum activity throughout the pH range of 8 to 12, developed by Novo Industries A/S and sold under the trade name ESPERASE. The preparation of this and similar enzymes is described in British patent Specification 1,243,784 to Novo. Commercial products of proteolytic enzymes suitable for removal of protein-based stains include ALCALASE and SAVINASE sold from Novo Industries A/S (Denmark) and MAXATASE sold from International Bio-Synthesis, Inc (the Netherlands). Other proteases include protease A (see European patent application 130,756 published on 9.1.1985) and protease B (see European patent application Ser. No. 87303761.8 filed on 28.4.1987 and European patent application 130,756 published on 9.1.1985 by Bott et al).

Amylases include, for example, α -amylase (described in British patent Specification No. 1,296,839(Novo)), commercially available as RAPIDASE (International Bio-Synthesis, Inc.) and TERMAMYL (Novo industries).

Cellulases usable in the present invention include bacterial cellulases or fungal cellulases. Preferably they have an optimum pH between 5 and 9.5. Suitable cellulases are disclosed in U.S. patent No. 4,435,307 issued to barbesgoaard et al at 3/6 1984, which discloses the production of fungal cellulases (Dolabella Auricula Solander) from Humicola (Humicola insolens) and Humicola strain DSM1800, or the production of cellulase 212 from a fungus belonging to the genus Aeromonas (genus Aeromonas) and cellulase extracted from the liver pancreas of marine mollusks, respectively. Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247.832, CAREZYME (Novo) being particularly useful.

Lipases suitable for detergents include those produced by microorganisms of the genus Pseudomonas (Pseudomonas group) such as Pseudomonas stutzeri (Pseudomonas aeruginosa) ATCC 19.154 as disclosed in British patent 1,372,034. See also lipase, published in the public consulted Japanese patent application 53,20487, 2, 24, 1978. This Lipase is available under the trade name Lipase P "Amano" (hereinafter referred to as "Amano-P") from Amano Pharmaceutical Co.Ltd. of Nagoya, Japan. Other suitable commercial lipases include Amano-CES, lipases derived from Chromobacterium viscosum (Chromobacterium viscosum) such as the Chromobacterium viscosum variant NRRLB 3673 from Toyo Jozo Co., of Tagata, Japan; chromobacterium viscosum lipases from U.S. Biochemical Corp. and Disoynth Co. of the Netherlands and lipases from Pseudomonas gladioli. Preferred for use herein is the LIPOLASE enzyme commercially available from Novo (see also EPO 341,947) and derived from Humicola lanuginosa.

Peroxidase enzymes are used in conjunction with oxygen sources such as percarbonates, perborates, persulfates, hydrogen peroxide, and the like. They are used for "solution bleaching", i.e. to prevent dyes or pigments removed from a substrate during a washing process from transferring to other substrates in the wash solution. Peroxidases are familiar to those skilled in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro-and bromo-peroxidase. Detergent compositions containing peroxidase are disclosed in, for example, PCT International application WO89/099813, published on 19.10.1989, assigned to Novo Industries A/S by O.Kirk.

Various enzymatic materials and methods for their incorporation into synthetic detergent compositions are also disclosed in U.S. patent 3,553,139 issued to McCarty et al, 1, 5, 1971. Also disclosed in Place et al, U.S. Pat. No. 4,101,457 at 18.7.1978 and U.S. Pat. No. 4,507,219 at 26.3.1985 to Hughes. Enzyme materials useful in liquid detergent formulations and their incorporation into such formulations are disclosed in U.S. patent 4,261,868 issued to Hora et al, 4/14, 1981. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Pat. No. 3,600,319 issued to Gedge et al at 8.17.1971 and in European patent application publication No. 0199405, application No. 86200586.5 to Venegas at 10.29.1986. Enzyme stabilization systems are also described, for example, in U.S. Pat. No. 3,519,570. Flocculating agent

The detergent composition may contain a clay flocculating agent, preferably present at a level of from 0.005% to 10%, more preferably from 0.05% to 5%, most preferably from 0.1% to 2% by weight of the composition.

The function of clay flocculants is to bind together the clay compound particles in the wash solution and thus aid their deposition on the surface of the fabrics being washed. This functional requirement is therefore different from the clay-dispersing compounds which are normally added to laundry detergent compositions to aid in the removal of clay soils from fabrics and to allow them to be dispersed in the wash solution.

Preferred clay flocculants herein are organic polymeric materials having an average molecular weight of 100,000-10,000,000, preferably 150,000-5,000,000, more preferably 200,000-2,000,000.

Suitable organic polymeric materials include homopolymers or copolymers containing monomeric units selected from alkylene oxides, especially ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinylpyrrolidone and ethyleneimine. Homopolymers of ethylene oxide, acrylamide and acrylic acid are particularly preferred.

European patent Nos. EP-A-299,575 and EP-A-313,146 to Procter and Gamble Company describe preferred organoclay flocculants for use herein.

Inorganic clay flocculants are also suitable for this purpose, typical examples include lime and alum.

The flocculating agent is preferably present in a detergent base particle, such as a detergent agglomerate, extrudate or spray-dried granule, typically comprising one or more surfactants and a builder.

It may also be preferred that the flocculating agent is comprised in a granule or particle comprising clay.

When present, the weight ratio of clay to flocculating polymer is preferably from 1000: 1 to 1: 1, more preferably from 500: 1 to 1: 1, most preferably from 300: 1 to 1: 1, or more preferably from 80: 1 to 10: 1, and in some applications even from 60: 1 to 20: 1. Highly soluble compounds

The tablet may contain a highly soluble compound. Such compounds may be formed from mixtures or from individual compounds. The highly soluble compounds are defined as follows:

solutions were prepared from deionized water and 20g/L of the specified compound as follows: 1-20 g of the specified compound were placed in a Sotax beaker. The beaker was placed in a thermostatic bath set at 10 ℃. A stirrer with a marine propeller was placed in the beaker such that the paddle of the stirrer was 5mm above the bottom of the Sotax beaker. The rotation rate of the mixer was set at 200 revolutions per minute. 2-980 g of deionized water were introduced into the Sotax beaker. 3-after 10s of introduction of the water, the conductivity of the solution was measured using a conductivity meter. 4-repeat step 3 at 20, 30, 40, 50, 1 minute, 2 minutes, 5 minutes and 10 minutes after step 2. The measurement values from 5 to 10 minutes were used as plateau or maximum values.

According to the invention, the specific compound is highly soluble when the conductivity of the solution reaches 80% of its maximum value within 10 seconds after complete addition of deionized water to the compound. In fact, when the conductivity is monitored in this way, it reaches a plateau value after a period of time, which is considered to be the maximum value. Preferably, such compounds are in a form flowable at between 10 and 80 ℃ comprised of solid particles for ease of handling, but other forms such as pastes or liquids may be used.

Examples of the high-solubility compound include sodium diisoalkylbenzene sulfonate (DIBS) or sodium toluene sulfonate. Adhesion effect

The tablet may comprise a compound having an adhesive effect on the particulate matter forming the detergent matrix of the tablet. The adhesion effect on the particulate matter of the detergent matrix forming the tablet or layer of the tablet is characterized by the force required to break the tablet or layer being based on the detergent matrix being tested pressed together under controlled compression conditions. At a given compressive force, a high sheet or layer strength indicates that the particles are tightly adhered together during their compression, and thus a strong adhesion effect occurs. In the pharmaceutical dosage forms edited by h.a. lieberman et al: a method for assessing the strength of a sheet or layer, also known as the radial rupture stress, is given in tablets (Pharmaceutical docange forms: tables) (first roll, published 1989).

The adhesion effect was determined by comparing the strength of a sheet or layer of the raw base powder but not containing the compound having the adhesion effect with the strength of a sheet or layer of a powder mixture containing 97 parts of the raw base powder and 3 parts of the compound having the adhesion effect. The compound having an adhesive effect is preferably added to the matrix in a substantially water-free form (water content below 10% (preferably below 5%)). The temperature of addition is 10 to 80 deg.C, more preferably 10 to 40 deg.C.

According to the present invention, a compound having an adhesive effect on a particulate material is defined as having an adhesive effect on said particulate material when a tablet product having a 50g weight of detergent particulate material and a diameter of 55mm increases the tablet tensile strength by more than 30% (preferably 60% and more preferably 100%) given a compressive force of 3000N by the presence of 3% of the compound having an adhesive effect in the base particulate material.

An example of a compound having an adhesive effect is sodium diisoalkylbenzene sulfonate.

When highly soluble compounds having an adhesive effect on the particulate matter are added to the tablet or layer formed by compressing the particulate matter containing the surfactant, the dissolution of the tablet or layered product in an aqueous solution is significantly improved.

In a preferred embodiment at least 1% by weight of the tablet or layered product is formed by the highly soluble compound, more preferably at least 2%, even more preferably at least 3% and most preferably at least 5% by weight of the tablet or layered product is formed by the highly soluble compound having an adhesive effect on the particulate matter.

It should be noted that compositions containing highly soluble compounds as well as surfactants are described in EP-A-0524075, which compositions are liquid compositions.

The highly soluble compounds having an adhesive effect on particulate matter can give a detergent tablet having a higher tensile strength at a constant compressive force or an equivalent tensile strength at a lower compressive force, compared to conventional detergent tablets. Generally the overall sheet product has a tensile strength of greater than 5kPa, preferably greater than 10kPa, more preferably greater than 15kPa (particularly for laundry applications), even more preferably greater than 30kPa and most preferably greater than 50kPa (particularly for dishwasher or automatic dishwasher applications); and a tensile strength of less than 300kPa, preferably less than 200kPa, more preferably less than 100kPa, even more preferably less than 80kPa, and most preferably less than 60 kPa. In fact, in the case of laundry applications, the detergent tablets should be less compressed than in the case of e.g. automatic dishwashers (where dissolution is more accessible), and therefore in laundry applications it is preferred that the tensile strength is less than 30 kPa.

This makes it possible to produce tablets or layered products having the same hardness or mechanical resistance as conventional tablet detergents, but with less compressed tablets or layers (and therefore more readily soluble). Furthermore, since the compounds are highly soluble, they in turn facilitate the dissolution of the sheet or layer, with the result that the dissolution of the sheet product of the invention is synergistically facilitated. Production of sheet-like products

The sheet-like product may comprise several layers. For the production of a single layer product, the layer may be considered as the sheet product itself.

A tablet detergent may be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press (as used in the pharmaceutical industry). Preferably the base ingredient, in particular the gelling surfactant, is used in particulate form. Any liquid ingredient, such as a surfactant or suds suppressor, can be incorporated into the solid particulate ingredient in a conventional manner.

Especially for laundry soaps in tablet form, the ingredients (e.g. builders and surfactants) can be spray dried in conventional manner and subsequently compressed under suitable pressure. Preferably the detergent tablets of the invention are compressed with a force of less than 100000N, more preferably less than 50000N, even more preferably less than 5000N and most preferably less than 3000N. In practice, the most preferred embodiment is a detergent tablet suitable for laundry, compressed using a force of less than 2500N, but for example detergent tablets for automatic dishwashing machines are also contemplated, wherein such automatic dishwashing machine detergent tablets are typically more compressed than laundry soap tablets.

The particulate material used to prepare the tablets may be prepared by any granulation or prilling method. Examples of such processes are spray drying (carried out in co-current or counter-current spray drying towers), which generally result in lower bulk densities of 600g/L or less. The higher density particulate material may be granulated and densified in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g., using Lodige)^®CB and/or Lodige^®KM mixer). Other suitable methods include fluidized bed processes, powder extrusion processes (e.g., roller powder extrusion), extrusion, and any particulate material prepared by any chemical process (e.g., flocculation, crystallization, etc.). The individual particles may also be any other particles, granules, pellets or granules.

The components of the particulate material may be mixed together by any conventional method. For example, the batch mode is suitable for use in concrete mixers, nauta mixers, ribbon mixers, or any other mixer. Alternatively, the mixing process may be carried out continuously by metering the weight of each component onto a conveyor belt and mixing them in one or more drums or mixers. A non-gelling binder may be sprayed onto some or all of the mixture of particulate matter components. The other liquid components may also be sprayed on the mixture of said components, either separately or after pre-mixing. For example, a perfume and fluorescer slurry may be sprayed. After spraying the binder (preferably towards the end of the treatment), finely divided flow aids (dusting powders such as zeolites, carbonates, silicas) may be added to the particulate material to render the mixture less viscous.

The sheet-like product can be obtained by using any powderExtrusion methods, such as tableting, briquetting or extrusion, preferably tableting. Suitable equipment includes standard single stroke or rotary tablet presses (e.g., Courtoy)^®、Korch^®、Manesty^®Or Bonals^®). Preferably the tablets prepared according to the invention have a diameter of from 20mm to 60mm, preferably at least 35 to up to 55mm and a weight of from 25 to 100 g. Preferably the sheet-like product has a height to diameter (or width) ratio of greater than 1: 3, more preferably greater than 1: 2. The compression pressure required for preparing these tablets does not exceed 100000kN/m²Preferably not more than 30000kN/m²More preferably not more than 5000kN/m²Even more preferably not more than 3000kN/m²And most preferably not more than 1000kN/m². In a preferred embodiment according to the present invention, the tablet has a density of at least 0.9g/cc, more preferably at least 1.0g/cc, and preferably less than 2.0g/cc, more preferably less than 1.5g/cc, even more preferably less than 1.25g/cc and most preferably less than 1.1 g/cc.

Multilayer tablets are typically formed in a rotary tablet press by placing each layer of matrix one after the other in a matrix positive feed bottle. As processing proceeds, the substrates are then laminated together to a pre-compressed or compressed state to form the multilayer sheet product. In some rotary tablet presses it is also possible to compress the first feed layer before compressing the entire tablet. Hydrotrope compounds

Highly soluble compounds having an adhesive effect, which are also a hydrotrope compound, can be incorporated into the tablet detergent. Such hydrotrope compounds are typically used to facilitate surfactant solubilization while avoiding gelation. The following specific compounds were defined as hydrotropes (see S.E.Friberg and M.Chiu, J.Dispersion science and Technology, 9(5&6), pp. 443-:

1. a solution containing 25% by weight of the specific compound and 75% by weight of water was prepared.

2. Octanoic acid (added at a rate of 1.6 times the weight of the particular compound in solution) was then added to the solution, which was at a temperature of 20 ℃. The solution was mixed in a beaker equipped with a stirrer with a marine propeller (the paddle was about 5mm above the bottom of the Sotax beaker) and the rotation rate of the mixer was set at 200 revolutions per minute.

3. If the octanoic acid is completely solubilized, i.e. if the solution contains only one phase, the specific compound is a hydrotrope when the phase is a liquid phase.

It should be noted that in a preferred embodiment of the invention, the hydrotrope compound is a flowable material prepared from solid particles at operating conditions of 15 to 60 ℃.

Hydrotrope compounds include the compounds listed below:

see McCutcheon's Emulsifiers and Detergents (published by McCutcheon division of Manufacturing conditioners Company) for commercial hydrotropes.

Related compounds also include: 1. a nonionic hydrotrope having the structure:

R·O(CH2CH2O)x(CH·CH2O)yH

CH3 wherein R is C₈-C₁₀Alkyl chains, x is 1-15 and y is 3 to 10. 2. Anionic hydrotropes such as alkali metal aryl sulfonates. This includes benzoic acid, salicylic acid, benzenesulfonic acid and many of its derivatives, naphthoic acid, and alkali metal salts of various hydrogenated aromatic acids. Examples of these are sodium, potassium and ammonium benzenesulfonates from the group consisting of toluenesulfonic acid, xylenesulfonic acid, isopropylbenzenesulfonic acid, 1,2, 3, 4-tetrahydronaphthalenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, trimethylnaphthalenesulfonic acid.

Other examples include dialkylbenzene sulfonates such as diisopropylbenzene sulfonic acid, ethylmethylbenzeneSulfonic acids, alkylbenzenesulfonic acids having an alkyl chain length of 3 to 10 (preferably 4 to 9) carbon atoms, salts of linear or branched alkylsulfonic acids having an alkyl chain of 1 to 18 carbon atoms. 3. Solvent hydrotropes, e.g. alkoxylated glycerol and alkoxylated glycerides, ester slaloxylated glycerol, alkoxylated fatty acids, glycerides, polyglycerides. Preferred alkoxylated glycerols have the following structure:

wherein l, m, n are each a number from 0 to about 20, and l + m + n is from about 2 to about 60, preferably from about 10 to about 45 and R represents H, CH₃Or C₂H₅。

Preferred alkoxylated glycerides have the following structure:

in the formula R₁And R₂Each is C_nCOO or- (CH)₂CHR₃-O)₁-H, wherein R₃＝H、CH₃Or C₂H₅And 1 is a number from 1 to about 60, and n is a number from about 6 to about 24. 4. Polymeric hydrotropes such as those described in EP 636687:wherein E is a hydrophilic functional group, R is H or C₁-C₁₀Alkyl or is a hydrophilic functional group;R₁is H, lower alkyl or aryl, R₂Is H, cycloalkyl or aryl, typically the polymer has a molecular weight of about 1000 to 1000000. 5. Having an abnormal structure such as 5-carboxy-4-hexyl-2-cyclohexen-1-yl octanoic acid (Diacid)^®) Hydrotrope of (1)

The use of such compounds in the present invention will further increase the dissolution rate of the tablet, for example as a hydrotrope compound which facilitates the dissolution of the surfactant. Such compounds may be formed from mixtures or from a single compound. Tensile strength

To measure the tensile strength of a layer, the layer can be considered to be the sheet itself.

Depending on the composition of the raw material and the shape of the tablet, the compression force used can be adjusted to have no effect on the tensile strength and the disintegration time in the washing machine. The process can be used to produce uniform or laminar sheet products of any size or shape.

For cylindrical sheets, the tensile strength corresponds to the radial rupture stress (DFS, which is one way to express the strength of a sheet or layer) and is determined by the following equation:

tensile strength 2F/pi Dt formula F is the maximum force (newtons) that causes tensile failure (fracture) and is measured by a VK 200 sheet hardness tester (supplied by Van Kell industries inc.). D is the diameter of the sheet or layer and t is the thickness of the sheet or layer. For non-circular patches,. pi.D may simply be replaced by the perimeter of the patch. (the process is from the pharmaceutical dosage form: tablet, Vol.2, p.213 to 217). A sheet having a radial rupture stress of less than 20kPa is considered brittle and tends to result in some rupture of the sheet upon delivery to the consumer. Preferably a radial rupture stress of at least 25 kPa.

The definition of tensile strength of a non-cylindrical type sheet (where the cross section perpendicular to the height of the sheet is not circular and where a force is applied in the direction perpendicular to the height of the sheet and to the side of the sheet perpendicular to the non-circular cross section) is similar. Detergent tablet dosing

The dosing rate of the detergent tablets can be determined as follows:

two tablets, nominally 50g each, were weighed and subsequently placed in a Baucknecht^®Dispenser of WA9850 washing machine. The water supply to the washer was set at a temperature of 20 c and a hardness of 21 grains per gallon, and the feeder water inlet flow rate was set at 8L/min. The residual content of the tablets in the dispenser was checked by turning on the washing machine and setting the washing cycle to a washing program 4 (white/color, short cycle). The percent residue of the feed was determined as follows:

percent feed ═ weight of residue x 100/weight of original tablet

The level of residue was determined by repeating the method 10 times and calculating the average residue level from the 10 independent measurements. A 40% residue by weight of the original sheet was considered acceptable in this stress test. Preferably less than 30% and more preferably less than 25% residue.

It should be noted that the water hardness measurements given are in units of the traditional "grains/gallon" where 0.001 moles/liter to 7.0 grains/gallon represents Ca in solution²⁺The concentration of the ions. Effervescent agent

The tablet detergent may also contain an effervescent agent.

Effervescence, as defined herein, refers to the release of gas bubbles from a liquid as a result of the production of carbon dioxide gas as a result of a chemical reaction of a soluble acid source with an alkali metal carbonate.

Namely, it is

Other examples of acid and carbonate sources and other effervescent systems are found in: (pharmaceutical dosage form: tablet, volume 1, pages 287 to 291).

In addition to the detergent ingredients, an effervescent agent may be added to the detergent tablet mixture. The addition of an effervescent agent to the tablet detergent improves the disintegration time of the tablet. Preferably the amount added is from 5 to 20%, most preferably from 10 to 20% by weight of the tablet. Preferably the effervescent is added as an agglomerate of different granules or as a compact rather than as separate granules.

The tablets can have a higher d.f.s and still have the same disintegration time as without the effervescent agent due to gas generation by the effervescent agent in the tablet. The disintegration of the effervescent tablet will be faster when the d.f.s of the effervescent tablet remains the same as that of the tablet without effervescent.

Additional dissolution aids may be provided by using compounds such as sodium acetate or urea. Suitable dissolution aids may also be found in pharmaceutical dosage forms edited by H.A Lieberman et al: tablet, volume 1, second edition, ISBN 0-8247-8044-2.

Other components commonly used in detergent compositions and which may be added to tablet detergents include chelating agents, soil release agents, stain anti-redeposition agents, dispersants, suds suppressors, fabric softeners, dye transfer inhibitors and mixtures thereof. Coating layer

The firmness of the tablet can be improved by preparing a coated tablet, the coating covering the non-coated tablet, thus further improving the mechanical properties of the tablet while maintaining or further improving dissolution.

This is very advantageous for a multi-layer tablet according to the invention, wherein the mechanical properties of the higher elastic layer can be transferred to other parts of the tablet through the coating, thereby combining the advantages of the coating with the advantages of the higher elastic layer. Indeed, mechanical stress may be transmitted through the coating, thereby improving the mechanical integrity of the sheet product.

In one embodiment of the invention, the sheet product may then be coated so that it does not absorb moisture, or absorbs moisture at a very slow rate. The coating is also so strong that only very low levels of fracture or abrasion are produced under moderate mechanical shock to which the sheet product is subjected during handling, packaging and shipping. Finally it is preferred that the coating is so brittle that it breaks when the tablet is subjected to strong mechanical shock. In addition, it is advantageous if the coating dissolves under alkaline conditions or is easily emulsified by surfactants. This avoids the problem of residues being visible at the window of a front-loading washing machine during the wash cycle and avoids sedimentation of insoluble particles or clots of coating material in the washing machine load.

Water solubility is determined according to the following ASTM E1148-87 test procedure, entitled "Standard method for measuring Water solubility".

The cracking of the coating in the wash is improved by adding a disintegration agent to the coating. The disintegrant will swell upon contact with water and break the coating into small pieces. This will improve the dissolution of the coating in the wash solution. Typically the decomposing agent is suspended in the coating melt in an amount of up to 30%, preferably 5 to 20%, most preferably 5 to 10% by weight.

The clay inorganic compound as described above is a decomposer used herein.

In addition to the clay-decomposing agents as described in Handbook of Pharmaceutical Excipients (1986), other useful decomposing agents may be used. Examples of suitable disintegrating agents include starch: native, modified or pregelatinized starch, sodium starch gluconate; gum: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose sodium, crospovidone, cellulose, carboxymethylcellulose, alginic acid and its salts (including sodium alginate), silica, clays, polyvinylpyrrolidone, soybean polysaccharides, ion exchange resins, polymers containing cationic groups (such as quaternary ammonium), amine-substituted polyacrylates, polymeric cationic amino acids (such as poly-L-lysine, polyallylamine hydrochloride) and mixtures thereof.

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

"melting point" refers to the temperature at which the material is slowly heated within the capillary tube to become a clear liquid.

Preferably the coating material having a melting point of at least 40 ℃ is an acid. Examples of acids having a melting temperature of at least 40 ℃ are dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from 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 crystalline structure. By crystalline structure, it is understood that the coating comprises a material that is solid at room temperature (25 ℃) and has some ordered structure. It can be detected by typical crystallographic imaging techniques on the material itself, such as X-ray analysis. In a more preferred embodiment, the material forming the crystalline structure does not co-crystallize or only partially co-crystallize with the optional components having a liquid at 25 ℃ as described above. It is actually preferred that the optional components remain liquid at 25 ℃ in the coating crystal structure to provide structural flexibility and resistance to mechanical stress. Most preferably, the acid having a melting point of at least 40 ℃ comprises a crystalline structure.

It is clear that substantially insoluble materials having a melting point below 40 c do not remain sufficiently solid at room temperature, and materials having a melting point above about 200 c are not found practical. Acids with melting points above 90 c such as azelaic acid, sebacic acid, dodecanedioic acid are preferred. However, for the purposes of the present invention, sebacic acid is less preferred because it gives the resulting product an unpleasant odor. According to the present invention, acids having a melting point of greater than 145 deg.C, such as adipic acid, have been found to be particularly useful.

The coating may be applied by several methods. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of said material.

In a), the coating material is applied to the sheet-like product at a temperature above the melting point of the coating material and cured, and in b) the coating is carried out with the solution and the solvent is dried away from the adherent coating. The substantially insoluble material may be applied to the sheet-like product by, for example, spraying or dipping. The molten material typically solidifies rapidly to form an adherent coating when sprayed onto the sheet-like product. When the sheet-like product is immersed in the molten material and subsequently removed, rapid cooling again causes rapid solidification of the coating material. During this curing stage, the coating is subjected to some internal (e.g., shrinkage upon cooling) and external (e.g., relaxation of the sheet product) stresses. If the coating material is too brittle to withstand these mechanical stresses, some cracking such as edge cracking (edge splitting) may occur in the structure, which occurs when the coating is prepared from only components that are solid at 25 ℃. It is therefore preferred that the coating comprises a component which is liquid at 25 ℃. It is believed that this liquid component allows the coating to better withstand and absorb mechanical stresses by imparting greater flexibility to the coating structure. The amount of the component which is liquid at 25 ℃ added to the coating material is preferably less than 10%, more preferably less than 5%, most preferably less than 3% by weight of the coating. The proportion of the component which is liquid at 25 ℃ added to the coating material is preferably greater than 0.1%, more preferably greater than 0.3%, most preferably greater than 0.5% by weight of the coating.

Examples of optional components that are liquid at 25 ℃ include polyethylene glycol, hot oils, silicone oils, esters of dicarboxylic acids, monocarboxylic acids, paraffins, triacetin, fragrances, or alkaline solutions. Particularly good results are obtained, for example, by using NaOH solution as alkaline solution.

The structure of the component, which is preferably liquid at 25 ℃, is adjacent to the material forming the crystalline structure so that the structure is not unduly disrupted.

In another embodiment, the optional component which is liquid at 25 ℃ may advantageously have a function for laundry washing, such as a silicone oil or a sesame oil which may provide an antifoaming effect. When present, the fragrance oil may be a fragrance composition as described herein or a fragrance composition different from that already contained in the tablet, provided that it contains less than 0.6% by weight of schiff bases.

The coating may also include some other materials in addition to the optional components described above (liquid at 25 ℃). It is therefore further preferred to add reinforcing fibres to the coating to further strengthen the structure.

In the most preferred embodiment, the crystal structure is formed from adipic acid, and the optional component that is liquid at 25 ℃ is available from Coosol from Chemoxy International^TM(trade name) which is a mixture of diisobutyl esters of glutaric, succinic and adipic acids. The advantage of using such a component is a good dispersion in adipic acid providing flexibility. It should be noted that the reagent is made by Coasol^TMThe content of medium adipic acid esters further improves the decomposition of adipic acid.

According to a preferred embodiment of the invention, the coating comprises an acid having a melting point of at least 145 ℃ (such as adipic acid) and a clay (such as bentonite), wherein the clay acts as a disintegrant and also makes the adipic acid structure more accessible to water penetration, thereby improving the dispersion of the adipic acid in the aqueous medium. Preferably the clay has a particle size of less than 75 microns, more preferably less than 53 microns, to achieve the desired effect of the acid structure. Preferably the clay is a bentonite clay. The acid, which actually has a melting point, causes thermal degradation of the conventional cellulolytic agents during coating, while the clay has better thermal stability. In addition, conventional cellulolytic agents such as Nymcel at these temperatures^TMIt becomes brown.

In another preferred embodiment, the coating further comprises reinforcing fibers. It was found that these fibers can further improve the resistance of the coating to mechanical stress and minimize fracture defects. The preferred length of these fibers is at least 100 microns, more preferably at least 200 microns, and most preferably at least 250 microns to strengthen the structure. The preferred length of these fibers is less than 500 microns, more preferablyPreferably less than 400 microns and most preferably less than 350 microns so as not to interfere with the dispersion of the coating in the aqueous medium. Materials that may be used for these fibers include viscous rayon, natural nylon, synthetic nylon (polyamide 6 and 6,6 types), acrylic, polyester, nylon,Cotton and cellulose derivatives such as CMC. Most preferably from Fibers Sales&Development is named Solka-Floc^TMThe article of commerce of (1). It should be noted that these fibers generally do not need to be pre-compressed to strengthen the coating structure. These fibers are preferably added at a level of less than 5%, more preferably less than 3% by weight of the coating. These fibers are preferably added at a level of greater than 0.5%, more preferably greater than 1% by weight of the coating.

Any desired thickness of the coating may be applied according to the invention. For most purposes, the coating is 1% to 10%, preferably 1.5% to 5% by weight of the sheet product.

The coating of the sheet-like product is extremely hard and provides the sheet-like product with great strength. Method of producing a composite material

A preferred method of preparing a sheet-like product according to the invention comprises the steps of:

(a) forming a core by compressing a particulate material, the particulate material comprising a surfactant and a detergency builder;

(b) applying a coating material to the core, the coating material being in the form of a melt;

(c) solidifying the molten coating material;

characterized in that the coating comprises clay.

Another preferred method of preparing a sheet-like product according to the invention comprises the steps of:

(a) forming a core by compressing a particulate material, the particulate material comprising a surfactant and a detergency builder;

(b) applying a coating material to the core, the coating material having been dissolved in a solvent or water;

(c) evaporating the solvent or water;

characterized in that the coating comprises clay.

The compounds disclosed above are preferably packaged as products in a packaging system.

The packaging system may be formed from a sheet of flexible material. Materials suitable for use as the flexible sheet include single layer, coextruded or laminated films. These films may include various components such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate. Preferably, the packaging system is comprised of a coextruded film of polyethylene and bi-directional polypropylene having an MVTR of less than 5g/day/m². What is preferredThe MVTR of the packaging system is less than 10g/day/m²More preferably less than 5g/day/m². The membrane (2) may have different thicknesses. The thickness is typically 10 to 150 microns, preferably 15 to 120 microns, more preferably 20 to 100 microns, even more preferably 25 to 80 microns, most preferably 30 to 40 microns.

Preferably the packaging system comprises a barrier layer having a low oxygen permeation rate, typically less than 300cm, common in packaging materials³/m²Day, preferably less than 150cm³/m²Day, more preferably less than 100cm³/m²Day, even more preferably less than 50cm³/m²/day, most preferably less than 10cm³/m²And/day. Typical materials having such a barrier layer include bi-directional polypropylene, polyethylene terephthalate, nylon, poly (ethylene vinyl alcohol), or a laminate comprising one of these materials, and siox (silicon oxides) or a metal foil such as aluminum foil. These packaging materials may have a beneficial effect on e.g. the stability of the product upon storage.

The processes used are typically the wrapping processes disclosed in WO92/20593, including flow wrapping (flow wrapping) or over wrapping (over wrapping). When using these methods, a longitudinal seal is provided, which may be a lock-in (fin) seal or a lap seal, after which a first end of the packaging system is enveloped with a first end seal, followed by a second end of the packaging system with a second end seal. The packaging system may comprise a re-wrapping device as described in WO 92/20593. In particular, cold sealing or gluing with twist is particularly suitable. In fact, a cooling sealing strip or tape may be applied to the surface of the packaging system near the second end position of the packaging system, such that the strip may provide an initial sealing and re-enclosure of the packaging system. In this case, the adhesive tape or the cooling seal tape may correspond to a region having an adhesive surface, i.e. only one surface to which the other adhesive surface adheres. Such a re-encapsulation device also includes a space (spacer) to prevent unwanted adhesion. Such intervals are described in WO 95/13225, published at month 5 and 18 of 1995. There are also many spaces and many strips of adhesive material. It is a major requirement to minimize the exterior and interior of the package even after the first opening of the packaging system. A cold seal, in particular a cold seal grate, may be used, whereby the cold seal is used to facilitate the opening of the packaging system.

Examples

The following are non-limiting examples of suitable perfume compositions for use in the following non-limiting tablet detergent examples of the present invention.

Perfume component	Percentage in perfume composition%
		Geraniol	5.0
Citronellol	5.0
		Acetic acid 4-tert-butylcyclohexyl ester	5.0
Phenylethanols	10.0
		Hexahydro-4, 7-Methano (Methano) -inden-5-ylethyl Acid esters, sold under the trade name Cyclacet	6.0
Citronellyl acetate	2.5
		Geraniyl acetate	2.5
Hexyl cinnamic aldehyde	4.5
		P-hydroxyphenyl butanone	3.0
PT lily aldehyde	24.0
		Methylionone	10.0
Rosalva	2.0
		Dihydrojasmonic acid methyl ester	7.0
Undecenal	0.5
		Methyl isobutenyl tetrahydropyran	1.0
Acetic acid tert-butyl cyclohexyl ester	6.0
		Salicylic acid hexyl ester	6.0
Total of	100.0

Abbreviations used in the following detergent examples 1-6

In detergent compositions, the abbreviations components indicated have the following meanings:

anionic agglomerate 1 comprising 40% anionic surfactant, 27% zeolite and 33% carbonate

Anionic agglomerate 2 comprising 40% anionic surfactant, 28% zeolite and 32% carbonate

Non-ionic agglomerates comprising 26% non-ionic surfactant, 6% Lutensitt K-HD 96, 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite

Cationic agglomerate comprising 20% cationic surfactant, 56% zeolite and 24% sulfate

Layered silicate comprising 95% SKS 6 and 5% silicate

Bleach activator agglomerate comprising 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water

Ethylenediamine N, N-disuccinic acid sodium salt/sulfate particles comprising 58% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water

Suds suppressor comprising 11.5% silicone oil (available from Dow Corning), 59% zeolite and 29.5% water

An adhesive spray system comprising 16% by weight of a polymer having the formula

68% by weight of PEG4000 and 16% by weight of DIBS (sodium diisoalkylbenzene sulfonate or sodium toluene sulfonate)

Abbreviations used in detergent example 7 below

In detergent compositions, the abbreviations components indicated have the following meanings:LAS straight chain C_11-13Sodium alkyl benzene sulfonate TAS tallow alkyl sodium sulfate C_xyAS C_1x-C_1ySodium alkyl sulfate C₄₆SAS C₁₄-C₁₆Sodium secondary (2, 3) alkylsulfate C_xyE_zS C_1x-C_1yCondensation C of sodium alkyl sulfate with z moles of ethylene oxide_xyE_z C_1x-C_1yCondensation of predominantly linear primary alcohols with an average of z moles of ethylene oxideQAS R₂.N⁺(CH₃)₂(C₂H₄OH)，R₂＝C₁₂-C₁₄QASl R₂.N⁺(CH₃)₂(C₂H₄OH)，R₂＝C₈-C₁₁SADS formula 2- (R). C₄H₇-1，4-(SO₄)₂C of (A)₁₄-C₂₂The sodium alkyl sulfate is added with the sodium hydrogen alkyl sulfate,

wherein R is C₁₀-C₁₈SADE2S formula 2- (R). C₄H₇-1，4-(SO₄)₂C of (A)₁₄-C₂₂The sodium alkyl sulfate is added with the sodium hydrogen alkyl sulfate,

wherein R is C₁₀-C₁₈Condensation of MES C with z mol of ethylene oxide₁₈X-sulfomethyl ester of fatty acids APA C₈-C₁₀Amidopropyl Dimethylamide soap is derived from the linear alkane of 80/20 mixture of tallow and coconut fatty acids

Sodium polycarboxylate STS sodium toluenesulfonate CFAA C₁₂-C₁₄(Coco) alkyl N-methylglucamide TFAA C₁₆-C₁₈Alkyl N-methylglucamides TPKFA C₁₆-C₁₈Topping full cut fraction fatty acid STPP anhydrous sodium tripolyphosphate TSPP tetrasodium pyrophosphate Zeolite A formula Na₁₂(AlO₂SiO₂)₁₂.27H₂Hydrated sodium aluminosilicate of O, primary

Particle size 0.1-10 microns (weight based on anhydride) NaSKS-6 formula delta-Na₂Si₂O₅The crystalline layered silicate citric acid anhydrous citric acid borate sodium borate carbonate anhydrous sodium carbonate has a particle size of 200 to 900 micrometers of bicarbonate anhydrous sodium bicarbonate, and a particle size distribution of 400 to 1200 micrometers of silicate amorphous sodium Silicate (SiO)₂∶Na₂O2.0: 1) sulfate anhydrous sodium sulfate magnesium sulfate anhydrous magnesium sulfate citrate trisodium citrate dihydrate with an activity of 86.4% and a particle size distribution of 425

Micrometer-850 micrometer MA/AA 1: 4 maleic/acrylic acid copolymer, average molecular weight of about 70,000MA/AA (l) 4: 6 maleic/acrylic acid copolymer, average molecular weight of about 10,000AA sodium polyacrylate polymer, methyl cellulose ether with average molecular weight of 4,500CMC sodium carboxymethyl cellulose ether degree of polymerization of 650, available from Shin Etsu

Chemicals protease proteolytic enzyme having 3.3% by weight of active enzyme, from NOVO

Industries A/S sold protease I proteolytic enzyme under the trade name Savinase, having 4% by weight active enzyme, is described in WO

95/10591 Alcalase proteolytic enzyme sold by Genencor int.Inc. having 5.3% by weight of active enzyme, produced by NOVO

Industries A/S sells cellulase cellulolytic enzymes with 0.23% by weight of active enzyme from NOVO

Industries A/S sold amylase starch hydrolase under the trade name Carezyme, having 1.6% by weight active enzyme, from NOVO

Starch Hydrolase Lipase Lipohydrolase, commercially available from Industries A/S under the trade name Termamy 120T, disclosed in PCT/US9703635, having 2.0% by weight of active enzyme, consisting of NOVO

Industries A/S Lipase II lipolytic enzyme sold under the trade name Lipolase, having 2.0% by weight of active enzyme, from NOVO

Industries A/S sold as Endolase endoglucanase under the trade name Lipolase Ultra, with 1.5% by weight of active enzyme, from NOVO

Industrial A/S sold PB4 Standard NaBO₂.3H₂O.H₂O₂Sodium perborate tetrahydrate PB1 standard NaBO₂.H₂O₂Anhydrous sodium perborate bleach percarbonate of the formula 2Na₂CO₃.3H₂O₂Sodium percarbonate bleach (DOBS decanoyloxybenzenesulfonic acid sodium salt DPDA diperoxydodecanedioic acid)NOBS nonanoyloxybenzenesulfonic acid sodium salt NACA-OBS (6-nonanoylhexanoyl) oxybenzenesulfonic acid LOBS dodecanoyloxybenzenesulfonic acid sodium salt DOBS decanoyloxybenzenesulfonic acid sodium salt DOBA dodecanoyloxybenzoic acid TAED tetraacetylethylenediamine DTPA diethylenetriamine pentaacetic acid DTPMP diethylenetriamine penta (methylene phosphonate) prepared by Monsanto as

Desquest 2060 sold under the trade name EDDS ethylenediamine-N, N ' -disuccinic acid, (S, S) isomer photoactivator as sodium salt Encapsulated in Bleach (1) dextrin soluble Polymer sulfonated Zinc phthalocyanine photoactivator Encapsulated in Bleach (2) dextrin soluble Polymer sulfonated aluminum phthalocyanine brightener 14, 4 ' -bis (2-sulfostyryl) Biphenyl disodium brightener 24, 4 ' -bis (4-anilino-6-morpholinyl-1.3.5-triazin-2-yl) amino) stilbene-

2: 2' -disodium disulfonate HEDP 1, 1-hydroxyethane diphosphonic acid PEG_xPolyethylene glycol, PEO polyethylene oxide of molecular weight x (typically 4,000), TEPAE tetraethylenepentamine ethoxylate PVI polyvinylimidazole of average molecular weight 50,000, PVP polyvinylpyrrolidone polymer of average molecular weight 20,000, polyvinylpyridine N-oxide polymer of average molecular weight 60,000PVNO, poly (vinylpyridine N-oxide) of average molecular weight

50,000PVPVI copolymer of polyvinylpyrrolidone and vinylimidazole, average

The quantum size was 20,000QEA bis ((C)₂H₅O)(C₂H₄O)_n)(CH₃)-N⁺-C₆H₁₂-N⁺-(CH₃)

Bis ((C)₂H₅O)(C₂H₄O))_nWherein n is 20-30PEI, polyethyleneimine having an average molecular weight of 1800, degree of ethoxylation

Clay I bentonite clay II bentonite clay II smectite clay flocculant I with 7 ethylene oxide residues per nitrogen polyethylene oxide flocculant II with an average molecular weight of 200,000-400,000 polyethylene oxide flocculant II with an average molecular weight of 400,000-1,000,000 polyethylene oxide flocculant III with an average molecular weight of 200,000-400,000 polyethylene oxide SRP I anion terminated polyester soil release polymer SRP II polysaccharide soil release polymer SRP 1 nonionic terminated polyester SRP 2 diethoxylated poly (1, 2-propylene terephthalate) short block poly

Compound silicone defoamer polydimethylsiloxane with siloxane-oxyalkylene copolymer as dispersant

A foam control agent, the ratio of the foam control agent to the dispersant being

10: 1 to 100: 1 sunscreen Water-based Monostyrene latex mixture from BASF

Aktiengesellschaft sells wax paraffin Speckle colored carbonate or organic carboxylic acid/salt under the trade name Lytron 621

Example 1

i) A detergent base powder of composition a was prepared as follows: with the exception of the binder spray system, fluorescer or brightener and photobleach zinc phthalocyanine sulfonate, all of the particulate materials of the base composition are mixed together in a mixing drum or in a spray drum to form a homogeneous particulate mixture. The particle mixture was thereafter divided into two equal parts, one for the preparation of the white layer and the other for the preparation of the green layer. White layer material is obtained by spraying a whitening agent and a fluorescent agent together with a semi-adhesive. The green layer material was obtained by spraying the photobleach zinc phthalocyanine sulfonate with the remaining binder. This layer was separately placed on Loedige KM 600^®The processing treatment is carried out.

ii) using Bonals^®The press was rotated to fill two substrates into two separate pressure feed bottles. The two layers are compressed in a pre-pressing and compression station to form a two-layer sheet product.

iii) in this particular example, the sheet product has a cross-sectional edge of 45 mm, a height of 24 mm and a weight of 45 gr. The height of the green bottom layer corresponds to 50% of the total height of the sheet product, and the tensile strength of the uncoated sheet product is 13 kpa.

iv) the sheet product was thereafter coated with 2.5 grams of a coating formed from 90% by weight of adipic acid and 10% by weight of bentonite from the CSM.

	Composition A (%)
		Anionic agglomerates 1	9.1
Anionic agglomerates 2	22.5
		Nonionic agglomerates	9.1
Cationic agglomerates	4.6
		Layered silicate	9.7
Sodium percarbonate	12.2
		Bleach activator agglomerates	6.1
Sodium carbonate	7.67
		EDDS/sulfate particles	0.5
Tetra sodium hydroxy ethane diphosphonate	0.6
		Soil release polymers	0.3
Fluorescent agent	0.2
		Phthalocyanine sulfonic acid zinc salt	0.03
Soap powder	1.2
		Suds suppressor	2.8
Citric acid	5.5
		Protease enzyme	1
Lipase enzyme	0.35
		Cellulase enzymes	0.2
Amylase	1.1
		Adhesive spray system	4.75
Perfume spray	0.5

Example 2

i) The detergent base powder of composition a was prepared as follows: all of the particulate materials of the base composition are mixed together in a mixing or spray drum to form a homogeneous particulate mixture. After which the adhesive system is sprayed thereon. Then in Loedige KM 600^®The treatment is carried out.

ii) using an Instron^®A laboratory bench press, filling the detergent powder into the mould. The powder was compressed hard to give a sheet product with a tensile strength of 10 kpa.

iii) in this particular example, the cross-section of the sheet product is 54 mm on a side, 24 mm high and 45gr heavy.

iv) the tablet was then coated with 2.5g of a coating formed from 90% by weight adipic acid and 10% by weight clay from CSM.

Example 3

i) The detergent base powder of composition a was prepared as follows: all of the particulate materials of the base composition are mixed together in a mixing or spray drum to form a homogeneous particulate mixture. After which the adhesive system is sprayed thereon. Then in Loedige KM 600^®The treatment is carried out.

ii) using an Instron^®A laboratory bench press, filling the detergent powder into the mould. The powder was compressed hard to give a sheet product with a tensile strength of 10 kpa.

iii) in this particular example, the cross-section of the sheet product is 54 mm on a side, 24 mm high and 45gr heavy.

Thereafter 2.5g of a mixture of 89% by weight of adipic acid, 10% by weight of bentonite and l% by weight of Coasol were used^TMThe coating formed coats the sheet-like product.

Example 4

i) The detergent base powder of composition a was prepared as follows: all of the particulate materials of the base composition are mixed together in a mixing or spray drum to form a homogeneous particulate mixture. After which the adhesive system is sprayed thereon. Then in Loedige KM 600^®Inner proceeding departmentAnd (6) processing.

ii) using an Instron^®A laboratory bench press, filling the detergent powder into the mould. The powder was compressed hard to give a sheet product with a tensile strength of 10 kpa.

iii) in this particular example, the cross-section of the sheet product is 54 mm on a side, 24 mm high and 45gr heavy.

Thereafter using 2.5g of a mixture of 87% by weightAdipic acid, 10% by weight of bentonite from, 1% by weight of Coasol^TMAnd 2% Solka-Floc^TM1016 to coat the sheet-like product.

Example 5

i) The detergent base powder of composition a was prepared as follows: all of the particulate materials of the base composition are mixed together in a mixing or spray drum to form a homogeneous particulate mixture. After which the adhesive system is sprayed thereon. Then in Loedige KM 600^®The treatment is carried out.

ii) using an Instron^®A laboratory bench press, filling the detergent powder into the mould. The powder was compressed hard to give a sheet product with a tensile strength of 10 kpa.

iii) in this particular example, the cross-section of the sheet product is 54 mm on a side, 24 mm high and 45gr heavy.

Thereafter 2.5g of a mixture of 78% by weight of adipic acid, 18.5% by weight of bentonite from, 1% by weight of Coasol^TMAnd 2.5% by weight NaOH (1M) to coat the sheet-like product.

Example 6

i) The detergent base powder of composition a was prepared as follows: all of the particulate materials of the base composition are mixed together in a mixing or spray drum to form a homogeneous particulate mixture. After which the adhesive system is sprayed thereon. Then in Loedige KM 600^®The treatment is carried out.

ii) using an Instron^®A laboratory bench press, filling the detergent powder into the mould.The powder was compressed hard to give a sheet product with a tensile strength of 10 kpa.

iii) in this particular example, the cross-section of the sheet product is 54 mm on a side, 24 mm high and 45gr heavy.

Thereafter 2.5g of a mixture of 88% by weight of adipic acid, 10% by weight of bentonite from, 1% by weight of Coasol^TMAnd 1% of ethane 1-hydroxy diphosphonic acid tetrasodium salt.

Example 7

The following are some detergent compositions of the present invention that may be used as or in place of composition a of any of examples 1-6 as described above.

All water levels in the following examples are in weight percent of the composition.

	B	C	D	E
					Blown powder
Clay I or II	7.0	10.0	6.0	2.0
					Flocculating agents I or II	0.3	1.0	1.0	0.5
LAS	16.0	5.0	11.0	6.0
					TAS	-	5.0	-	2.0
Zeolite A	-	20.0	-	10.0
					STPP	24.0	-	14.0	-
Sulfates of sulfuric acid	-	2.0	-	-
					MA/AA	-	2.0	1.0	1.0
Silicates of acid or alkali	4.0	7.0	3.0	-
					CMC	1.0	-	0.5	0.6
Whitening agent	0.2	0.2	0.2	0.2
					Sodium carbonate	10.0	10.0	20.0	-
DTPMP	0.4	0.4	0.2	-

Spray mist
					Whitening agent	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 agent	0.3	-	-	-
Dry additives
					QEA	-	-	-	1.0
HEDP/EDDS	0.3	-	-	-
					Sulfates of sulfuric acid	2.0	-	-	-
Carbonate salt	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 salts	-	-	-	9.0
					PB4	-	-	5.0	-
NOBS	-	-	-	1.3
					TAED	-	-	2.0	1.5
Protease enzyme	1.0	1.0	1.0	1.0
					Lipase enzyme	-	0.4	-	0.2
Amylase	0.2	0.2	0.2	0.4
					Whitening agent	0.05	-	-	0.05
Perfume	1.0	0.2	0.5	0.3
					Granules	1.2	0.5	2.0	-
Trace/small amount of components to 100%

The following are compositions suitable for this purpose.

F G H I J K L

C11-C13Alkyl benzene sulfonic acid Sodium salt	12.0	16.0	23.0	19.0	18.0	20.0	16.0
								C14-C15Sodium alcohol sulfate		4.5	-		-	-	4.0
C14-C15Alcohol ethoxy group Sulfuric acid (0.5)			-	-	-	-	-
								C14-C15Alcohol ethoxy group Sulfate salt of (3)	-	-	2.0	-	1.0	1.0	1.0
C14-C15Alcohol ethoxy group Sodium salt	2.0	2.0	-	1.3	-	-	5.0
								C9-C14Alkyl dimethyl Hydroxyethyl quaternary ammonium salt			-	-	1.0	0.5	2.0
Tallow fatty acid			-	-	-	-	1.0
								Tallow alcohol ethoxylation Thing (50)	-	-	-	-	-	-	-
Sodium tripolyphosphate/zeolite	23.0	25.0	14.0	22.0	20.0	10.0	20.0
								Sodium carbonate	25.0	22.0	35.0	20.0	28.0	41.0	30.0
Polysodium acrylate (45%)	0.5	0.5	0.5	0.5	-	-	-
								Polysodium acrylate/maleic acid Sodium acid polymer	-	-	1.0	1.0	1.0	2.0	0.5
Sodium silicate (1: 6) NaO/SiO2)(46％)	3.0	6.0	9.0	8.0	9.0	6.0	8.0
								Sodium sulfate	-	-	-	-	-	2.0	3.0
Sodium perborate/percarbonic acid Sodium salt	5.0	5.0	10.0	-	3.0	1.0	-
								A poly (ethylene glycol) having a high degree of polymerization, MW～4000(50％)	1.5	1.5	1.0	1.0	-	-	0.5

sodium carboxymethylcellulose	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	-
								Clay I or II	5.0	6.0	12.0	7.0	10.0	4.0	3.0
Flocculating agents I or III	0.2	0.2	3.0	2.0	0.1	1.0	0.5
								Wetting agent	0.5	1.0	0.5	1.0	0.5	0.5	-
Wax	0.5	0.5	1.0	-	-	0.5	0.5
								Moisture content	7.5	7.5	6.0	7.0	5.0	3.0	5.0
Magnesium sulfate	-	-	-	-	-	0.5	1.5
								Chelating agents	-	-	-	-	0.8	0.6	1.0
Enzymes, including starch Enzyme, cellulase, EggWhite enzyme and lipase	-	-	-	-	2.0	1.5	2.0
								Speckle	2.5	4.1	4.2	4.4	5.6	5.0	5.2
Minor ingredients, e.g. perfumes Material, PVP, PVPVI/PVNO、 Brightener and photobleaching Agent for treating cancer	2.0	1.0	1.0	1.0	2.5	1.5	1.0

The following are detergent compositions suitable for use herein.

M N O P

C11-C13Sodium alkyl benzene sulfonate	23.0	13.0	20.0	18.0
					C14-C15Sodium alcohol sulfate	-	4.0	-	-
Clay I or II	5.0	10.0	14.0	6.0
					Flocculating agents I or II	0.2	0.3	0.1	0.9

Wax	0.5	0.5	1.0	-
					Humectant (Glycerol/silicon dioxide)	0.5	2.0	1.5	-
C14-C15Alcohol ethoxylated sulfates	-		-	2.0
					C14-C15Alcohol ethoxy sodium	2.5	3.5	-	-
C9-C14Alkyl dimethyl hydroxyethyl quaternary ammonium salt	-	-	-	0.5
					Tallow fatty acid	0.5	-	-	-
Tallow alcohol ethoxylate (50)	-	-	-	1.3
					Sodium tripolyphosphate	-	41.0	-	20.0
Zeolite A, hydrate (0.1-10 microns) Particle diameter of (1)	26.3	-	21.3	-
					Sodium carbonate	24.0	22.0	35.0	27.0
Polysodium acrylate (45%)	2.4	-	2.7	-
					Polysodium acrylate/sodium maleate polymer	-	-	1.0	2.5
Sodium silicate (1: 6 or 2 or 2.2 ratio) NaO/SiO2)(46％)	4.0	7.0	2.0	6.0
					Sodium sulfate	-	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 carboxymethylcellulose	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 polymers	-	1.5	1.0	1.0
Moisture content	7.5	3.1	6.1	7.3
					Magnesium sulfate	-	-	-	1.0
Chelating agents	-	-	-	0.5
					Speckle	1.0	0.5	0.2	2.7

Enzymes, including amylases, cellulases, enzymes, Protease and lipase	-	1.0	-	1.5
					Minor ingredients, e.g. brighteners, photobleaches Agent for treating cancer	1.0	1.0	1.0	1.0

The following are 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
						Flocculating agents II or III	0.5	0.2	0.9	1.5	-
LAS	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 carbonate	5.0	20.0	20.0	10.0	-
Whitening agent	0.05	-	-	0.05	0.05
						Clay 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
						Defoaming agent (Silicone)	1.0	1.0	-	2.0	0.5
Agglomerates
						Clay clay	9.0	-	-	4.0	10.0
Wax	0.5	-	-	0.5	1.5
						Glycerol	0.5	-	-	0.5	0.5
Agglomerates
						LAS	-	5.0	5.0	-	-
TAS	-	2.0	1.0	-	-

Silicates of acid or alkali	-	3.0	4.0	-	-
						Zeolite A	-	8.0	8.0	-	-
Carbonate salt	-	8.0	4.0	-	-
						Spray mist
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
						Clay I or II	-	5.0	5.0	-	-
Flocculating agents I or II	-	-	-	-	0.2
						Bicarbonate salt	-	3.0	-	-	-
Carbonate salt	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 enzyme	0.3	1.0	1.0	0.3	0.3
Lipase enzyme	-	0.4	0.4	-	-
						Amylase	0.2	0.6	0.6	0.2	0.2
Cellulase enzymes	0.2	0.6	0.6	0.2	0.2
						Silicone antifoam agent	-	5.0	5.0	-	-
Spice (starch)	0.2	0.3	1.0	0.2	0.2
						Speckle	0.5	0.5	0.1	-	1.0
SKS-6 (silicate 2R)	3.5	-	-	-	3.5
						Photobleaches	0.1	-	-	0.1	0.1
Soap	0.5	2.5	-	0.5	0.5
						Sodium sulfate	-	3.0	-	-	-

Trace/small amount of components to 100%	100.0	100.0	100.0	100.0	100.0
						Density (g/L)	850	850	850	850	850

Claims (16)

1. A perfumed detergent tablet, the tablet comprising a clay mineral compound; wherein said perfume comprises less than 0.6% Schiff base by weight of said perfume composition.

2. A perfumed detergent tablet according to claim 1, wherein said tablet further comprises a coating.

3. A tablet according to one of claims 1 or 2, wherein the clay inorganic compound is present in the coating in particles having a particle size of less than 75 microns.

4. A tablet according to any one of claims 1 to 3, wherein the tablet is a softened tablet.

5. A tablet according to any one of claims 1 to 4, wherein the perfume composition is substantially free of Schiff bases.

6. A tablet according to any one of claims 1 to 5, wherein the perfume composition is free of perfume ingredients selected from: methyl anthranilate and hydroxycitronellal, methyl anthranilate and methylnonyl acetaldehyde, methyl anthranilate and PT lily aldehyde, methyl anthranilate and neo-lily aldehyde, methyl anthranilate and ligustral, and mixtures thereof.

7. A tablet according to any one of claims 2-6, wherein the coating further comprises an acid having a melting point of at least 40 ℃, preferably at least 145 ℃.

8. A tablet according to claim 7, wherein the acid having a melting point of at least 40 ℃ has a crystalline structure.

9. A tablet according to claim 8, wherein the acid forming the crystal structure is a dicarboxylic acid, preferably adipic acid.

10. A tablet according to any one of claims 2-9, wherein the coating consists essentially of adipic acid.

11. A tablet according to any one of claims 2 to 10, wherein the coating further comprises a component which is liquid at 25 ℃.

12. A tablet according to any one of claims 2-11, wherein the coating further comprises reinforcing fibres.

13. A tablet according to any one of claims 1-12, wherein the tablet further comprises a heavy metal ion sequestrant, preferably selected from organic phosphonates.

14. A tablet according to any one of claims 1 to 13, wherein the detergent further comprises a flocculating agent.

15. A method of making a sheet-like product according to any one of claims 2 to 14, said method comprising the steps of:

(a) forming a core by compressing a particulate material comprising a surfactant and a builder;

(b) applying a coating material to the core, the coating material being in the form of a melt;

(c) curing the molten coating material; characterized in that the coating comprises clay.

16. A method of making a sheet-like product according to any one of claims 2 to 14, said method comprising the steps of:

(a) forming a core by compressing a particulate material comprising a surfactant and a builder;

(b) applying a coating material to the core, the coating material being dissolved in a solvent or water;

(c) evaporating the solvent or water; characterized in that the coating comprises clay.