ES2310935T3 - PERFUMED DETERGENT PAD. - 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

Scented detergent tablet.

Technical Field of the Invention

The present invention relates to tablets of scented detergent, especially those adapted tablets for use in clothes washers, and to processes to manufacture these pills

Background of the invention

Scented products are well known in The technique. However, consumer acceptance of these scented products, such as laundry products and cleaning, is determined not only by the performance obtained with these products but also for the aesthetics associated with them. The Perfume components are therefore an important factor for the Successful formulation of these commercial products.

In addition, a clay mineral compound is a Desirable ingredient of this product for laundry and cleaning, particularly those products that are in the form of tablet. In fact, clay can provide an advantage. softener but can also serve as a disintegrant of these detergent tablets

However, a problem encountered with the scented detergent tablets containing a compound clay ore is that clay can have a negative effect on the action of the perfume contained therein. Therefore without pretend to impose any theory, it is believed that due to the narrow physical proximity determined by the pill, the perfume is absorbed in clay where it can interact with metal ions heavy and acid or base sites within the clay, being able to produce a discoloration of the clay. Also the interaction between the perfume and the clay can make the tablet have a less attractive smell

Therefore, an object of the invention is provide a scented detergent tablet comprising a clay mineral compound that exhibits good yield of perfume and reduced clay discoloration.

In addition, compositions have often been proposed pill-shaped cleaners although they have not had (except soap bars for personal hygiene) an important success to despite the different advantages of the products in a way of unit dispensing. One of the reasons for this may be that detergent tablets require a manufacturing process relatively complex. In particular, it is often desirable provide the tablet with a coating and this adds manufacturing difficulties

Although the uncoated tablets are fully effective in their use, they usually lack the hardness surface necessary to withstand the abrasion that the normal processes of preparation, packaging and handling. He result is that the uncoated tablets suffer abrasion during these processes giving rise to chipped tablets and a loss of active material.

Finally, it is often desirable to coat the pills for aesthetic reasons to improve the appearance of the pill or to achieve some particular aesthetic effect.

Numerous methods have been proposed to coat pills and many of them have been suggested for pills Detergent. However, all these methods have some Disadvantages, as will be explained below.

The patent GB-A-0 989 683, published on 22 April 1965, describes a process for preparing a detergent in particle form from surfactants and inorganic salts, spray a water soluble silicate and compress the particles of detergent in a solid tablet that retains the shape. Finally, an organic film-forming polymer easily soluble in water (for example, polyvinyl alcohol) provides a coating to make the detergent tablet resistant to abrasion and accidental fractures.

The patent EP-A-0 002 293, published on 13 June 1979, describes a coating of tablets comprising hydrated salt such as acetate, metaborate, orthophosphate, tartrate and sulfate.

The patent EP-A-0 716 144, published on 12 June 1996, also describes detergent tablets for laundry with water soluble coatings that can be organic polymers that include acrylic / maleic copolymer, polyethylene glycol, PVPVA and sugar.

WO9518215, published July 6 from 1995, provides water soluble coatings for tablets solid molded. The tablets are provided with coatings hydrophobes that include wax, fatty acid, fatty acid amides and polyethylene glycol

In EP-A-0 846 754, published on June 10, 1998, a pill is provided having a coating comprising a dicarboxylic acid, in where the coating material typically has a point melting from 40 ° C to 200 ° C.

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

In EP-A-0 846 756, published on June 10, 1998, a pill is provided having a coating comprising a disintegrating material and preferably an effervescent material.

Recently a medium has been discovered by the which coated tablets can be provided with a coating so that they can be stored, transported and handled without damage, where the coating can break easily when the pill is in the clothes washer for Release the active ingredients to the wash solution. Aspects Typical of this description can be found in the applications European patent pending EP 99870017.3, EP 99870018.1 and EP 99870019.9.

However, although they provide results satisfactory, it has now been discovered that when a compound clay ore is present in the coating of the tablet of detergent, clay, for the same reasons mentioned previously, it can have a negative effect on the action of the perfume contained therein as well as on the appearance of coating, as it discolors the coating.

These problems have been observed to be exacerbated over time and more especially when the coating also it comprises an acid with a melting point of at least 40 ° C, more especially with a melting point of at least 145 ° C.

Therefore, the detergent formulator must also face the problems of providing a pill coated with a satisfactory coating, that is hard enough to protect the tablet against mechanical forces when stored, transported and handled and easily dispersed in an aqueous solution while providing perfume performance satisfactory.

In addition, the scented pill of Detergent is a problem for the detergent formulator. By Therefore, the presence of the coating on the tablet can reduce the diffusion of the perfume of the tablet giving rise to a less odor attractive.

It has now been discovered surprisingly that perfume compositions containing less than 0.6% in weight of the Schiff base perfume in a detergent tablet They suffer these problems. This finding is surprising because Schiff's bases, which are generally known, were not expected by having a yellow color at the beginning, they will give rise to clay discoloration, especially along the weather.

Summary of the invention

The present invention is a pill of scented detergent, the tablet comprising a mineral compound  of clay and where the perfume comprises less than 0.6% base of Schiff by weight of the perfume composition.

The expression "detergent tablet scented "means 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 ingredient of the pill Detergent is a clay. The clay may be present in the detergent composition, in the coating if present, or in both of them.

The expression "clay mineral compound" (or abbreviated "clay") means herein memory a hydrated phyllosilicate, typically that has a crystal structure of two or three layers. It should be noted that the expression "clay mineral compound", herein memory, excludes additive compounds that reinforce the sodium aluminosilicate zeolite type detergency, which, without However, they can be included in the compositions of the invention as optional components. A more detailed description of the Clays can be found in Encyclopaedia of Chemical Technology by Kirk-Othmer, 4th edition, volume 6, page 381, published by John Wiley and Sons.

The mineral clay compound is preferably a smectite clay compound. Clays smectite type are described in the patents US 3,862,058, US 3,948,790, US-3,954,632 and US-4,062,647 and in European patents EP-A-299,575 and EP-A-313,146, all in name from The Procter and Gamble Company.

The term "smectite type clays" herein includes clays in which aluminum oxide is present in a silicate network and clays in which magnesium oxide is present in a silicate network. Typical smectite clay compounds include compounds having the general formula Al 2 (Si 2 O 5) 2
(OH) 2 .nH 2 O and the compounds having the general formula Mg 3 (Si 2 O 5) 2 (OH) 2 .nH 2 }OR. Smectite type clays tend to adopt an expandable structure in three layers.

Specific examples of type clays Suitable smectite include those selected from the classes of Montmorillonites, hectorites, volchonscoites, nontronites, saponites and sauconites, particularly those with a metal ion alkaline or alkaline earth within its crystalline structure reticulate Sodium or calcium montmorillonites are particularly preferred.

The appropriate smectite clays, especially montmorillonites, are marketed by different suppliers including English China Clays, Laviosa, Fordamin, Georgia Kaolin and Colin Stewart Minerals (CSM).

The preferred smectite clays are marketed under the name of White Bentonite STP by Fordamin, and with the name of Detercal P7 by Laviosa Chemical Mining SPA.

Clays for use in the present invention can be subjected to an acid wash treatment with any suitable mineral or organic acid. These clays produce a pH acid when dissolved in distilled water. A "clay acid "of this type is marketed under the name Tonsil P by Sud Chemie AG.

The replacement of small cations such as protons, sodium ions, potassium ions, magnesium ions and calcium ions and of certain organic molecules, including those with groups functional with positive charge, can typically take place within the reticular crystal structure of type clays smectite A clay can be chosen for its ability to absorb preferably a certain type of cation, being able to assess this capacity due to its relative ion exchange capacity. Smectite type clays suitable in the present invention they typically have a cation exchange capacity of at minus 50 meq / 100 g. US Patent 3,954,632 describes a method to measure exchange capacity cationic

In a preferred embodiment, the structure Crystalline lattice of clay mineral compounds can have a cationic fabric softener substituted therein. These substituted clays are called clays "hydrophobically activated". The cationic softeners of tissues are typically present with a weight ratio between the cationic fabric softener and the clay from 1: 200 to 1:10 and preferably from 1: 100 to 1:20. Cationic softeners Suitable tissues include insoluble tertiary amines in water or the amides of two long chains as described in GB-A-1 514 276 and EP-B-0 011 340.

A "hydrophobically activated" clay Preferred commercial is a bentonite clay containing approximately 40% by weight of a salt of quaternary ammonium dimethyl-disebo marketed Named Claytone EM by English China Clays International

Preferably, the clay that is present in the detergent composition is present in an intimate mixture or in a particle with a humectant and a hydrophobic compound, preferably a wax or oil, such as paraffin oil. The Preferred humectants are organic compounds, including propylene glycol, ethylene glycol, dimers or trimers of glycol and with highest preference glycerol. The particle is preferably a agglomerate. Alternatively, the particle can be so that the wax or oil and optionally the humectant form a encapsulated on the clay or, alternatively, the clay be an encapsulation for wax or oil and humectant. May it is preferred that the particle comprises 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 reinforcing additives of the detergency and optionally water, in which case the mixture is preferably then dried. In addition, preferably process this mixture by a spray drying method to obtain a spray dried particle comprising the clay.

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

Depending on its final use, clay preferably it will be present with different sizes of particles Therefore, when you want to perform a smoothing, you prefers that at least 50% by weight, preferably practically the all (eg at least 90% or 95%) by weight of the clay is Present as granules. The term "granule" means that the particles of the clay mineral compound that is present in the detergent composition are included as components of agglomerated particles that optionally contain other compounds detergents If they are present as such components, the expression "maximum particle size" of the mineral compound clay refers to the maximum size of the mineral component of clay as such and not to the particle agglomerated as a whole. From Typically, the granules will have a particle size of at minus 100 micrometers, usually 100 to 1700 micrometers.

When a coating is present, often it is desired to have a clay as a disintegrant in the coating. In In this case, the clay is preferably present in the coating with a particle size of less than 75 µm, more preferably less than 53 µm.

Preferably, the tablet is a tablet softener. The expression "softener tablet" means that the clay level will typically be at least 5%, preferably at least 8% and most preferably at least 10%, by weight of the tablet. The amount can be less than 25%, normally less than 20% and preferably not more than 15%, by weight of the pill.

Fragrance

The tablets of the present invention also they comprise a perfume composition that may be present in the coating if present or in the detergent composition, or even in both the coating and the composition Detergent. Suitable perfumes in the present invention include materials that provide an olfactory aesthetic advantage for make these pills aesthetically more enjoyable by consumer, transmit a pleasant fragrance to the tissues treated with them and / or cover any "chemical" smell that the product may have.

In this report the perfume includes a aromatic substance or a mixture of aromatic substances, including  natural odoriferous substances (i.e. those obtained by extraction of flowers, herbs, leaves, roots, barks, wood, buds or plants), artificial (i.e., a mixture of different natural oils or oily components) and synthetic (that is, obtained by synthesis). These materials usually go accompanied by auxiliary materials such as fasteners, extenders, stabilizers and solvents. These auxiliary substances too They are included in the term "perfume" herein. Typically, perfumes are complex mixtures of a plurality of organic compounds.

For the purpose of the present invention, the perfume composition contains less than 0.6% by weight of the Schiff base perfume composition. The perfume of use in the The present invention is used at a level of up to 5 grams per tablet and preferably is virtually free of bases Schiff

The expression "practically exempt" means that the perfume composition comprises less than 0.4% in Schiff base weight and more preferably free of bases from Schiff.

Schiff's bases are the products of condensation of a perfume aldehyde ingredient with a anthranilate In US-4853369 you can find a typical description. Schiff bases can be added directly to the perfume composition or can be formed in situ in the perfume composition adding to it an anthranilate such as methyl or ethyl anthranilate along with an aldehyde that can react with the anthranilate to form the base of Schiff.

Without pretending to impose any theory, it is believed that when this compound comes into contact with the clay it can undergo reactions most likely catalyzed by ions of metal present in the clay and that in these reactions They form much more colored by-products.

Typical Schiff bases are selected from bases from Schiff's 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde  and methyl anthranilate; condensation products of hydroxycitronellal and methyl anthranilate; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde  and methyl anthranilate; methyl anthranilate and hydroxycitronellal marketed under the trade name Aurantiol; anthranilate methyl and methyl nonyl acetaldehyde marketed with the commercial name Agrumea; methyl anthranilate and bucinal PT marketed under the trade name Verdantiol; anthranilate methyl and liral marketed under the trade name Lyrame; methyl anthranilate and ligustral marketed under the name Ligantral commercial, and mixtures thereof.

Preferably, the perfume composition is free of perfume ingredients selected from anthranilate methyl and hydroxycitronella marketed under the trade name Aurantiol; methyl anthranilate and methyl nonyl acetaldehyde marketed under the trade name Agrumea; methyl anthranilate and bucinal PT marketed under the name Verdantiol commercial; methyl and liral anthranilate marketed under the trade name Lyrame; methyl and ligustral anthranilate marketed under the trade name Ligantral, and mixtures of same.

Of course, the perfume composition It will contain one or more perfume ingredients. Perfume ingredients  suitable are described in US-5,500,138, being said patent incorporated by reference herein memory.

Examples of perfume ingredients useful in perfume compositions include, but are not limited to, hexyl cinnamic aldehyde; cinnamic amyl aldehyde; 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- (para-tert-butylphenyl) -propionaldehyde; 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde; tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde; 2-methyl-2- (para-isopropylphenyl) -propionaldehyde; ethyl-3-methyl-3-phenyl glycidate; 4- (para-hydroxyphenyl) -butan-2-one; 1- (2,6,6-Trimethyl-2-cyclohexen-1-yl) -2-buten-1-one; para-methoxyacetophenone; para-methoxy-alpha-phenylpropene; methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; gamma undecalactone.

Additional examples of fragrance materials include, but not limited to, orange oil; oil of lemon; grapefruit oil; bergamot oil; clove oil; gamma-dodecalactone; acetate methyl-2- (2-pentyl-3-oxo-cyclopentyl);  beta-naphthol methyl ether; methyl beta-naphthyl ketone; coumarin; decyl aldehyde; benzaldehyde; acetate 4-tert-butylcyclohexyl; acetate alpha, alpha-dimethylphenethyl; acetate methylphenylcarbinyl; cyclic acid ethylene glycol diester tridecandioic; 3,7-dimethyl-2,6-octadiene-1-nitrile; methyl gamma-ionone; alpha-ionone; beta-ionone; petitgrain; methyl cedrilone; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; methyl ionone; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl  ketone; 7-acetyl-1,1,3,4,4,6-hexamethyltetraline; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone; 6-acetyl-1,1,2,3,3,5-hexamethylindane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal; 7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexyl carboxaldehyde; formil tricyclodecane; cyclopentadecanolide; acid lactone 16-hydroxy-9-hexadecenoic; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; ambroxane; dodecahydro-3a, 6,6,9a-tetramethylnaphtho- [2,1b] furan;  cedrol; 5- (2,2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol;  Caryophilic alcohol; cedrile acetate; acetate para-tert-butylcyclohexyl; patchouli; incense resinoid; laudanum; vetivert; balsam of copaiba; spruce balm; hydroxycitronellal and indole; phenylacetaldehyde e indole

Other examples of perfume components are the geraniol; geranyl acetate; linalool; linalyl acetate; tetrahydrolinalol; citronellol; citronellyl acetate; di-hydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; acetate 2-phenylethyl; benzyl alcohol; acetate benzyl; benzyl salicylate; Benzyl benzoate; acetate stiralyl; dimethylbenzylcarbinol; acetate trichloromethylphenylcarbinyl methylphenylcarbinyl; acetate isononyl; vetiveryl acetate; vetiverol; 2-methyl-3- (p-tert-butylphenyl) -propanal; 2-methyl-3- (p-isopropylphenyl) -propanal; 3- (p-tert-butylphenyl) -propanal; 4- (4-methyl-3-pentenyl) -3-cyclohexencarbaldehyde; 4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehyde dimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile; citronelonitrile; cedril acetal; 3-isocamfilcyclohexanol; cedril methyl ether; isolongifolanone; aubepine nitrile; aubepine; heliotropin; eugenol; vanillin; diphenyl oxide; hydroxycitronella ionones; methyl ionones; isomethyl ionones; ironas cis-3-hexenol and its esters; musk indane essences; musk tetralin aroma; aromas of isochroman musk; macrocyclic ketones; fragrances of musk macrolactone and ethylene brasylate.

The perfumes useful in the compositions of the present invention are practically free of products halogenated and nitroalmizcles.

Examples of solvents, diluents or vehicles suitable for the aforementioned perfume ingredients  they are ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc. Preferably the amount of said solvents, diluents or vehicles incorporated into perfumes are kept to the minimum level necessary to obtain a homogeneous perfume solution.

The tablets of the present invention as well as the coated tablets according to the invention provide better deposition of the perfume on the fabric.

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

The perfume can be incorporated into the tablet by any conventional means known to the expert in the technique. A preferred means is to spray the perfume composition on the pill

Heavy metal ion sequestrants

The scented detergent tablets of the invention also preferably contain as an optional component  a heavy metal ion sequestrant composition that is present in the coating if present or in the composition detergent, or even both in the coating and in the detergent composition The expression "ion sequestrant of heavy metal "means herein components that they act by sequestering (chelating) heavy metal ions. These components may also have the ability to chelate calcium ions and magnesium, although they are especially selective in their ion binding Heavy metal such as iron, manganese or copper.

Heavy metal ion sequestrants are generally present at a level of 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and with maximum preference from 0.5% to 5%, by weight of the tablet.

Heavy metal ion sequestrants that they are acidic and have for example acid functionalities phosphonic or carboxylic acid may be present in its form acidic or in the form of a complex / salt with a suitable counterpart as an alkali or alkali metal ion, ammonium or ammonium ion substituted or any mixture thereof. Preferably the salts / complexes are soluble in water. The molar relationship between said counter-cation and the heavy metal ion sequestrant is preferably at least 1: 1.

Heavy metal ion sequestrants Suitable in the present invention include organic phosphonates  such as the amino alkylene poly (alkylene phosphonates), the ethane-1-hydroxy diphosphonates of alkali metals and nitrile-trimethylene phosphonates.

Preferred species among the above are diethylene triamino penta (methylene phosphonate), the ethylenediamine-tri (methylene phosphonate), the hexamethylene diamine tetra (methylene phosphonate) and the hydroxyethylene-1,1-diphosphonate.

Other heavy metal ion sequestrants Suitable for use in the present invention include acid nitrilotriacetic and polyaminocarboxylic acids, such as acid ethylenediamine tetraacetic acid ethylenetriamine-pentaacetic acid ethylenediamine-disuccinic acid ethylenediamine diglutaric acid 2-hydroxypropylene diamino-disuccinic  or any salt thereof.

Especially preferred is acid ethylenediamino-N, N'-disuccinic (EDDS) or alkali metal, alkaline earth metal salts, of ammonium or substituted ammonium thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the salt of sodium or magnesium or complexes thereof. Examples of these salts of Preferred sodium EDDS include Na 2 EDDS and Na 3 EDDS. Examples of these preferred EDDS magnesium complexes include MgEDDS and Mg2 EDDS.

Other heavy metal ion sequestrants suitable for use in the present invention are derivatives of iminodiacetic acid such as acid 2-hydroxyethylacetic acid or glyceryl imino acid diacetic, described in EP-A-317,542 and EP-A-399,133.

The iminodiacetic acid-acid sequestrants N-2-hydroxy-propylsulfonic and aspartic acid-N-carboxymethyl acid N-2-hydroxy-propyl-3-sulfonic described in EP-A-516.102 also they are suitable in the present invention. Type kidnappers β-alanin-N acid, N'-diacetic acid aspartic-N, N'-diacetic acid aspartic-N-monoacetic acid iminodisuccinic described in EP-A-509,382 are also adequate.

In EP-A-476,257 suitable amino-based sequestrants are described. In EP-A-510,331 are described suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyliminodiacetic acid sequestrant. Acid dipicolinic and acid 2-phosphonobutane-1,2,4-tricarboxylic They are also suitable. Acid glycinamide-N, N'-disuccinic (GADS), the acid ethylenediamine-N-N'-diglutaric (EDDG) and acid 2-hydroxypropylene diamino-N-N'-disuccinic (HPDDS) are also suitable.

Heavy metal ion sequestrants more Preferred for use in the present invention are ethanes. 1-metal hydroxy diphosphonates alkaline, in particular when used together with diethylenetriamine-penta (methylene phosphonate). Most preferably, the heavy metal ion sequestrant It is present in the coating.

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Detergent ingredients

The tablets may comprise components such as surfactants, enzymes, detergents, etc. The typical tablet compositions for the preferred embodiment of The present invention is described, for example, in applications European patent pending applicants EP 96203471.6, EP 96203462.5, EP 96203473.2 and EP 96203464.1. The elements that of typical form enter the composition of detergent tablets or other forms of detergent such as liquids or granules are described in the following paragraph.

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Detersive Surfactants

Surfactants are typically comprised in a detergent composition. The dissolution of the Surfactants are favored by the addition of the compound highly soluble

Non-limiting examples of useful surfactants in the present invention typically at levels of about 1% to about 55% by weight include the Conventional C 11- C 18 alkylbenzenesulfonates ("LAS") and alkyl sulfates ("AS") C 10 {C} {20} Branched chain and random primary, alkyl sulfates C 10- C18 secondary (2.3) of formula CH 3 (CH 2) x (CHOSO_3- M +) CH 3 and CH 3 (CH2) y (CHOSO_3 M +) CH2CH3 where x e (y + 1) are integers of at least about 7, preferably at least about 9, and M It is a cation soluble in water, especially sodium, sulfates unsaturated such as oleyl sulfate, alkylalkoxysulfates C_ {10-} C_ {18} ("AE_ {x} S"; especially ethoxy sulfates EO 1-7), alkylalkoxycarboxylates C 10- C 18 (especially EO ethoxycarboxylates 1-5), glycerol ethers C 10-18, alkyl polyglycosides C 10- C 18 and their corresponding sulfated polyglycosides and alpha-sulphonated fatty acid esters C_ {12-} C_ {18}. If desired, they can also be included in the general compositions nonionic and amphoteric surfactants conventional such as alkyl C_ {12} -C_ {18} ethoxylates ("AE") included the so-called narrow-peak alkyl ethoxylates, and the alkyl C 6 -C 12 phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), betaines and sulphobetaines ("sultaines") C 12 -C 18 C 10 -C 18 amine oxides, and the like.  You can also use the N-alkyl C 10 -C 18 fatty acid polyhydroxyamides. Typical examples include N-methyl C 12 -C 18 glucamides (see document WO-9,206,154). Other surfactants derived from sugars include the N-alkoxy polyhydroxyamides of fatty acid such as N- (3-methoxypropyl) C 10 -C 18 glucamide. You can use the N-propyl to N-hexyl glucamides C_ {12} -C_ {18} to get a low formation of soaps. Conventional soaps can also be used C_ {10} -C_ {20}. If high training is desired of soaps, branched chain soaps can be used C_ {10} -C_ {16}. They are especially useful mixtures of anionic and nonionic surfactants. Others Useful conventional surfactants are described in the texts standard. In a preferred embodiment, the tablet comprises the less than 5% by weight of surfactant, more preferably at least 15% by weight, even more preferably at least 25% by weight and most preferably between 35% and 45% by weight, of surfactant

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Non-gelling binders

Non-gelling binders can be integrated into detergent compositions to facilitate additionally the solution.

If non-gelling binders are used, the suitable non-gelling binders include polymers organic synthetics such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and acrylate copolymers water soluble. In the Handbook of Pharmaceutical Excipients, 2nd ed., the following classification of binders is offered: gum arabic, alginic acid, carbomer, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, gelatin, guar gum, hydrogenated vegetable oil type I, hydroxyethylcellulose, hydroxypropyl methylcellulose, glucose liquid, magnesium aluminum silicate, maltodextrin, methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein The most preferred binders also have a function cleanser active in washing clothes like polymers cationic, for example, quaternary compounds of ethoxylated hexamethylenediamine, bishexamethylene triamines or others as pentaamines, ethoxylated polyethyleneamines and polymers Acrylic / Maleic

Non-gelling binder materials preferably they are pulverized and therefore have a melting point temperature below 90 ° C, preferably below 70 ° C and even more preferably below 50 ° C, so as not to damage or degrade the other active ingredients of the matrix. The More preferred binders are non-liquid binders. aqueous (i.e., not in aqueous solution) that can be spray in molten form. However, they can also solid binders incorporated into the matrix by addition in dry but that have binding properties within the tablet.

Non-gelling binder materials are preferably use in an amount in the range of 0.1% to 15% of the composition, more preferably below 5% and, especially if it is an active material not for laundry, in an amount less than 2% by weight of the tablet.

It is preferred to avoid binders gelling agents, such as non-ionic surfactants, in liquid form or cast. Nonionic surfactants and other binders gelling agents are not excluded from the compositions, but it is preferred process them in detergent tablets as components of particulate materials and not as liquids.

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Detergency builders

The compositions of the present invention include can add detergency builders to facilitate Mineral hardness control. Reinforcing additives can be used of inorganic and also organic detergency. Additives detergency builders are typically used in laundry compositions to help eliminate spots in the form of particles.

The amount of additive reinforcing the detergency can vary widely depending on the end use of the composition.

Additives strengthening detergency inorganic or containing P include, but not limiting, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, in certain cases it require phosphate-free detergency builder additives. Fits highlight that the present compositions act surprisingly well even in the presence of the so-called reinforcing additives of the "weak" detergency (compared to phosphates), such such as citrate, or in the so-called "and infrastructure" situation which may occur when additives are used to strengthen the Zeolite or laminar silicate detergency.

Examples of reinforcing additives of the detergency alkali metal silicates, especially those that have a SiO 2: Na 2 O ratio in the range of 1.6: 1 to 3.2: 1, and laminar silicates such as silicates sodium laminar described in the patent US 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the registered trademark of a crystalline laminar silicate marketed by Hoechst (hereinafter abbreviated as "SKS-6"). Unlike the Zeolite-type detergency builder additives, the additive Na silicate detergency builder SKS-6 does not contain aluminum. He NaSKS-6 presents the morphology delta-Na2 SiO5 laminar silicate. May be prepared by methods such as those described in the patents German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a very preferred laminar silicate for its use in the present invention, although in the present invention other laminar silicates of this type can also be used such as those in the general formula NaMSi_ {O} {2x + 1} \ cdotyH2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, e y is a number from 0 to 20, preferably 0. Other layered silicates of Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, such as alpha, beta and gamma forms. How indicated above, the form delta-Na2 {SiO5 {(NaSKS-6) is most preferred for use in the present invention. Others silicates can also be useful as, for example, silicate magnesium, which can serve as a potentiating agent for friability in granulated formulations, as agent stabilizer for oxygen releasing bleach and as component of the regulating systems of the soaps.

They are examples of reinforcing agents of the carbonate type detergency metal carbonates alkaline earth metals and alkali metal carbonates described in Patent application DE-2,321,001, published on November 15, 1973.

Aluminosilicate-type reinforcing additives They are useful in the present invention. The reinforcing additives of the aluminosilicate type detergency are of great importance in the most granular cleaning detergent compositions intensive currently marketed and can also be a significant detergency builder additive for liquid detergent formulations. The reinforcing additives of the aluminosilicate type detergency include those that have the empirical formula:

M_ {z} (zAlO2) y}] xH2 O

where z and y are whole numbers of at least 6, the molar relationship between z and y is in the range of 1.0 to about 0.5 and x is an integer of about 15 to about 264

Ion exchangers of Useful aluminosilicate are in the market. These aluminosilicates can have a crystalline or amorphous structure and they can be natural or synthetic aluminosilicates. In the patent US 3,985,669, granted to Krummel et al. on 12 of October 1976, a method for producing materials is described aluminosilicate ion exchangers. The materials crystalline aluminosilicate ion exchangers and Preferred synthetics, useful in the invention, are found available under the names Zeolita A, Zeolita P (B), Zeolita MAP and Zeolita X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material It has the formula:

Na 12 [(AlO 2) 12 (SiO 2) 12] xH 2 O

wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used in the present invention. Preferably, the aluminosilicate has a particle size of about 0.1 to 10 micrometers of
diameter.

Additives strengthening detergency organic ingredients suitable for the purposes of the present invention include, but not limited to, a wide variety of polycarboxylate compounds. Here the term "polycarboxylate" refers to compounds that have a plurality of carboxylate groups, preferably at least 3 carboxylates. The detergency reinforcing additive of type Polycarboxylate can generally be added to the composition in acid form, although it can also be added in salt form neutralized When used in the form of salt, salts are preferred alkali metal, such as sodium, potassium and lithium, or of alkanolammonium

Among detergency builders Different categories of polycarboxylate are included Useful materials An important category of reinforcing additives of the polycarboxylate detergency encompasses the ethers polycarboxylic acids, including oxydisuccinate, as described in the US Patent 3,128,287, issued to Berg on 7 April 1964, and US-3,635,830, granted to Lamberti et al. on January 18, 1972 (see also the Patent "TMS / TDS" detergency builder additives US 4,663,071, granted to Bush et al. May 5th of 1987). Among suitable polycarboxylic ethers are also they include cyclic compounds, in particular alicyclic compounds, as described in US Patents 3,923,679, US 3,835,163, US 4,158,635, US 4,120,874 and US 4,102,903.

Other useful additives are the ether-hydroxypolycarboxylates, the copolymers of maleic anhydride with ethylene or vinyl methyl ether, the acid 1,3,5-trihydroxybenzene-2,4,6-trisulfonic and carboxymethyloxysuccinic acid, the various metal salts alkali, ammonium and substituted ammonium of polyacetic acids such such as ethylenediaminetetraacetic acid and acid nitrilotriacetic, as well as polycarboxylates such as acid  melitic, succinic acid, oxidisuccinic acid, acid polyimaleic acid benzene-1,3,5-tricarboxylic acid, the carboxymethyloxysuccinic acid and soluble salts thereof.

Citrate additives, for example, acid citric and soluble salts thereof (especially salt sodium), they are additive builders of type detergency polycarboxylate of particular importance for formulations liquid detergents for intensive cleaning due to their availability to from renewable resources and their biodegradability. Can be used also citrates in granulated compositions, especially together with zeolite-type detergency builders and / or laminar silicate. Oxydisuccinates are also especially useful in this type of compositions and combinations.

In the detergent compositions herein invention are also suitable 3,3-dicarboxy-4-oxa-1,6-hexanedioates  and related compounds described in the patent US 4,566,984, granted to Bush on January 28, 1986. Additives reinforcing acid detergency Useful succinic include alkyl and alkenyl acids C 5 -C 20 succinic and salts thereof. A particularly preferred compound of this type is acid. dodecenyls succinic. Specific examples of reinforcing additives of Succinate type detergency include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. The lauryl succinates are detergency builders preferred from this group and are described in the application EP-6200690.5 / 0.200.263, published on November 5 of 1986.

Other suitable polycarboxylates are described in US Patent 4,144,226, issued to Crutchfield and cabbage. on March 13, 1979, and in US-3,308,067, granted to Diehl on March 7, 1967. See also the US-3,723,322 granted to Diehl.

They can also be incorporated into the compositions fatty acids, for example, monocarboxylic acids C_ {12} -C_ {18}, alone or together with the above detergency builder additives, especially citrate and / or reinforcing additives of succinate type, to obtain a additional reinforcing activity. Said use of fatty acids it will generally produce a decrease in soaps, which must be taken into account by the formulator.

When additives based on phosphorus and especially in the formulation of washing tablets by hand of the laundry, the various phosphates of alkali metals, such as the well known tripolyphosphates sodium, sodium pyrophosphate and sodium orthophosphate. Can be used also phosphonate-type detergency builders, such as the ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, US-3,159,581, US-3,213,030, US-3422,021, US-3,400,148 and US 3,422,137).

Bleach

The detergent compositions herein invention may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When they are present, the bleaching agents will typically be at levels of about 1% to about 30%, more typically about 5% to about 20%, of the composition detergent, especially for washing fabrics. If they are present bleach activators, its quantity will be of form typically from about 0.1% to about 60%, more typical of about 0.5% to about 40% of the bleaching composition comprising the bleaching agent plus the bleach activator.

The bleaching agents herein invention used can be any of the agents bleaching agents useful for cleaning detergent compositions of fabrics, cleaning of hard surfaces or other purposes of cleaning that are already known or become known. These they can be oxygen bleaching or other agents whitening In the present invention they can be used perborate type bleaches such as perborate sodium (for example, monohydrate or tetrahydrate).

Another category of bleaching agent that can used without restriction are acid bleaching agents percarboxylic and salts thereof. Among the appropriate examples of this class of agent is magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, the acid 4-nonylamino-4-oxoperoxybutyric  and diperoxidedecanedioic acid. Such bleaching agents are described in US Pat. Nos. 4,483,781, issued to Hartman on November 20, 1984, US-740,446, granted to Burns et al. on June 3, 1985, EP-0.133.354, granted to Banks et al. on 20 of February 1985, and US-4,412,934, granted to Chung and cabbage. on November 1, 1983. Among the bleaching agents very preferred also include acid 6-nonylamino-6-oxoperoxicaproic,  as described in US Patent 4,634,551, issued on January 6, 1987 to Burns et al.

Bleach can also be used peroxygenated Among peroxygenated bleaching compounds suitable are sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, the sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide A bleach of the type can also be used persulfate (for example, OXONE, marketed by DuPont).

A preferred percarbonate bleach It comprises dry particles with an average particle size between 500 micrometers and 1,000 micrometers, where as maximum approximately 10% by weight of said particles are less than 200 micrometers and at most approximately 10% in Weight of such particles are greater than 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water soluble surfactants. The percarbonate is marketed by various companies such as FMC, Solvay or Tokai Denka

Agent mixtures can also be used. whitening

Peroxygen bleaching agents, perborates, percarbonates, etc. they are preferably combined with bleach activators, which lead to production in peroxyacid site corresponding to the bleach activator in aqueous solution (that is, during the washing process). In US-4,915,854, issued April 10 from 1990 to Mao et al., and US 4,412,934 are described several non-limiting examples of activators. The activators of nonanoyloxybenzenesulfonate (NOBS) and tetracetylethylene diamine (TAED) are typical, mixtures thereof may also be used. See also the US-4,634,551 for other bleaches and activators typical useful in the present invention.

Bleach activators amidoderivatives very Preferred are those of the following formulas:

\hskip0.5cm

o

\hskip0.5cm

R^{1}C(O)N(R^{5})R^{2}C(O)LR 1 N (R 5) C (O) R 2 C (O) L

 \ hskip0.5cm 

or

 \ hskip0.5cm 

R 1 C (O) N (R 5) R 2 C (O) L

where R 1 is a group alkyl containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl or alkaryl containing from about 1 to about 10 carbon atoms and L is any suitable leaving group. A outgoing group is any group that is displaced from the trigger bleach as a result of nucleophilic anion attack of perhydrolysis on the bleach activator. A group preferred outbound is the phenylsulfonate.

Preferred examples of activators of bleach of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and mixtures thereof, as described in the US-4,634,551., Incorporated by reference in the present memory

Other class of bleach activators comprises the benzoxazine type activators described by Hodge and cabbage. in US-4,966,723, granted on October 30 of 1990, and incorporated by reference herein. A Very preferred activator of the benzoxazine type is:

one

Another class of bleach activators Preferred are acyl lactam activators, especially the acylcaprolactams and acilvalerolactamas of the formulas:

2

where R 6 is H or a group alkyl, aryl, alkoxyaryl or alkaryl containing from 1 to approximately 12 carbon atoms. Lactamic activators Very preferred include benzoyl caprolactam, octanoyl caprolactam,  3,5,5-trimethylhexanoyl caprolactam, nonanoil caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoil valerolactam, octanoil valerolactam, decanoil valerolactam, undecenoil valerolactama, nonanoil valerolactama, 3,5,5-tri-methylhexanoyl valerolactam and mixtures thereof. See also the patent US 4,545,784, granted to Sanderson on October 8 1985, which describes acylcaprolactams, including the benzoylcaprolactam, adsorbed in perborate sodium

Bleaching agents other than the agent oxygen releasing bleaches are also known in the technique and can be used in the present invention. A kind of oxygen bleaching agent of special interest includes photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. See US 4,033,718, issued July 5, 1977 to Holcombe et al. If detergent compositions are used, these they will typically contain approximately 0.025% at approximately 1.25%, by weight, of these bleaches, especially sulfonated zinc phthalocyanine.

If desired, the bleaching compounds can be catalyzed by a manganese compound. Such compounds are well known to the state of the art and include, for example, the manganese-based catalysts described in US-5,246,621, US-5,244,594, US-5,194,416, and US-5,114 .606; and European patent applications with no. of pub. EP-549.271A1, EP-549.272A1, EP-544.440A2 and EP-544.490A1; Preferred examples of these catalysts include Mn IV 2 (uO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6) {2}, Mn <3> (uO) 1
(u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 4) 2, Mn IV 4 (uO) 6 (1,4,7-triazacyclononane) 4 (ClO 4) 4, Mn III Mn IV 4 (uO) _ {1 (u-OAc) 2 - (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4) 3, Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane) -
(OCH 3) 3 (PF 6) and mixtures thereof. Other metal-based bleaching catalysts are those described in patents US-4,430,243 and US-5,114,611. The use of manganese with several complex ligands to improve bleaching is also described in the following patents: US-4,728,455, US-5,284,944, US-5,246,612, US-5,256,779, US-5,280,117, US 5,274,147, US 5,153,161 and US 5,227,084.

As a practical matter and not by way of limitation, the compositions and processes of the present invention can be adjusted to obtain at least one part of the order ten million of the active bleaching catalyst species in the aqueous wash solution, which will preferably involve about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalytic species in the laundry solution.

Enzymes

In the formulations of the present invention, They can include enzymes for different laundry purposes such as for example, the removal of protein stains, hydrates carbon or triglycerides or to avoid dye transfers or to restore tissue. The enzymes that can be incorporated are proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. Other types of enzymes These may be of any appropriate origin such as, e.g. eg, vegetable, animal, bacterial, fungal and yeast. Without However, your choice is dictated by several factors such as optimal values of pH activity and / or stability, thermostability, stability against active detergents, additives detergency builders, etc. In this respect they are preferred bacterial or fungal enzymes, such as amylases and Bacterial proteases and fungal cellulases.

Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically from about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Said of another Thus, the compositions in the present invention will comprise typical form of about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial preparation of enzyme. Protease enzymes are normally present in these commercial preparations at sufficient levels to provide 0.005 to 0.1 Anson units (AU; from English, Anson unit) of activity per gram of composition.

Suitable examples of proteases are subtilisin that are obtained from special strains of B. subtilis and B. licheniformis . Another suitable protease is that obtained from a Bacillus strain that has a maximum activity in the pH range 8-12, developed and sold by Novo Industries A / S under the trademark of ESPERASE. The preparation of this enzyme and analogous enzymes is described in patent GB-1,243,784 to Novo. Suitable proteolytic enzymes for removing commercially available protein stains are those that are marketed under the ALCALASE and SAVINASE brands of Novo Industries A / S (Denmark) and MAXATASE of International Bio-Synthetics, Inc. (Netherlands). Other proteases include Protease A (see application EP-130,756, published on January 9, 1985) and Protease B (see application EP-87303761.8, filed on April 28, 1987, and application EP-130,756, Bott et al., published January 9, 1985).

Amylases include, for example, α-amylases described in the patent GB-1,296,839 (Novo), RAPIDASE of International Bio-Synthetics, Inc. and TERMAMYL de Novo Industries

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH of 5 to 9.5. Suitable cellulases are described in US Pat. No. 4,435,307, issued to Barbesgoard et al. on March 6, 1984, which describes the fungal cellulose produced by Humicola insolens and the strain of Humicola DSM1800 or cellulase 212, produced by a fungus belonging to the genus Aeromonas and the cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander) . Other suitable cellulases are also described in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME (Novo) is especially useful.

Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in GB-1,372,034. See also lipases in patent application JP-53.20487, filed on February 24, 1978. This lipase can be purchased from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the name Lipasa P "Amano", hereinafter referred to as "Amano-P". Other commercial lipases are Amano-CES, Chromobacter viscosum lipases, p. eg, Chromobacter viscosum var. NRRLB 3673 lipoliticum, marketed by Toyo Jozo Co., Tagata, Japan; and other lipases from Chromobacter viscosum from US Biochemical Corp., USA, and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli . The LIPOLASE enzyme derived from Humicola lanuginosa and marketed by Novo (see also EP O 341,947) is a preferred lipase for use in the present invention.

Peroxidases enzymes are used together with sources of oxygen, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. These are used to "bleach the solution", that is, to prevent transfer  of dyes or pigments released from the substrates during washing operations to other substrates of the washing solution. Peroxidase enzymes are known in the art and include, for example, Horseradish peroxidase, ligninase and haloperoxidase such as chloro-peroxidase and bromo-peroxidase. Detergent compositions containing peroxidase are described, for example, in the international application PCT WO 89/099813, granted on October 19, 1989 to O. Kirk and assigned to Novo Industries A / S.

A wide range of enzymatic products and of means for incorporation into synthetic detergent compositions are also described in US-3,553,139, granted on 5 from January 1971 to McCarty et al. Other enzymes are also described in US 4,101,457, granted to Place et al. on July 18, 1978, and in US-4,507,219, granted  to Hughes on March 26, 1985. Useful enzyme materials for liquid detergent formulations and their incorporation into such formulations are described in the patent US 4,261,868, issued to Hora et al. on 14 of April 1981. The enzymes used in detergents can be stabilize by different techniques. The techniques of Enzymatic stabilization are described and illustrated in 3,600,319, issued August 17, 1971 to Gedge et al., And EP-0.199.405, EP-86200586.5, published October 29, 1986, granted to Venegas. Enzymatic stabilization systems they are also described, for example, in US 3,519,570.

Flocculating agent

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

The clay type flocculating agent acts agglutinating the clay compound particles in the solution washing, thus helping its deposition on the surface of the fabric in the wash. This operating requirement is, by therefore, different from that of clay-like dispersant compounds that they are usually added to detergent compositions for washing of clothes to improve the removal of clay stains from tissues and allow dispersion in the wash solution.

Preferred clay type flocculating agents in The present invention are organic polymeric materials that they have an average weight of 100,000 to 10,000,000, preferably of 150,000 to 5,000,000 and even more preferably 200,000 to 2,000,000

The appropriate organic polymeric materials comprise homopolymers or copolymers containing units selected monomers of alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone and ethylene imine. Homopolymers of, in particular ethylene oxide, but also those of acrylamide and Acrylic Acid

In the patents EP-A-299,575 and EP-A-313.146 of The Procter and Gamble Company describes polymeric flocculating agents Organic clay type preferred for use herein invention.

Inorganic clay flocculating agents they are also suitable in the present invention, being Typical examples of these are lime and alum.

The flocculating agent is preferably present in a detergent base granule such as, e.g. eg, a chipboard, an extrudate or a particle dried by detergent spray that generally comprises one or more surfactants and additives detergency builders.

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

If present, the weight ratio between the clay and the flocculating polymer is preferably 1000: 1 a 1: 1, more preferably 500: 1 to 1: 1, most preferably 300: 1 to 1: 1, or even more preferably from 80: 1 to 10: 1, or in certain applications even from 60: 1 to 20: 1.

Highly soluble compounds

The tablet may comprise a very compound soluble. Such a compound can be formed from a mixture or from A single compound. A very soluble compound is defined as next:

A solution is prepared as indicated by then, which comprises deionized water as well as 20 grams per liter of a specific compound:

one-

Be place 20 g of the specific compound in a beaker Sotax This beaker is put in a bath at a constant temperature regulated at 10 ° C. In the beaker, place a propeller agitator so that the bottom of the agitator 5 mm above the bottom of the Sotax beaker. He Mixer is set at a rotation speed of 200 rpm.

2-

Be pour 980 g of deionized water into the beaker Sotax

3-

10 s after entering the water, the conductivity of the solution using a conductivity meter.

4-

Be repeat stage 3 at 20, 30, 40, 50, 1 min, 2 min, 5 min and 10 min of finishing stage 2.

5-

He value measured at 10 min is used as a plateau value or value maximum.

According to the invention the specific compound is highly soluble if the conductivity of the solution reaches 80% of its maximum value in less than 10 seconds counted from the complete addition of deionized water to the compound. In fact, when the conductivity is monitored in this way, the conductivity reaches a plateau after a certain time, being considered This plateau as the maximum value. Such a compound is preferably  in the form of a fluid material consisting of solid particles at temperatures between 10 and 80 ° C to provide a easy handling, although other forms can also be used, such as A paste or a liquid.

Examples of very soluble compounds include the sodium diisoalkylbenzenesulfonate (DIBS) or toluenesulfonate sodium

Cohesive effect

The tablet may comprise a compound with a cohesive effect on the particulate material of a detergent matrix that forms the tablet. The cohesive effect on the particulate material of a detergent matrix that forms the tablet or a layer of the tablet is characterized by the force needed to break a pill or a layer based on a compression of the detergent matrix examined under conditions of compression controlled. For a given compression force, the presence of a high resistance of the tablet or the layer indicates that the granules agglomerated strongly when they were tablets existing, therefore, a strong cohesive effect. Means for assessing the strength of the tablet or the layer (also mentioned as diametral fracture tension) are presented in Pharmaceutical dosage forms: Tablets, vol. 1st ed. HE HAS. Lieberman et al., published in 1989.

The cohesive effect is measured by comparing the resistance of the tablet or the original base powder layer without compound that has a cohesive effect against the resistance of the tablet or layer of a powder mixture comprising 97 parts of the original base powder and 3 parts of the compound that has cohesive effect The compound that has a cohesive effect is added preferably to the matrix in a form virtually free of water (water content less than 10% [preferably less 5%]). The temperature of the addition is 10 to 80 ° C, plus preferably from 10 to 40 ° C.

According to the invention, it is said that a compound it has a cohesive effect on the particulate material when, when applying a given compaction force of 3,000 N, in tablets weighing 50 g of detergent material in the form of particles and a diameter of 55 mm increases the resistance to tensile at more than 30% (preferably 60% and more preferably 100%) thanks to the presence in the base material in the form of 3% particles of the compound having cohesive effect.

An example of a compound with cohesive effect it is sodium diisoalkylbenzenesulfonate.

When a very soluble compound is integrated that It also has a cohesive effect on the material in the form of particles used for a tablet or layer formed by compressing a particulate material comprising a surfactant, dissolution of the tablet or layer in an aqueous solution increases significantly.

In a preferred embodiment, at least 1% in weight of a pill or layer is formed from the compound very soluble, more preferably at least 2%, even more preferably at least 3% and most preferably at least 5%, by weight of the tablet or layer is formed from the compound very soluble that has a cohesive effect on the material in the form of particles

It should be noted that a composition comprising a very soluble compound as well as a surfactant is described in EP-A-0 524 075, this being Composition a liquid composition.

A very soluble compound that has an effect cohesive on the particulate material allows to obtain a tablet with a tensile strength greater than a force of constant compaction or with equal tensile strength at a lower compaction force, compared to Traditional pills Typically, a complete pill it will have a tensile strength of more than 5 kPa, preferably more than 10 kPa, more preferably, in particular for use in laundry applications, of more than 15 kPa, even more preferably more than 30 kPa and with maximum preference of more than 50 kPa, in particular for use in dishwashing or dishwashing applications; and one tensile strength of less than 300 kPa, preferably of less than 200 kPa, more preferably less than 100 kPa, even more preferably less than 80 kPa and most preferably less than 60 kPa In fact, in the case of washing applications of clothes, the pills should be less compressed than in the case of dishwasher applications, for example, where the dissolution is achieved more easily, so that in a wash application tensile strength is preferably less than 30 kPa.

This allows to produce pills or layers that they have a solidity and mechanical resistance similar to solidity  or the mechanical resistance of traditional tablets but at At the same time they are less compact and dissolve more easily. In addition, as the compound is very soluble, the dissolution of the tablet or layer is further facilitated resulting in a synergy that facilitates the dissolution of the tablet according to the invention.

Tablet manufacturing

The tablet can comprise several layers. When a single layer is manufactured, the layer can be considered Like the pill itself.

Detergent tablets can be prepared simply mixing the solid ingredients and compressing the mix in a conventional tablet press like the ones used, for example, in the pharmaceutical industry. Preferably the main ingredients, especially those gelling surfactants, are used in the form of particles. Any liquid ingredient, for example a surfactant or a soaps suppressant, can be incorporated so conventional to solid particulate ingredients.

In the particular case of the tablets for laundry, ingredients such as the reinforcing additive of the detergency and the surfactant can be dried by spraying conventional form and then compact at a pressure adequate. Preferably, the tablets according to the invention are compress using a force of less than 100,000 N, more preferably of less than 50,000 N, even more preferably of less than 5,000 N and most preferably less than 3,000 N. In fact, the most preferred embodiment is a tablet suitable for washing of compressed clothing manufactured using a force of less of 2,500 N, but tablets can also be contemplated for dishwasher, for example, wherein said tablets for dishwashers are usually more compressed than pills for washing clothes.

The particulate material used to make a tablet can be manufactured by any particle or granulation process. An example of a process of This type is spray drying (in a drying tower by spray flow to current or counter flow) which typically results in low apparent density values 600 g / l or less. The particulate materials of Higher density can be prepared by granulation and densification in a discontinuous mixer / granulator of high shear or by continuous granulation and densification procedures (for for example, with Lodige® CB and / or Lodige® KM mixers). Others suitable procedures include bed procedures fluid and compaction processes (for example, compaction with roller), extrusion as well as any material in the form of particles prepared by any chemical process like flocculation or sintering by crystallization. The particles individual can also be any other type of particles, granules, spheres or grains.

The components of the material in the form of particles can be mixed by any conventional means. He batch mixing process can be carried out properly, for example, with a horizontal mixer, a Nauta mixer, a belt mixer or any other mixer. Alternatively The mixing process can be carried out continuously dosing by weight and dispensing each component on a tape in movement and mixing the components in one or more drums or mixers A non-gelling binder may be sprayed on the mixture of some, or all, of the components of the material in form of particles. Other ingredients can also be sprayed liquids on the mixture of the components, either separately or premixed. For example, perfume and aqueous suspensions of optical brighteners. You can add a finely divided fluidizer (lubricants such as zeolites, carbonates, silicas) to the particulate material after spray the binder, preferably at the end of the process, to make the mixture less sticky.

The tablets can be manufactured using any compaction process such as compression, briquetting or extrusion, preferably compression. Suitable equipment includes a standard piston press or rotary press (such as Courtoy®, Korch®, Manesty® or Bonals®). The tablets prepared according to this invention preferably have a diameter between 20 mm and 60 mm, preferably at least 35 mm and up to 55 mm and a weight between 25 g and 100 g. The ratio between height and diameter (or width) of the pads is preferably greater than 1: 3, more preferably greater than 1: 2. The compaction pressure used to prepare these tablets should not exceed 100,000 kN / m2, preferably it should not exceed 30,000 kN / m2, more preferably it should not exceed 5,000 kN / m2 , even more preferably it should not exceed 3,000 kN / m2 and most preferably it should not exceed 1,000 kN / m2. In a preferred embodiment according to the invention, the tablet has a density of at least 0.9 g / cc, more preferably at least 1.0 g / cc and preferably less than 2.0 g / cc, more preferably less 1.5 g / cc, even more preferably less than 1.25 g / cc and most preferably less than
1.1 g / cc

Multi-layer pads are typically formed in rotary presses placing the matrices of each layer, one after the other, in forced feeding jars of matrices As the process continues, the matrix layers they are then compressed together at the stations of the stages of Pre compression and compression to form the multilayer tablet. In some rotary presses it is also possible to compress the first layer fed before compressing the entire tablet.

Hydrotrope compound

A very soluble compound with cohesive effect it can be integrated into a detergent tablet, this being also composed a hydrotrope compound. This hydrotrope compound It can be generally used to favor the dissolution of surfactant and prevent gelation. A specific compound is defined as hydrotrope as follows (see S.E. Friberg and M. Chiu, J. Dispersion Science and Technology, 9 (5 & 6), P. 443-457, [1988-1989]):

one.

Be prepares a solution comprising 25% by weight of the compound specific and 75% by weight of water.

2.

Then octanoic acid is added to the solution in a proportion of 1.6 times the weight of the compound specific solution, the solution being at a temperature of 20 ° C The solution is mixed in a Sotax beaker with a agitator with propeller that is located approximately 5 mm above the bottom of the beaker and fixed the mixer to a rotation speed of 200 revolutions per minute.

3.

He specific compound is hydrotrope if octanoic acid is completely dissolved, that is, if the solution comprises only one phase, this phase being a liquid phase.

It should be noted that in a preferred embodiment of the invention, the hydrotrope compound is a fluid material made of solid particles under operating conditions of between 15 and 60ºC.

Hydrotropic compounds include the Compounds indicated below:

A list of commercial hydrotropes is found in McCutcheon's Emulsifiers and Detergents, published by  the McCutcheon division of Manufacturing Confectioners Company.

Compounds of interest also include:

one.

Non-ionic hydrotrope with the following structure:

R - O - (CH2CH2O) x (CH - CH2O) and HCH3

where R is a C8-C10 alkyl chain, x is 1 to 15 e and 3 to 10.

2.

Anionic hydrotropes such as alkali metal arylsulfonates. Metal salts are included alkaline of benzoic acid, salicylic acid, acid benzenesulfonic acid and its multiple derivatives, naphthoic acid and Different hydroaromatic acids. Examples of these are salts sodium, potassium and ammonium benzenesulfonate acid derived toluenesulfonic acid, xylenesulfonic acid, cumensulfonic acid, acid tetralinsulfonic acid, naphthalenesulfonic acid, acid methyl naphthalene sulfonic acid, dimethyl acid naphthalene sulfonic acid and trimethyl naphthalene sulfonic acid.

Other examples include dialkyl benzenesulfonic acid salts such as salts of di-isopropylbenzenesulfonic acid, ethyl acid methylbenzenesulfonic acid, alkylbenzenesulfonic acid with a length alkyl chain of 3 to 10 carbons, (preferably 4 to 9 carbons) and linear or branched alkyl sulfonates with a chain 1 to 18 carbon alkyl.

3.

Solvent hydrotropes such as alkoxylated glycerins and alkoxylated glycerides, esters of alkoxylated glycerins, alkoxylated fatty acids, esters of glycerin, polyglycerol esters. Alkoxylated glycerins Preferred have the following structure:

3

where l, m and n are each a number from 0 to approximately 20, l + m + n = of about 2 to about 60, preferably of about 10 to about 45, and R represents H, CH 3 or C 2 H 5

Glycerides Preferred alkoxylates have the following structure:

4

where R1 and R2 are each C_ {n} COO or - (CH2CHR3 -O) l -H where R 3 = H, CH 3 or C 2 H 5 and l is a number of 1 at about 60, n is a number from about 6 to approximately 24.

Four.

Polymeric hydrotropes such as described in EP636687:

5

where E is a hydrophilic functional group,

R is H, a group C1-C10 alkyl or a functional group hydrophilic;

R1 is H, a lower alkyl group or an aromatic group,

R2 is H, a cyclic alkyl group or an aromatic group.

The polymer of typically has a molecular weight of between approximately 1,000 and 1,000,000.

5.

Hydrotrope of unusual structure such as acid 5-carboxy-4-hexyl-2-cyclohexene-1-yl octanoic (Diacid®)

The use of this compound in the invention would further increase the dissolution rate of the tablet since, for example, a hydrotrope compound facilitates dissolution of surfactants. Such a compound can be formed from a mixture or a single compound.

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Tensile strength

For the purpose of measuring tensile strength of a layer, the layer can be considered as the tablet itself.

Depending on the composition of the subject Premium and the shape of the pads, the compaction force used can be adjusted so that it does not affect the resistance to traction and disintegration time in the washing machine. This procedure can be used to prepare homogeneous tablets or Laminates of any size and shape.

In a cylindrical tablet, resistance to traction equals the tension of diametral fracture (DFS) which is a way of expressing the resistance of a pill or layer and it determined by the following equation:

Resistance to traction = 2 F / \ piDt

where F is the maximum force (Newtons) that produces traction failure (fracture) measured in a VK 200 pickup hardness analyzer from Van Kell industries, Inc. D is the diameter of the tablet or layer and t the thickness of the pill or layer. For a non-round tablet, \ piD can simply be replaced by the perimeter of the tablet.

(Method Pharmaceutical Dosage Forms: Tablets, vol. 2, p. 213 to 217). A pill with a fracture tension diametral less than 20 kPa is considered to be fragile so it is The consumer is likely to get some broken pills. Be prefers a minimum diametral fracture tension of 25 kPa.

This applies similarly to the pills non-cylindrical to define tensile strength, where the normal cross section at the height of the tablet is not rounded and where the force is applied along a direction perpendicular to the direction of the height of the tablet and normal next to the tablet, the side being perpendicular to the cross section not rounded.

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Tablet dispensed

The dispensing speed of a pill of Detergent can be determined as follows:

Two tablets are weighed, with a nominal weight of 50 grams each, and placed in the dispenser of a washing machine Baucknecht® WA9850. The water supply to the clothes washer is puts at a temperature of 20 ° C and a hardness of 0.003 moles / l (21 grains per gallon), the water inlet flow of the dispenser is adjust to 8 l / min. The level of pill waste that is checked is verified. are left in the dispenser turning on the washing machine and putting the wash cycle in wash program 4 (white / color, cycle short). The percentage residue dispensed is determined from the following way:

% dispensed = residue weight x 100 / pill weight original

The amount of waste is determined by repeating the procedure 10 times and calculating the average amount of residues of the ten individual determinations. In this test of effort, a residue of 40% of the initial weight of the tablet It is considered acceptable. A residue of less than 30% is preferable and less than 25% is even more preferable.

It should be noted that the hardness measurement of the water is given in the traditional units "grain by gallon", in which 0.001 moles per liter = 7.0 grains per gallon, which represents the concentration of Ca 2+ ions in solution.

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Effervescent

Detergent tablets can also Understand an effervescent agent.

Effervescence, as defined herein memory, indicates the release of gas bubbles in a liquid as a result of a chemical reaction between an acid source soluble and an alkali metal carbonate, with dioxide production carbon gas,

100

Na_{3}C_{6}H_{5}O_{7} + 3CO_{2}

101

+ 3H_{2}Op. ex. C 6 H 8 O 7 + 3 NaHCO 3

100

Na 3 C 6 H 5 O 7 {+ 3CO2}

101

+ 3H 2 O

Other examples of sources of acid and carbonate and Other effervescent systems can be found at: (Pharmaceutical  Dosage Forms: Tablets, vol. 1, p. 287-291)

In addition to detergent components, the Pill mixture can be added an effervescent. The addition of this effervescent agent to the detergent tablet improves the time of disintegration of the tablet. The amount will be preferably from 5% to 20% and most preferably from 10% to 20% in weight of the pill Preferably the effervescent agent should be added in the form of agglomerate of the different particles or as a compact material and not in the form of separate particles.

Due to the gas produced by the effervescence in the pill, the pill can have a higher DFS and follow presenting the same disintegration time as a pill without effervescence. When the DFS of the effervescent tablet is keeps the same as a pill without effervescence, the Effervescent tablet disintegration will be faster.

Dissolution aid can be provided additional using compounds such as sodium acetate or urea. A list of dissolution aids can also be found Pharmaceutical Dosage Forms: Tablets, volume 1, 2nd edition, edited by H.A. Lieberman et al. ISBN 0-8247-8044-2.

Other components that are usually used in detergent compositions and which can be Built-in detergent tablets include agents chelators, agents to release dirt, inhibitors of Redeposition of dirt, dispersing agents, suppressors of soaps, fabric softeners, agents that inhibit dye transfer and mixtures thereof.

Covering

The strength of a pill can be improved preparing a coated tablet, where the coating covers an uncoated tablet thus improving the characteristics mechanical of the pill and keeping at the same time or improving additionally the solution.

This applies very advantageously to multi-layer pads where features mechanics of a more elastic layer can be transmitted through from the coating to the rest of the tablet, thus combining the advantage of the coating with the advantage of a more elastic layer. In fact, mechanical limitations will be transmitted through the coating thus improving the mechanical integrity of the tablet.

In an embodiment of the present invention, the tablets can be coated so that the tablet does not absorb moisture or absorb moisture only at a very low speed. The coating is also strong enough to that the moderate mechanical shocks to which the pills during handling, conditioning and transport only produce very low levels of breakage or wear. Finally the coating is preferably brittle so the tablet will break quickly when subjected to a crash stronger mechanic. It is also advantageous that the material of coating dissolve in alkaline conditions or make it easily emulsified by surfactants. This contributes to avoid the problem of visible waste in the window of a front-loading washing machine during the wash cycle and also prevents the deposition of undissolved particles or lumps of coating material in the load of clothes.

Water solubility is measured by ASTM E1148-87 test protocol titled "Method standard test for the determination of water solubility. "

The fracture of the coating during washing It is improved by adding a disintegrant in the coating. This disintegrant will swell on contact with water and break Coating in small pieces. This will favor dissolution. of the coating in the wash solution. Typically, the disintegrant is suspended in the melt of the coating to a level of up to 30%, preferably between 5% and 20% and with maximum preference between 5% and 10%, by weight.

The clay mineral compound, as has been described above, is a disintegrant for use herein invention.

Other possible disintegrants that may be used in addition to the disintegrating clay are described in Handbook  of Pharmaceutical Excipients (1986). Examples of disintegrants Suitable include starches: (natural starch, modified or pregelatinized, sodium starch gluconate), rubber gum agar, rubber guar, locust bean gum, karaya gum, pectin gum, rubber tragacanth; croscarmellose sodium, crospovidone, cellulose, carboxymethyl cellulose, alginic acid and its salts including sodium alginate, silicone dioxide, clay, polyvinylpyrrolidone,  soy polysaccharides, ion exchange resins, polymers that contain cationic groups (e.g., quaternary ammonium), amine substituted polyacrylates, cationic amino acids polymerized such as poly-L-lysine hydrochloride polyallylamine) and mixtures thereof.

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

"Melting point" means the temperature at which the material when heated slowly, by  example in a capillary tube, it becomes a liquid transparent.

Preferably, the coating material having a melting point of at least 40 ° C is an acid. The acids that have a melting temperature of at least 40 ° C are, for example, dicarboxylic acids. Dicarboxylic acids especially suitable are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, subic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and acid tridecanedioic and mixtures thereof. The most preferred is the adipic acid

More preferably, the coating comprises a crystallized structure The term crystallized means that The coating comprises a material that is solid at temperature environment (25ºC) and has a structure that presents a certain order. This can typically be detected by techniques of usual crystallography such as, p. ex. X-ray analysis, in the own material. In a more preferred embodiment, the material that form the crystallized structure does not crystallize or does it only partially with the optional component that is liquid at 25 ° C previously mentioned. In fact, it is preferred that the component optional remain in a liquid state at 25 ° C in the structure crystalline coating to provide flexibility to the structure and resistance to mechanical stress. With maximum Preferably, the aforementioned acid having a temperature of melting of at least 40 ° C comprises a crystallized structure.

Obviously, the materials practically insoluble with a melting point below 40 ° C are not sufficiently solid at room temperature and it has been observed that materials that have a melting point higher than approximately 200 ° C cannot be used. Preferably a acid with a melting point greater than 90 ° C such as acid azelaic, sebacic acid or dodecanedioic acid. But nevertheless, for the purposes of the present invention, the use of sebacic acid It is less preferred since it provides a negative smell to the product resulting. According to the invention, it has been discovered that an acid that it has a melting point of more than 145 ° C such as adipic acid It turns out to be especially suitable.

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

In a) the coating material is applied to a temperature higher than its melting point and solidifies on The pill. In b) the coating is applied as a solution and The solvent is dried to leave a uniform coating. He virtually insoluble material can be applied to the tablet, by example, by spraying or immersion. Normally when the molten material is sprayed on the tablet, it solidifies quickly forming a uniform coating. When the pills they are immersed in the molten material and then removed, the fast cooling again produces rapid solidification of the coating material During the solidification phase the coating suffers a certain internal tension (eg shrinkage when cooling) and a certain external tension (eg relaxation of the tablet). This will probably cause some cracks in the structure such as edge fragmentation if the material of coating is too brittle to resist this tension mechanical, which is the case when the coating is done only with solid components at 25 ° C. Therefore, it is preferred that the coating comprises a component that is liquid to 25 ° C Therefore, it is believed that this liquid component will allow coating resist and absorb mechanical stress better making the structure of the coating more flexible. He component that is liquid at 25 ° C is preferably added to the coating material in percentages of less than 10% by weight, more preferably less than 5% by weight and most preferably less than 3% by weight of the coating. The component that is liquid at 25 ° C is preferably added to the material of coating in percentages of more than 0.1% by weight, more preferably more than 0.3% by weight and most preferably more than 0.5% by weight of the coating.

Examples of optional components that are liquids at 25 ° C include polyethylene glycols, thermal oil, oil silicone, esters of dicarboxylic acids, acids monocarboxylic, paraffin, triacetin, perfumes or solutions alkaline For example, results have been obtained especially good using NaOH solution as alkaline solution.

It is preferred that the structure of the components that are liquids at 25 ° C be close to the material that forms the crystallized structure so that the structure does not result excessively altered

In another embodiment, the optional component that it is liquid at 25 ° C it can advantageously have a functionality in washing clothes, for example silicone oil, which provides advantages of suppressing soaps, or oil scented. If present, the scented oil may be the perfume composition as described herein, or a perfume composition different from that already contained in the tablet, provided it contains less than 0.6% by weight of bases of Schiff

The coating can also comprise materials other than the optional component that is liquid at 25 ° C. Therefore, more preferred is the addition of reinforcing fibers to the coating to further reinforce the structure.

In a more preferred embodiment, the structure Crystallized is manufactured with adipic acid, where the component which is liquid at 25 ° C is marketed under the name Coasol ™ by Chemoxy International and is a mixture of esters of di-isobutyl of glutaric, succinic and adipic The advantage of using this component is the good dispersion in adipic acid to provide flexibility. Fits note that the disintegration of adipic acid is improved additionally by the adipate content of Coasol ™.

According to a preferred embodiment of the invention, The coating comprises an acid having a temperature of melting of at least 145 ° C, such as adipic acid for example, as well like a clay, such as a bentonite clay for example, where the clay is used as a disintegrant and also to make that the structure of adipic acid is more favorable for water penetration, thus improving the dispersion of adipic acid in an aqueous medium. Clays having a size are preferred of particles less than 75 µm, more preferably less than 53 µm, to obtain the desired effect on the structure of the acid. Preferred clays are bentonite clays. From made the acid has a melting point such that the disintegrants Traditional cellulosics suffer thermal degradation during coating process, while these clays turn out to be more thermostable. In addition, cellulosic disintegrants traditional methods such as Nymcel ™, for example, acquire a brown coloration at these temperatures.

In another preferred embodiment, the coating It also includes reinforcing fibers. It has been discovered that you are fibers further improve the resistance of the coating to the mechanical stress and minimize the occurrence of defects of fragmentation. These fibers preferably have a length of at least 100 µm, more preferably at least 200 µm and with maximum preference of at least 250 µm, to be able to reinforce the structure. These fibers preferably have a length of less than 500 µm, more preferably less than 400 µm and most preferably less than 350 µm, so as not to affect the dispersion of the coating in an aqueous medium. The materials that can be used for these fibers include viscose rayon, natural nylon, synthetic nylon (polyamide types 6 and 6.6), Acrylic, polyester, cotton and cellulose derivatives such as CMCs Most preferred is a cellulosic material marketed with the trademark Solka-Floc? by Fibers Sales & Development It should be noted that these fibers do not need normally a previous compression to reinforce the structure of covering. These fibers are preferably added at a level. less than 5% by weight, more preferably less than 3% by weight, of the coating. These fibers are preferably added to a level of more than 0.5% by weight, more preferably more than 1% in weight of the coating.

According to the present invention, a coating with any desired thickness. For most of the For purposes, the coating represents 1% to 10%, preferably of 1.5% to 5%, of the weight of the tablet.

The coatings of the tablet are very hard and provide additional resistance to the tablet.

Process

A preferred process for making a tablet according to the invention it comprises the steps of:

(to)

form a nucleus compressing a particulate material, the material comprising of surfactant particles and additive reinforcing the detergency;

(b)

apply a coating material to the core, the coating material being in the form of dough cast

(C)

let the coating material molten solidify;

characterized in that the coating comprises a clay.

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Another preferred process for manufacturing a tablet according to the invention comprises the steps of:

(to)

form a nucleus compressing a particulate material, the material comprising of surfactant particles and additive reinforcing the detergency;

(b)

apply a coating material to the core, the coating material being dissolved in a solvent or water;

(C)

evaporate the solvent or the Water;

characterized in that the coating comprises a clay.

The compounds described above for a product are advantageously packaged in a system of packing.

A packaging system can be formed from of a sheet of flexible material. The right products to use As flexible sheet include layered monolayer films or co-extruded These movies can understand different components, such as polyethylene, polypropylene, polystyrene or polyethylene terephthalate. Preferably, the packaging system is made up of a film co-extruded polyethylene and polypropylene bioriented with an MVTR of less than 5 g / day / m2. The MVTR of packaging system is preferably less than 10 g / day / m2, more preferably less than 5 g / day / m2. The Film (2) can have different thicknesses. The thickness should typically be between 10 and 150 µm, preferably of between 15 and 120 µm, more preferably between 20 and 100 µm, even more preferably between 25 and 80 µm and with maximum preference between 30 and 40 µm.

A packaging material preferably it comprises a barrier layer that is typically found in the packaging materials that have a low transmission speed of oxygen, typically less than 300 cm 3 / m2 / day, preferably less than 150 cm3 / m2 / day, more preferably less than 100 cm3 / m2 / day, even more preferably less than 50 cm3 / m2 / day and with maximum preference of less than 10 cm3 / m2 / day. The materials Typical having these barrier properties include polypropylene biorientado, polyethylene terephthalate, nylon, poly (alcohol ethylene vinyl) or laminated materials comprising one of these, as well as SiOx (silicon oxides) or metal sheets, such as example, aluminum sheets. This type of material conditioning can have a beneficial effect on the product stability, for example, during storage.

Among the conditioning methods used wrapper methods are typically found described in WO92 / 20593, including the type wrap flow-wrap (pillow) or type over-wrap. When these processes are used, a longitudinal joint is provided which can be a thin joint or an overlapping joint, after which a first end of the packaging system is closed with a first terminal gasket and then the second end is closed with a second joint terminal. The packaging system may comprise means for close it again as described in WO92 / 20593. In particular, it consider it especially appropriate to use a roller seal or Cold sealing or adhesive. In fact, a cold sealing band or a surface adhesive band of the packaging system in a position adjacent to the second end of the packaging system so that this band can provide the initial seal and subsequent closure of the system packing. In this case, the adhesive or cold closing strip they can correspond to an area that has a cohesive surface, that is, a surface that will adhere only to another surface cohesive These means for subsequent closures may comprise also spacers that prevent unwanted adhesion. Sayings Spacers are described in WO 95/13225, published May 18,  1995. There can also be a plurality of spacers and a plurality of strips of adhesive material. The main requirement is that the communication between the outside and the inside of the packaging is minimum, even after the first opening of the system packing. A cold seal can be used and in particular a cold sealing grid, the cold sealing being adapted for facilitate the opening of the packaging system.

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Examples

The following is a non-limiting example of a suitable perfume composition that is used in the following non-limiting examples of detergent tablet according to the present invention:

6

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Abbreviations used in the following examples 1-6 detergent compositions

In detergent compositions, the component abbreviations have the meanings following:

Anionic agglomerates 1 comprise 40% of anionic surfactant, 27% zeolite and 33% carbonate.

Anionic agglomerates 2 comprise 40% of anionic surfactant, 28% zeolite and 32% carbonate.

The non-ionic agglomerate comprises 26% of non-ionic surfactant, 6% Lutensit K-HD 96, 40% of anhydrous sodium acetate, 20% carbonate and 8% zeolite.

Cationic agglomerates comprise 20% of cationic surfactant, 56% zeolite and 24% sulfate.

The laminar silicate comprises 95% of SKS 6 and 5% silicate

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The bleach activator agglomerates comprise 81% TAED, 17% acrylic / maleic copolymer (form acid) and 2% water.

Acid Sodium Salt Particles ethylenediamine-N, N-disuccinic / sulfate comprise 58% acidic sodium salt ethylenediamine-N, N-disuccinic, 23% sulfate and 19% water.

The suds suppressor comprises 11.5% of silicone oil (from Dow Corning); 59% zeolite and 29.5% of Water.

The binder spray system It comprises 16% by weight polymer of the following type:

8

68% by weight of: PEG4000 and 16% by weight of: DIBS (sodium diisoalkylbenzenesulfonate or sodium sulfonate of Toluene).

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Abbreviations used in the following examples 7 of detergent compositions:

In detergent compositions, the component abbreviations have the meanings following:

THE

: C 11-13 alkyl benzene linear sodium sulphonate

TAS

: Sodium tallow alkyl sulfate

CxyAS

: C 1x-C 1 alkyl sulfate sodium

C46SAS

: (2,3) C 14 -C 16 alkyl secondary sodium sulfate

CxyEzS

: C 1x-C 1 alkyl sulfate condensed sodium with z moles of ethylene oxide

CxyEz

: C_ {1x} -C_ {1y} Alcohol predominantly linear primary condensed with an average of z {} \ moles of ethylene oxide

QAS

: R 2 .N + (CH 3) 2 (C 2 H 4 OH) with R2 = C_12 -C14

QAS 1

: R 2 .N + (CH 3) 2 (C 2 H 4 OH) with R2 = C_ {8} -C_ {11}

SADS

: Alkyl C_ {14} -C_ {22} sodium disulfate of formula 2- (R) .C4 H_ {7} .- 1,4- (SO_ {4}) where R = C_ {10-} C_ {18}

SADE2S

: Alkyl C_ {14} -C_ {22} sodium disulfate of formula 2- (R) .C4 H_ {7} .- 1,4- (SO_ {4}) where R = C_ {10} -C_ {18}, {} \ hskip0.1cm condensed with z moles of ethylene oxide

MONTH

: fatty acid x-sulfomethyl ester C_ {18}

APA

: Amidopropyl dimethylamine C_ {8} -C_ {10}

Soap

: Linear sodium alkylcarboxylate derived from a 80/20 mixture of tallow and fatty acids of {} \ hskip0.1cm coconut

STS

: Sodium toluenesulfonate

CFAA

: Alkyl N-methylglucamide C_ {12} -C_ {14} (coconut)

TFAA

: Alkyl-N-methylglucamide C_ {16} -C_ {18}

TPKFA

: C 16 -C 18 fatty acids of complete distilled fraction

STPP

: Anhydrous sodium tripolyphosphate

TSPP

: Tetrasodium pyrophosphate

Zeolite A

: Hydrated sodium aluminosilicate of formula Na 12 (AlO 2 SiO 2) 12 .27H 2 O with a size of {} \ hskip0.1cm primary particles in the interval 0.1 to 10 micrometers (weight expressed on a {} \ hskip0.1cm anhydrous base)

NaSKS-6

: Crystalline laminar silicate of formula δ- Na_ {2} Si_ {2} O_ {5}

Citric acid

: Anhydrous citric acid

Borate

: Sodium Borate

Carbonate

: Anhydrous sodium carbonate with a size of particles between 200 µm and 900 µm

Baking soda

: Anhydrous sodium bicarbonate with a distribution particle size from 400 \ mum to {} \ hskip0.1cm 1200 \ mum

Silicate

: Amorphous sodium silicate (SiO2: Na2O = 2.0: 1)

Sulfate

: Anhydrous sodium sulfate

Magnesium sulphate

: Anhydrous magnesium sulfate

Citrate

: Trisodium citrate dihydrate with one activity of 86.4% and a size distribution of {} \ hskip0.1cm 425 µm particles at 850 µm

MA / AA

: 1: 4 copolymer of maleic / acrylic acids with a average molecular weight of approximately {} \ hskip0.1cm 70,000

MA / AA (1)

: 4: 6 maleic acid / acrylic acid copolymer with an average molecular weight of apro- {} \ hskip0.1cm exceeding 10,000

AA

: Sodium polyacrylate polymer with a weight average molecular 4,500

CMC

: Sodium carboxymethylcellulose

Cellulose ether

: Methylcellulose ether with a degree of polymerization of 650, marketed by Shin {} \ hskip0.1cm Etsu Chemicals

Protease

: Proteolytic enzyme with 3.3% by weight enzyme active, marketed by NOVO {} \ hskip0.1cm Industries A / S with the name Savinase

Protease I

: Proteolytic enzyme with 4% enzyme weight active, as described in document {} \ hskip0.1cm ment ment WO 95/10591, marketed by Genencor Int. Inc.

Alcalase

: Proteolytic enzyme with 5.3% enzyme weight active, marketed by NOVO {} \ hskip0.1cm Industries ACE

Cellulase

: Cellulite enzyme with 0.23% by weight enzyme active, marketed by NOVO {} \ hskip0.1cm Industries A / S with the trade name Carezyme

Amylase

: Amylolytic enzyme with 1.6% by weight enzyme active, marketed by NOVO {} \ hskip0.1cm Industries A / S with the trade name Termamyl 120T

Amylase II

: Amylolytic enzyme according to the description of PCT / US9703635

Lipase

: Lipolytic enzyme with 2.0% enzyme weight active, marketed by NOVO {} \ hskip0.1cm Industries A / S with the trade name Lipolase

Lipase II

: Lipolytic enzyme with 2.0% enzyme weight active, marketed by NOVO {} \ hskip0.1cm Industries A / S with the trade name Lipolase Ultra

Endolasa

: Endoglucanase enzyme with 1.5% by weight of active enzyme, marketed by NOVO {} \ hskip0.1cm Industries A / S

PB4

: Sodium perborate tetrahydrate of formula nominal NaBO_2 .3H2 {2} O.H2 {O2}

PB1

: Anhydrous sodium perborate bleach Nominal formula NaBO_2 .H2 {2}

Percarbonate

: Sodium percarbonate of nominal formula 2Na2CO3 .3H2O2

DOUBS

: Decanoyl oxybenzene sulfonate in the form of the sodium salt

DPDA

: Diperoxidedecanedioic acid

NOBS

: Nonanoyloxybenzenesulfonate in salt form sodium

NACA-OBS

: (6-nonamidocaproil) oxybenzene sulfonate

WOLVES

: Dodecanoyloxybenzene sulfonate in the form of the sodium salt

DOUBS

: Decanoyloxybenzene sulfonate in the form of the Sodium salt

DOBA

: Decanoyl Oxybenzoic Acid

TAED

: Tetraacetylethylene diamine

DTPA

: Acid diethylene triamine pentaacetic

DTPMP

: Dietilen-triamino-pentamethylene phosphonate, marketed by Monsanto with the name {} \ hskip0.1cm commercial Dequest 2060

EDDS

: Acid ethylenediamino-N, N'-disuccinic, isomer (S, S) in the form of its sodium salt.

Photoactivated

: Sulfonated zinc phthalocyanine encapsulated in soluble bleach dextrin polymer {{\ hskip0.1cm te (one)

Photoactivated

: Aluminum sulphonated phthalocyanine encapsulated in whitening dextrin soluble polymer of {{} \ hskip0.1cm (2)

Brightener 1

: 4,4'-bis (2-sulfoestyryl) biphenyl disodium

Brightener 2

: 4,4'-Bis (4-anilino-6-morpholino-1.3.5-triacin-2-yl) amino) stilbene-2,2'-disulfonate disodi- {} \ hskip0.1cm co

HEDP

: Acid 1,1-hydroxyethane diphosphonic

PEGx

: Polyethylene glycol, with a molecular weight of x (of typical form 4,000)

PEO

: Polyethylene oxide, with an average molecular weight of 50,000

TEPAE

: Ethoxylated tetraethylenepentaamine

PVI

: Poly (vinylimidazole) with a molecular weight 20,000 average

PVP

: Polyvinylpyrrolidone polymer, with a weight average molecular of 60,000

PVNO

: Polyvinylpyridine N-oxide polymer, with a average molecular weight of 50,000

PVPVI

: Polyvinylpyrrolidone copolymer and vinylimidazole, with an average molecular weight of {} \ hskip0.1cm 20,000

QEA

: bis ((C 2 H 5 O) (C 2 H 4 O) n) (CH 3) -N + - C 6 H 12 -N + - (CH 3) bis ((C 2 H 5 O) - (C 2 H 4 O)) n, where n is {} \ hskip0.1cm from 20 to 30

PEI

: Polyethyleneimine with an average molecular weight of 1800 and an average degree of ethoxylation {} \ hskip0.1cm of 7 ethylene oxides by nitrogen

Clay I

: Bentonite clay

Clay II

: Smectite clay

Flocculating agent I

: Polyethylene oxide with a weight molecular average between 200,000 and 400,000

Flocculating agent II

: Polyethylene oxide with a weight molecular average between 400,000 and 1,000,000

Flocculating agent III

: Acrylamide and / or acid polymer acrylic with an average molecular weight of 200,000 to {} \ hskip0.1cm 400,000

SRP I

: Polyester polymer with terminal protection anionic for dirt release

SRP II

: Polysaccharide polymer for the release of dirt

SRP 1

: Polyesters with terminal protection no ionic

SRP 2

: Short block polymer poly (1,2-propylene terephthalate) diethoxylated

Defoamer {} \ hskip0.3cm silicone

: Controller of polydimethylsiloxane foam with copolymer siloxane-oxyalkylene co- {} \ hskip0.1cm mo dispersing agent with a relationship between said foam regulator and said 10: 1 dispersing agent {} \ hskip0.1cm a 100: 1

Opacifying

: Mix of water-based monostyrene latex, marketed by BASF Aktienge- {} \ hskip0.1cm sellschaft under the trade name Lytron 621

Wax

: Paraffin Wax

Mottled compound

: Carbonate or organic carboxylic acid colored / salt

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Example one

i)

A detergent base powder of composition A is prepared as follows: all material in the form of particles of the base composition was mixed in a mixing drum or in a spray drum to form a mixture in the form of homogeneous particles, apart from the spray system of binder, fluorescent or brightener and photobleach sulfonated zinc phthalocyanine. The particulate mixture is then divided into two equal parts, one part for make a white layer and another part to make a green layer. The white layer material is obtained by spraying the brightener or fluorescent along with half of the binder. The green layer material is obtained by spraying the Photoblanking sulphonated zinc phthalocyanine together with the rest of the binder. The layer was then independently processed in  a Loedige KM 600®.

ii)

Using a Bonals® rotary press both matrices were filled in two forced feeding jars independent. Both layers are compressed together at the stations Pre-compression and compression to form a double pill cap.

iii)

In this particular example, the pills have a 45 mm square cross section on one side, a height of 24 mm and a weight of 45 g. The height of the green bottom layer equals at 50% of the total height of the tablet. Resistance to traction of the uncoated tablets was 13 kPa.

iv)

The tablet was then coated with 2.5 g of coating formed by 90% by weight of adipic acid and 10% by CSM bentonite clay weight.

9

10

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Example 2

i)

A detergent base powder of composition A is prepared as follows: all material in the form of particles of the base composition was mixed in a mixing drum or in a spray drum to form a mixture in the form of homogeneous particles. The binder system was after pulverized The powder was then processed in a Loedige KM 600®.

ii)

Using a laboratory bench press Instron® filled the detergent powder into the matrix. Dust had been compressed with a force such that resistance to Pickup of the tablet outside 10 kPa.

iii)

In this particular example, the pills have a 54 mm diameter on one side, a height of 24 mm and a weight of 45 g.

iv)

The tablet was then coated with 2.5 g of coating formed by 90% by weight of adipic acid and 10% by CSM bentonite clay weight.

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Example 3

i)

A detergent base powder of composition A is prepared as follows: all material in the form of particles of the base composition was mixed in a mixing drum or in a spray drum to form a mixture in the form of homogeneous particles. The binder system was after pulverized The powder was then processed in a Loedige KM 600®.

ii)

Using a laboratory bench press Instron® filled the detergent powder into the matrix. Dust had been compressed with a force such that resistance to Pickup of the tablet outside 10 kPa.

iii)

In this particular example, the pills have a 54 mm diameter on one side, a height of 24 mm and a weight of 45 g.

The tablet was then coated with 2.5 g of coating formed by 89% by weight of adipic acid, 10% by weight of bentonite clay and 1% by weight of Coasol ™.

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Example 4

i)

A detergent base powder of composition A is prepared as follows: all material in the form of particles of the base composition was mixed in a mixing drum or in a spray drum to form a mixture in the form of homogeneous particles. The binder system was after pulverized The powder was then processed in a Loedige KM 600®.

ii)

Using a laboratory bench press Instron® filled the detergent powder into the matrix. Dust had been compressed with a force such that resistance to Pickup of the tablet outside 10 kPa.

iii)

In this particular example, the pills have a 54 mm diameter on one side, a height of 24 mm and a weight of 45 g.

The tablet was then coated with 2.5 g of coating formed by 87% by weight of adipic acid, 10% by weight of bentonite clay and 1% Coasol ™ and 2% by weight of Solka-Floc? 1016.

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Example 5

i)

A detergent base powder of composition A is prepared as follows: all material in the form of particles of the base composition was mixed in a mixing drum or in a spray drum to form a mixture in the form of homogeneous particles. The binder system was after pulverized The powder was then processed in a Loedige KM 600®.

ii)

Using a laboratory bench press Instron® filled the detergent powder into the matrix. Dust had been compressed with a force such that resistance to Pickup of the tablet outside 10 kPa.

iii)

In this particular example, the pills have a 54 mm diameter on one side, a height of 24 mm and a weight of 45 g.

The tablet was then coated with 2.5 g of coating formed by 78% by weight of adipic acid, 18.5% by weight of bentonite clay and 1% Coasol? and 2.5% in NaOH weight (1M).

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Example 6

i)

A detergent base powder of composition A is prepared as follows: all material in the form of particles of the base composition was mixed in a mixing drum or in a spray drum to form a mixture in the form of homogeneous particles. The binder system was after pulverized The powder was then processed in a Loedige KM 600®.

ii)

Using a laboratory bench press Instron® filled the detergent powder into the matrix. Dust had been compressed with a force such that resistance to Pickup of the tablet outside 10 kPa.

iii)

In this particular example, the pills have a 54 mm diameter on one side, a height of 24 mm and a weight of 45 g.

The tablet was then coated with 2.5 g of coating formed by 88% by weight of adipic acid, 10% by weight of bentonite clay and 1% by weight of Coasol ™ and 1% in tetrasodium ethane salt weight 1-hydroxy diphosphonate.

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Example 7

Below are compositions detergents according to the invention that can be used as is or in place of composition A, described above, in any of the Examples 1-6.

In the following examples, all concentrations are expressed as% by weight of the composition:

eleven

12

13

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Below are compositions suitable for use in the present invention.

14

fifteen

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Below are compositions detergents suitable for use in the present invention.

16

17

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Below are compositions detergents suitable for use in the present invention.

18

19

Claims (16)

1. A scented detergent tablet, the tablet comprising a clay mineral compound; and in where the perfume comprises less than 0.6% of Schiff base by weight of the perfume composition. 2. A scented detergent tablet according to the claim 1, wherein said tablet further comprises a covering. 3. One tablet according to one of the claims 1 or 2, wherein the clay mineral compound is present in the coating on particles that have a size smaller than 75 µm in diameter. 4. A tablet according to any one of the claims 1-3, wherein the tablet is a softener tablet 5. A tablet according to any one of the claims 1-4, wherein the composition of perfume is practically free of Schiff bases, which comprises less than 0.4% by weight of the base perfume composition of Schiff 6. A tablet according to any one of the claims 1-5, wherein the composition of perfume is exempt from perfume ingredients selected from methyl anthranilate and hydroxycitronellal; methyl anthranilate and methyl nonyl acetaldehyde; methyl anthranilate and PT bucinal; methyl and liral anthranilate; methyl anthranilate and ligustral; and mixtures thereof. 7. A tablet according to any one of the claims 2-6, wherein the coating It also comprises an acid having a melting temperature of at minus 40 ° C, preferably at least 145 ° C. 8. A tablet according to claim 7, in where the acid having a melting temperature of at least 40 ° C It has a crystallized structure. 9. A tablet according to claim 8, in where the acid that forms the crystallized structure is an acid dicarboxylic, preferably adipic acid. 10. A tablet according to any one of the claims 2-9, wherein the coating It consists practically of adipic acid. 11. A tablet according to any one of the claims 2-10, wherein the coating it also comprises a component that is liquid at 25 ° C. 12. A tablet according to any one of the claims 2-11, wherein the coating It also includes reinforcing fibers. 13. A tablet according to any one of the claims 1-12, wherein the tablet in addition contains a heavy metal ion sequestrant, preferably selected from organic phosphonates. 14. A tablet according to any one of the claims 1-13, wherein the composition detergent further comprises a flocculating agent.

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15. A process for making a tablet according to any one of claims 2-14, which It comprises the stages of:

(to)

form a nucleus compressing a particulate material, the material comprising of surfactant particles and additive reinforcing the detergency;

(b)

apply a coating material to the core, the coating material being in the form of dough cast

(C)

let the coating material molten solidify;

characterized in that the coating comprises a clay.

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16. A process for making a tablet according to any one of claims 2 to 14, comprising the stages of:

(to)

form a nucleus compressing a particulate material, the material comprising of surfactant particles and additive reinforcing the detergency;

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(b)

apply a coating material to the core, the coating material being dissolved in a solvent or water;

(C)

evaporate the solvent or the Water;

characterized in that the coating comprises a clay.