ES2300138T3 - PERFUMED DETERGENT PAD. - Google Patents

Abstract

A coated perfumed detergent tablet, the tablet comprising a clay mineral compound and a heavy metal ion sequestrant, wherein the coating comprises the heavy metal ion sequestrant.

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.

In GB-A-0 989 683, published on April 22, 1965, describes a process for prepare a particulate detergent from surfactants and inorganic salts; spray on soluble silicate in water; and compress the detergent particles in a tablet that Keep the solid shape. Finally, a film forming polymer organic easily soluble in water (for example, poly (vinyl alcohol)) provides a coating for make the detergent tablet abrasion resistant 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 of 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, now it has also been discovered that when a clay mineral compound is present in the coating of the detergent tablet, clay, for the same reasons mentioned above, can have a negative effect on the perfume action contained therein as well as on the appearance of the 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.

Now it has been surprisingly discovered that the adding a heavy metal ion sequestrant to the tablet Scented detergent solves these problems.

Summary of the invention

The present invention is a pill of scented coated detergent, the tablet comprising a clay mineral compound and a metal ion sequestrant heavy and where the coating comprises the sequestrant of heavy metal ions

The expression "detergent tablet scented "means that the perfume may be present in the coating or in the detergent composition, or 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 or both.

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 softening agents of cationic tissues are typically present in a relationship weight between cationic tissue softening agent and clay from 1: 200 to 1:10, preferably from 1: 100 to 1:20. The agents Suitable cationic fabric softeners include amines tertiary or amides with double long chain not soluble in water as those described in GB-A-1 patents 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.

It is often desirable to have a clay like disintegrant in the coating. In this case, the clay is preferably present in the coating with a size of particles less than 75 µm, more preferably less than 53 \ mum.

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.

Heavy metal ion sequestrants

Tablet of detergent compositions of the invention also contains a metal ion sequestrant heavy present in the coating. The ion sequestrant of heavy metal may be present 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 counter-cation such 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 for use in the present invention include phosphonates organic, such as aminoalkylene poly (alkylene phosphonates), ethane 1-metal hydroxy diphosphonates alkaline 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 acid β-alanin-N, N'-diacetic, aspartic acid-N, N'-diacetic, aspartic acid-N-monoacetic acid and iminodisuccinic acid described in EP-A-509,382 are also appropriate.

Application EP-A-476,257 describes kidnappers based on appropriate amino. 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.

The most preferred heavy metal ions to use in the present invention are ethanes 1-metal hydroxy diphosphonates alkaline, in particular when used together with diethylenetriamine-penta (methylene phosphonate).

Fragrance

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

Suitable perfumes are described in US 5,500,138, said patent being incorporated as Reference herein.

Examples of perfume ingredients useful in the perfume composition include, but are not limited to, hexyl cinnamic aldehyde; amylcinamic 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) -butan2-one; 1- (2,6,6-Trimethyl-2-cyclohexen-1-yl) -2-buten1-one; para-methoxyacetophenone; para-methoxy-alpha-phenylpropene; methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.

Other examples of fragrance materials include, but not limited to, orange oil; oil of lemon; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma; 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 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-dimethylindane; 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; phenyl acetaldehyde e indole;

More examples of perfume components are geraniol; geranyl acetate; linalool; linalyl acetate; tetrahydrolinalol; citronellol; acetate citronellyl; di-hydromyrcenol; acetate dihydromyrcenyl; 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; isobutyrate of phenoxyethyl; dimethylacetal phenylacetaldehyde; diethylacetal phenylacetaldehyde; geranonitrile; citronelonitrile; cedril acetal; 3-isocanfilcyclohexanol; cedril methyl ether; isolongifolanone; hawthorn nitrile; Hawthorn; heliotropin; eugenol; vanillin; diphenyl oxide; hydroxycitronella ionone; methyl ionones; isomethyl ionomas; ironas cis-3-hexenol and esters of themselves; fragrances of indane musk; musk fragrances tetralin; isocroman musk fragrances; ketones macrocyclic; musk fragrances of macrolactone; brazilian ethylene.

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

Preferably, the perfume composition Contains less than 0.6% by weight of the base perfume composition from Schiff. The perfume for use in the present invention is used to a level of up to 5 grams per pill and preferably is virtually free of Schiff bases.

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 condensation products of an aldehyde perfume ingredient with an anthranilate. A typical description can be found in US Patent 4,853,369. Schiff bases can be added directly to the perfume composition or they can be formed in situ in the perfume composition by adding thereto an anthranilate such as a methyl or ethyl anthranilate together with an aldehyde that can react with the anthranilate to form the base from 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 Schiff bases of 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde  and methyl anthranilate; condensation products of: hydroxycitronellal and methyl anthranilate; 4- (4-hydroxy-4-methyl pentyl) -3-cyclohexene-1-carboxaldehyde and methyl anthranilate; methyl anthranilate and hydroxycitronellal marketed under the name Aurantiol; methyl anthranilate and methyl nonyl acetaldehyde sold under the name Agrumea; methyl anthranilate and PT Bucinal marketed under the name Verdantiol; methyl and liral anthranilate marketed with the name Lyrame; methyl anthranilate and ligustral marketed with the name Ligantral; and mixtures thereof.

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

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

Detergent ingredients

The pads can 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.

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 a level of about 1% to about 55%, by weight, include C 11 -C 18 alkyl benzenesulfonates ("LAS") conventional and alkyl C 10 -C 20 primary, chain sulfates branched and random ("AS"), the alkyl C 10 -C 18 secondary sulfates (2.3) of formula CH 3 (CH 2) x (CHOSO 3 -M +) CH 3 and CH 3 (CH2) y (CHOSO_3 M +) CH_ {CH} {3} where x e (y + 1) are integers of at minus about 7, preferably at least about 9, and M is a water-soluble cation, especially sodium, unsaturated sulfates such as oleyl sulfate, C 10 -C 18 alkyl alkoxy sulfates ("AE_ {S}"; especially EO ethoxy sulfates 1-7), C 10 -C 18 alkyloxy carboxylates (especially EO ethoxycarboxylates 1-5), the C 10-18 glycerol ethers, the C 10 -C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides and esters of C 12 -C 18 fatty acids alpha-sulphonates If desired, they can also Surfactants not included in the general compositions ionic and conventional amphoteric 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 polyhydroxyamides of acids fatty Typical examples include N-methyl C 12 -C 18 glucamides. See document WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy fatty acid polyhydroxyamides, such like C_ {10} -C_ {18} N- (3-methoxypropyl) 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

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.

Detergency builders

Optionally, to the compositions of the present invention, additives reinforcing the detergency to facilitate the control of mineral hardness. They can inorganic detergent builder additives and also organic Detergent builder additives are used in typical way in laundry compositions to help Remove stains 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 "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, particularly those with a SiO2: Na2O 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, granted to H. P. Rieck. NaSKS-6 is the registered trademark of a silicate crystalline laminar marketed by Hoechst (hereinafter abbreviated  like "SKS-6"). Unlike additives Zeolite-type detergency builders, the booster additive  of Na SKS-6 silicate type detergency no contains aluminum NaSKS-6 presents the morphology delta-Na2 SiO5 laminar silicate. This it can be prepared by methods such as those described in DE-A-3,417,649 and DE-A-3,742,043. He SKS-6 is a very preferred laminar silicate, although so are other layered silicates, such as those with general formula NaMSi_ {O} {2x + 1}. and H2O, 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 Hoechst's 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} \ cdotxH2 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. A method for produce aluminosilicate ion exchange materials se described in US 3,985,669, granted to Krummel and cabbage. on October 12, 1976. The exchange materials of preferred crystalline aluminosilicate ions useful in the The present invention are those marketed as Zeolite A, Zeolite P (B), Zeolita MAP and Zeolita X. In one embodiment especially preferred, the aluminosilicate ion exchange material Crystalline has the formula:

Na 12 [(AlO 2) 12 (SiO 2) 12] \ x 2 O

where x is about 20 to about 30, especially about 27. This material is known as Zeolite A. They can also be used in the present invention dehydrated zeolites (x = 0-10). Preferably, the aluminosilicate has a particle size of approximately 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 type detergency encompasses the ether polycarboxylates, including oxidisuccinate, as described in US 3,128,287, granted to Berg on April 7, 1964, and in US-3,635,830, granted to Lamberti et al. on January 18, 1972. See also the reinforcing additives of the "TMS / TDS" type detergency of US 4,663,071, granted to Bush et al. May 5th from 1987. Suitable polycarboxylate ether also includes cyclic compounds, especially alicyclic compounds such as described in US 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.

They are also suitable in the compositions detergents of the present invention the 3,3-dicarboxy-4-oxa-1,6-hexanedioates  and related compounds described in US 4,566,984, granted to Bush on January 28, 1986. Additives reinforcing acid detergency Useful succinic include alkyl and alkenyl acids C5 {C} {C20} succinic and salts of same. A particularly preferred compound of this type is the dodecenylsuccinic acid. Specific examples of additives Succinate type detergency builders 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.

In US 4,144,226, granted to Crutchfield et al. on March 13, 1979, and in US 3,308,067, granted to Diehl on March 7, 1967, other suitable polycarboxylates are described. See also 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 and one or more bleach activators. When present, the bleaching agents will be in shape typical at levels of about 1% to about 30%, of most typical form of about 5% to about 20%, of the detergent composition, especially for washing fabrics. Yes bleach activators are present, their quantity will be typically from about 0.1% to about 60%, of more typically 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 be used without restriction are percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agent include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic acid. Such bleaching agents are described in US-4,483,781, issued to Hartman on November 20, 1984, US-740,446, issued to Burns et al. and presented on June 3, 1985, EP-0.133.354, granted to Banks et al. and published on February 20, 1985, and US-4,412,934, granted to Chung et al. on November 1, 1983. Very preferred bleaching agents also include 6-nonylamino-6-oxoperoxicaproic acid as described in US-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 result in the in situ production of the peroxyacid corresponding to the bleach activator in aqueous solution (ie, during the washing process). Several non-limiting examples of activators are described in US 4,915,854, issued to Mao et al. on April 10, 1990, and US-4,412,934. Nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylenediamine (TAED) activators are typical and mixtures thereof can also be used. See also US-4,634,551 for other typical bleach and activators useful in the present invention.

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

\hskip1cm

o

\hskip1cm

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

 \ hskip1cm 

or

 \ hskip1cm 

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

       \ newpage
    

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, bleaching compounds may be catalyzed by a manganese compound. Sayings Compounds are well known in the art and include, for example, the manganese based catalysts described in US 5,246,621, US 5,244,594; US 5,194,416; US-5,114,606 and in EP-549.271A1, EP-549.272A1, EP-544.440A2 and EP-544.490A1. Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6) 2, Mn III 2 (uO) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 2) 4) 2, Mn IV 4 (u-O) 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 bleach catalysts Metal based include those described in US 4,430,243 and US 5,114,611. The use of manganese with various complex ligands to reinforce the Whitening is also described in the 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-based spots, carbohydrates or triglycerides or to prevent transfers of dyes or to regenerate tissues. The enzymes that can be incorporate are proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. Can also be Include other types of enzymes. These can be of any origin appropriate as, p. eg, vegetable, animal, bacterial, fungal and yeast. However, your choice is dictated by several factors as the optimal values of pH activity and / or stability, thermostability, stability against active detergents, additives detergency builders, etc. In this regard, the bacterial or fungal enzymes, such as amylases and proteases Bacterial 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 the subtilisin that are obtained from special strains of B. subtilis and B. licheniformis. Another suitable protease is that obtained of a strain of Bacillus that has 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 the Novo patent GB-1,243,784. Enzymes Proteolytics suitable for removing protein stains available on the market 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 EP-130,756, Bott et al., published on 9 January 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 The present invention includes both bacterial cellulases and the fungi. Preferably, they will have an optimum pH between 5 and 9.5. Suitable cellulases are described in US 4,435,307, issued to Barbesgoard et al. the 6 of March 1984, which describes the fungal cellulase produced at from Humicola insolens and Humicola strain DSM1800 or a 212 cellulase producing fungus that belongs to the genus Aeromonas and the cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME (de Novo) It is especially useful.

Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as described in patent GB-1,372,034. See also lipases in the patent JP-53.20487, submitted for public inspection on February 24, 1978. This Lipase is marketed by Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the name Lipasa P "Amano", hereinafter referred to like "Amano-P". Other commercial lipases are Amano-CES, Chromobacter viscosum lipases, p. eg, Chromobacter viscosum var. NRRLB 3673 lipolyticum, marketed by Toyo Jozo Co., Tagata, Japan; and other lipases of U.S. Chromobacter viscosum 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 US 4,261,868, granted to Hora et al. on April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques Enzymatic stabilization techniques are described in illustrated in US-3,600,319, granted on August 17 from 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 polymeric flocculating agents are described 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.

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.

Very 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 put 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 20.9 rad / s (200 revolutions per minute).

2-

Be introduce 980 g of deionized water into the beaker Sotax

3-

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

4-

The stage 3 is repeated at 20, 30, 40, 50, 1 min, 2 min, 5 min and 10 min of finishing stage 2.

5-

The measurement taken at 10 min is used as a plateau value or as maximum value.

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 whole pill it will have a tensile strength of more than 5 kPa, preferably more than 10 kPa, more preferably, and 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, and in particular for use in dishwashing or dishwashing applications; Y a tensile strength of less than 300 kPa, preferably less than 200 kPa, more preferably less than 100 kPa, even more preferably less than 80 kPa and with maximum preference of less than 60 kPa. In fact, in the case of laundry applications, the tablets should be less tablets that in the case of dishwasher applications, for example, where dissolution is most easily achieved, so that in a washing application the resistance to Traction 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. The right equipment include a standard piston press or a rotary press (such as Courtoy®, Korch®, Manesty® or Bonals®). Pills prepared according to this invention preferably have a diameter between 20 mm and 60 mm, preferably at least 35 and up to 55 mm and a weight between 25 and 100 g. The relationship between height and diameter (or width) of the tablet is preferably larger than 1: 3, more preferably greater than 1: 2. Compaction pressure used to prepare these pills does not need to exceed 100,000 kN / m2, preferably does not need to exceed 30,000 kN / m2, more preferably it does not need to exceed 5,000 kN / m2, even more preferably it does not need to exceed 3,000 kN / m2 and with Maximum preference does not need to 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 of less than 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 turning speed of 20.9 rad / s (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:

       \ newpage
    

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) y H CH3

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.

Hydrotropic solvents 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

       \ newpage
    

in where

E is a group hydrophilic functional,

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.

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.

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 inlet to the clothes washer is fixed at a temperature of 20ºC and a hardness of 21 grains per 3.8 l (gallon), the water inlet flow of the dispenser being set at 8 l / min. The level of remaining pill residues is checked in the dispenser turning on the washing machine and setting the cycle of wash in wash program 4 (white / color, short cycle). He percentage residue dispensed is determined in the manner next:

% 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 measure of water hardness it is expressed in the traditional unit "grain per 3.8 l (gallon)", where 0.001 moles per liter = 7.0 grains per 3.8 l (gallon), which represents the concentration of Ca 2+ ions in solution.

Effervescent agent

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,

p. \ ex. \ C_ {H} {8} O_ {7} + 3NaHCO_ {3} → Na_ {3} C_ {6} H_ {5} + 3CO_ {2} \ uparrow + \ 3H 2 O

Other examples of sources of acid and carbonate and Other effervescent systems can be found in 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.

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, modified or pregelatinized, sodium starch gluconate; rubber bands: agar rubber, guar gum, 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 (eg 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 from 40 ° C to 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 present in the coating and having a particle size of less than 75 um, more preferably less than 53, to obtain the desired effect on acid structure. The preferred clays They are bentonite clays. In fact the acid has a point of fusion such that traditional cellulosic disintegrants suffer a thermal degradation during the coating process, while these clays turn out to be more thermostable. Further, traditional cellulosic disintegrants 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 because the coating comprises a clay.

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

(to)

form a nucleus compressing a particulate material, where the material in the form of particles comprises surfactant 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 because 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 a means of repeated closure as described in WO92 / 20593. In particular, the use of a turning device, cold sealing or adhesive It is especially suitable. In fact, a band can be applied cold sealing or a band of adhesive to the surface 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 packaging system. In In this case, the adhesive or cold seal strip can correspond to an area that has a cohesive surface, is 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. These Separators are described in WO 95/13225, published May 18, 1995. There may also be a plurality of separators and a plurality of strips of adhesive material. The main requirement is that the communication between the outside and the inside of the packaging be minimal, 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 to facilitate the opening of the packaging system.

Examples

The following is a non-limiting example of a suitable perfume composition A which is used in the following examples 1 and 2 non-limiting detergent tablets according to the present invention:

6

7

Abbreviations used in the following examples 1-6 detergent compositions

In detergent compositions, the abbreviated identifications of the components have the following meanings:

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

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% in Weight of: DIBS (sodium diisoalkylbenzenesulfonate or sodium sulfonate from Toluene).

Abbreviations used in the following examples 7 of detergent compositions

       \ global \ parskip0.960000 \ baselineskip
    

In detergent compositions, the abbreviated identifications of the components have the following meanings:

THE

: Rent C_ {11-13} linear sodium benzenesulfonate

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}, {} \ hskip1mm condensed with z moles of ethylene oxide

MONTH

: fatty acid x-sulfomethyl ester C_ {18}

APA

: Amidopropyl dimethyl C 8 -C 10 amine

Soap

: Linear sodium alkylcarboxylate derived from a 80/20 mixture of tallow and {} \ hskip1mm fatty acids coconut

STS

: Sodium toluenesulfonate

CFAA

: Alkyl C 12 -C 14 N-methylglucamide (coconut)

TFAA

: Alkyl-N-methyl C 16 -C 18 glucamide

TPKFA

: C 16 -C 18 fatty acids crude distillation derivatives

STPP

: Anhydrous sodium tripolyphosphate

TSPP

: Tetrasodium pyrophosphate

Zeolite A

: Hydrated sodium aluminosilicate of formula Na 12 (A1O 2 SiO 2) 12 .27H 2 O which It has a size of {} \ sk main particle size in the range of 0.1 to 10 micrometers (weight expressed with respect to {} \ hskip1mm to the anhydrous substance)

NaSKS-6

: Crystalline laminar silicate of formula? Na_ {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 {} \ hskip1mm 1200 \ mum

Silicate

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

Sulfate

: Anhydrous sodium sulfate

Sulfate magnesium

{} \ hskip1.2cm: Sulfate anhydrous magnesium

Citrate

: Trisodium citrate dihydrate with one activity of 86.4% and a size distribution of {} \ hskip1mm 425 µm particles at 850 µm

MA / AA

: 1: 4 copolymer of maleic / acrylic acids with a average molecular weight of approx. 70,000

MA / AA (1)

: 4: 6 maleic acid / acrylic acid copolymer with an average molecular weight of apro- {} \ hskip1mm exceeding 10,000

AA

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

CMC

: Sodium carboxymethylcellulose

       \ newpage
    

Ether of cellulose

: Methylcellulose ether with a polymerization degree of 650, marketed by Shin Etsu {} \ hskip1mm Chemicals

Protease

: Proteolytic enzyme with 3.3% by weight enzyme  active, marketed by NOVO {} \ Hskip1mm Industries A / S with the name Savinase

Protease I

: Proteolytic enzyme with 4% enzyme weight active, as described in document {} \ WOskip1mm WO 95/10591, marketed by Genencor Int. Inc.

Alcalase

: Proteolytic enzyme with 5.3% enzyme weight active, marketed by NOVO {} \ hskip1mm Industries ACE

Cellulase

: Cellulite enzyme with 0.23% by weight enzyme active, marketed by NOVO {} \ Hskip1mm Industries A / S with the trade name Carezyme

Amylase

: Amylolytic enzyme with 1.6% by weight enzyme active, marketed by NOVO {} \ Hskip1mm 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 Indus- {} \ hskip1mm tries A / S with the trade name Lipolase

Lipase II

: Lipolytic enzyme with 2.0% enzyme weight active, marketed by NOVO Indus- {} \ hskip1mm tries A / S with the trade name Lipolase Ultra

Endolasa

: Endoglucanase enzyme with 1.5% by weight of active enzyme, marketed by NOVO {} \ hskip1mm 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-nonamidocaproyl) oxybenzene sulphonate

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 {} \ hskip1mm 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 {} \ hskip1mm (one)

Photoactivated

: Encapsulated aluminum sulfonated phthalocyanine in soluble dextrin polymer of blan- {} \ hskip1mm queante (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 disodium

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 {} \ hskip1mm 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 {} \ hskip1mm from 20 to 30

PEI

: Polyethyleneimine with an average molecular weight 1800 and an average degree of ethoxylation {} \ hskip1mm of 7 ethylene oxides by nitrogen

Clay I

: Bentonite clay

Clay II

: Smectite clay

Flocculating agent I

{} \ hskip1cm: Polyethylene oxide with an average molecular weight between 200,000 and 400,000

Flocculating agent II

{} \ hskip1cm: Polyethylene oxide with an average molecular weight between 400,000 and 1,000,000

Flocculating agent {} \ hskip-1mm III

{} \ acrylamide and / or acid polymer acrylic with an average molecular weight of 200,000 to {} \ hskip1.1cm 400,000

SRP I

: Polyester polymer with terminal protection anionic for dirt release

SRP II

: Polysaccharide polymer for the release of The dirt

SRP 1

: Polyesters with terminal protection no ionic

SRP 2

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

Defoamer silicone

{} \ hskip1mm: Driver polydimethylsiloxane foam with copolymer siloxane-oxyalkylene as {} \ hskip3mm dispersing agent with a relationship between said foam regulator and said agent disperse {} \ sap from 10: 1 to 100: 1

Opacifying

: Mix of water-based monostyrene latex, marketed by BASF Aktiengesells- {} \ hskip1mm chaft under the trade name Lytron 621

Wax

: Paraffin Wax

Compound mottled

{} \ hskip0.4cm: Carbonate or Colored carboxylic organic acid / salt.

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Example 1

i)

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

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ii)

Using a rotary press Bonals® both matrices were filled in two bottles of independent forced feeding. Both layers are compressed joints in the pre-compression and compression stations for form a double layer pill.

iii)

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

iv)

The tablet was then coated with 2.5 g of coating formed by 89% by weight of adipic acid and 10% by weight of bentonite clay of CSM and 1% by weight of ethane 1-hydroxy diphosphonate.

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9

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Example 2

i)

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

ii)

Using a rotary press Bonals® both matrices were filled in two bottles of independent forced feeding. Both layers are compressed joints in the pre-compression and compression stations for form a double layer pill.

iii)

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

iv)

The tablet was then coated with 2.5 g of coating formed by 89% by weight of adipic acid and 10% by weight of bentonite clay of CSM and 0.5% by weight of ethane 1-hydroxy diphosphonate and 0.5% by weight of diethylenetriamine penta (methylene phosphonate).

Example 3

i)

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

ii)

Using a rotary press Bonals® both matrices were filled in two bottles of independent forced feeding. Both layers are compressed joints in the pre-compression and compression stations for form a double layer pill.

iii)

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

iv)

The tablet was then coated with 2.5 g of coating formed by 89% by weight of adipic acid and 10% by weight of bentonite clay of CSM and 0.5% by weight of ethane 1-hydroxy diphosphonate and 0.5% by weight of diethylenetriamine penta (methylene phosphonate).

Example 4

i)

A detergent base powder of composition A was prepared as next: all the particulate material of the base composition was mixed in a mixing drum or in a drum sprayer to form a particulate mixture homogeneous The binder system was then pulverized. Dust It was then processed in a Loedige KM 600®.

ii)

Using a bench press of Instron® laboratory filled the powder detergent in the matrix. The powder had been compressed with a force such that the tensile strength of the tablet out of 10 kPa.

iii)

In In this particular example, the pads have a diameter of 54 mm 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 weight of bentonite clay of CSM.

The tablet was then coated with 2.5 g of coating formed by 77% by weight of adipic acid, 18.5% by weight of bentonite clay, 1% by weight of Coasol ™, 2.5% by weight NaOH (1M) and 1% by weight of ethane 1-hydroxy diphosphonate.

Example 5

i)

A detergent base powder of composition A was prepared as next: all the particulate material of the base composition was mixed in a mixing drum or in a drum sprayer to form a particulate mixture homogeneous The binder system was then pulverized. Dust It was then processed in a Loedige KM 600®.

ii)

Using a bench press of Instron® laboratory, powder detergent was introduced into the matrix.  The powder had been compressed with a force such that the Tensile strength of the tablet outside 10 kPa.

iii)

In In this particular example, the pads have a diameter of 54 mm 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, 1% Coasol ™ and 1% by weight ethane 1-hydroxy diphosphonate.

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Example 6

i)

A detergent base powder of composition A was prepared as next: all the particulate material of the base composition was mixed in a mixing drum or in a drum sprayer to form a particulate mixture homogeneous The binder system was then pulverized. Dust It was then processed in a Loedige KM 600®.

ii)

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

iii)

In In this particular example, the pads have a diameter of 54 mm 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 86% by weight of adipic acid, 10% by weight of bentonite clay, 1% by weight of Coasol ™, 2% by weight of Solka-Floc? 1016, 0.5% by weight of ethane 1-hydroxy diphosphonate and 0.5% by weight of diethylenetriamine penta (methylene phosphonate).

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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.

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(Table goes to page next)

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

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

twenty

Claims (15)

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1. A scented detergent tablet coated, the tablet comprising a mineral compound of clay and a heavy metal ion sequestrant, where the coating comprises the metal ion sequestrant heavy. 2. A tablet according to claim 1, in where the clay mineral compound is present in the Coating on particles that are smaller than 75 um in diameter. 3. A tablet according to any one of the claims 1-2, wherein the tablet is a softener tablet 4. One tablet according to any of the claims 1-3, wherein the sequestrant of Heavy metal ions are selected from organic phosphonates, preferably ethane 1-metal hydroxy diphosphonates alkaline, diethylenetriamine penta (methylene phosphonate) and mixtures thereof. 5. A tablet according to any one of the claims 1-4, wherein the composition of perfume comprises less than 0.4% by weight of Schiff bases. 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 bucinal PT; methyl and liral anthranilate; methyl anthranilate and ligustral; Y mixtures thereof. 7. A tablet according to any one of the claims 1-6, 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 1-9, wherein the coating It consists practically of adipic acid. 11. A tablet according to any one of the claims 1-10, wherein the coating It also comprises a component that is liquid at 25 ° C. 12. A tablet according to any one of the claims 1-11, wherein the coating It also includes reinforcing fibers. 13. A tablet according to any one of the claims 1-12, wherein the composition detergent further comprises a flocculating agent. 14. A process for making a tablet according to any one of claims 1-13, 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. 15. A process for making a tablet according to any one of claims 1 to 13, comprising the steps from:

(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.