ES2215782T3 - DETERGENT COMPOSITIONS. - Google Patents

Abstract

A multi-region detergent tablet of compressed particulate composition is provided comprising a detergent active compound, a detergency builder, particles which contain sodium tripolyphosphate with a content of the Phase I form which is more than 40 % by weight of the sodium tripolyphosphate in the said particles, at least one salt which is fully hydrated and optionally other detergent ingredients, where in one or more of the regions which contains the particles which contain sodium tripolyphosphate there is less than 10 % by weight of that region of fully hydrated salts, and there is at least one region containing at least 10 % by weight of that region of fully hydrated salts.

Description

Detergent compositions.

This invention relates to compositions of detergent in the form of cleaning tablets, and in particular textile washing tablets and dishwasher tablets automatic The manufacture of such tablets is known as compress or compact an amount of detergent composition in particulate form

It is desirable that the tablets have a adequate mechanical strength when dry, before using, but disintegrate and disperse / dissolve quickly when Add to the wash water. It has not been easy to achieve both properties simultaneously. The more pressure is used when compact one tablet, the density of the tablet and the resistance increase, but the rate of disintegration / dissolution when the tablet comes into contact with the wash water decreases.

The published European application EP-A-839906 describes tablets of a particulate and compacted detergent composition whose purpose is washing of textile material in which the tablet comprises particles containing sodium tripolyphosphate with a content substantial of the phase I form, and this tripolyphosphate is partially hydrated to contain hydration water in a amount between 1% and 5% by weight of sodium tripolyphosphate in those particles

It is demonstrated by examples in that patent application that the tablets incorporating particles with a substantial content of the phase I form of tripolyphosphate of sodium and with some partial hydration of tripolyphosphate it disintegrate and dissolve during use much faster than comparative tablets that use sodium tripolyphosphate with a higher content of the phase II form. Therefore it is possible achieve pills that disintegrate quickly at the time of use.

Normally these pills will contain particles of base powder incorporating active detergent surfactant organic together with some tripolyphosphate detergency adjuvant, individual particles containing sodium tripolyphosphate which is rich in the phase I form and is also partially hydrated, and Thirdly particles of other ingredients. A proportion substantial of the other ingredients is constituted by peroxygen bleach which can be perborate tetrahydrate sodium These pills have been sold commercially. To use it place one or two pills in a net bag, closed with a cord. The bag containing these pills is placed in the washing machine, with the textile material to be washed.

The joint processing document WO01 / 02524 describes some automatic dishwasher tablets comprising less than 5% by weight of surfactant and tripolyphosphate particles of sodium as described above. The examples in this request also demonstrate an improvement in dissolution time for pills containing sodium tripolyphosphate rich in phase I content and partially hydrated instead of sodium tripolyphosphate with a higher phase II content. The tablets exemplified in this processing request together contain a considerable amount of sodium disilicate as a detergency adjuvant, as well as a bleach peroxygen, sodium perborate, and sodium carbonate.

The document EP-A-957159 describes tablets of multilayer detergent comprising sodium tripolyphosphate in a layer and also being present salts in the tablet.

It has now surprisingly been found to be beneficial to partially or completely separate any salts that are completely hydrated ("salts completely hydrated ") in a tablet of sodium tripolyphosphate which is rich in the form of phase I and that can also be partially hydrated Through this separation, it has been discovered that it is possible to increase the dissolution rate of the tablets detergent containing these components.

This separation of the ingredients can be achieve by isolating most fully hydrated salts, if not all, in a region of the tablet that can be a layer, core or insert while sodium tripolyphosphate which is Rich in the form of phase I is in another region of the pill.

Therefore, according to the present invention, provides a particulate composition detergent tablet tablet comprising an active detergent compound, a detergency adjuvant, particles containing tripolyphosphate sodium with a phase I form content that is greater than 40% in weight of sodium tripolyphosphate in said particles, at least one salt that is completely hydrated, and optionally others detergent ingredients, where the tablet comprises a plurality of discrete regions, characterized in that in one or more of the discrete regions containing said particles that contain sodium tripolyphosphate there is less than 10% by weight of that region of fully hydrated salts, and there is at least one region discrete that contains at least 10% by weight of that region of salts fully hydrated

It is conceived that all discrete regions that they contain said particles containing sodium tripolyphosphate they will contain less than 10% by weight of that region of salts completely hydrated However, this may not be the case, in particular if there is a very small discrete region that contains said particles containing sodium tripolyphosphate, or the discrete regions contain a minor amount of sodium tripolyphosphate, for example less than 5% by weight.

The region that contains at least 10% by weight of fully hydrated salts may also contain a system disintegrant that does not comprise said particles containing said sodium tripolyphosphate.

It is further preferred that there be less than 5% by weight, or even not fully hydrated salts in the regions of the tablet containing said tripolyphosphate particles of sodium.

Preferably sodium tripolyphosphate in said particles have a content of the phase I form which is at minus 50% by weight of the sodium tripolyphosphate in said particles. It is also preferred that the amount of hydration water in the sodium tripolyphosphate particles are in a range between 0.5% and 5% by weight, preferably between 2 and 4%, of tripolyphosphate of sodium in those particles.

Aspects will now be described in more detail of this invention, suitable materials and preferences additional.

Sodium tripolyphosphate with high phase I content

As discussed in the document EP-A-839906, tripolyphosphate from sodium can be converted to the phase I form by heating up to above the transition temperature at which tripolyphosphate of phase II anhydrous sodium is transformed into the form of phase I. A procedure for the manufacture of particles containing a high proportion of the phase I form of sodium tripolyphosphate when spray dehydrated below 420 ° C it is provided in US-A-4536377.

The right material is available commercially Distributors include Rhone-Poulenc, Courbevoie, France and Albright & Wilson, Warley, West Midlands, United Kingdom. Preferably the sodium tripolyphosphate is partially hydrated, but the form Anhydrous phase I must also be present. In this way, the sodium tripolyphosphate in the particles can incorporate between 0.5% to at least 5% (by weight of sodium tripolyphosphate in these particles) of hydration water. Degree of hydration it is desirably between 1% and 4%, 5% or 7% by weight.

The sodium tripolyphosphate in these particles is preferably hydrated by a procedure that leads to a homogeneous distribution of hydration water within the tripolyphosphate.

This can be accomplished by exposing the anhydrous sodium tripolyphosphate with steam or moist air. The particles are preferably formed solely by sodium tripolyphosphate with a high content of the phase I form. However, it may be preferred that only at least 80% or 90% by weight of the particles is sodium tripolyphosphate. It is possible that only at least 50% by weight of the particles are tripolyphosphate of sodium.

The particles preferably contain sodium tripolyphosphate in a porous form so that it has a large Superficial area. This can be achieved by spray drying. tripolyphosphate as a mixture with a blowing agent, that is a compound such as ammonium carbonate that decomposes to provide a gas during the course of dehydration by aspersion. This gives the dry material a porous structure, with greater surface area than hollow tripolyphosphate beads obtained without blowing agent.

The apparent density of the particles of sodium tripolyphosphate is preferably 0.75 kg / m3 or less, preferably between 0.52 and 0.72 kg / m 3.

The particles that contain or are formed by sodium tripolyphosphate may have a small particle size medium, such as not exceeding 300 µm, better not exceeding at 250 µm. A small particle size can be achieved if it was necessary by crushing. Uniform prehydration and the high phase I content promotes rapid hydration when tripolyphosphate comes into contact with water. A test Conventional for rapidity of hydration is the Olsen test. It is desirable that in said test the tripolyphosphate reaches 90% of the final value (i.e. 90% of complete hydration when exposed to water at 80 ° C) at 60 seconds.

"Rhodiaphos HPA 3.5" is a class of Rhone-Poulenc sodium tripolyphosphate that has been discovered that it is particularly suitable. It is made up porous particles of small particle size (average size less than 250 µm) with 70% phase I and prehydrated with 3.5% of hydration water

Preferably said particles containing sodium tripolyphosphate with more than 40% phase I material provides sodium tripolyphosphate, including tripolyphosphate from phase I, in an amount that is between 20% to 45% or 50%, or even 60% by weight of the whole tablet. An amount of at least 30% have been found useful in some pills. The amount of these particles in some region of the tablet may be larger than these limits, to provide an adequate level of particles throughout The pill.

The rest of the tablet composition can include additional sodium tripolyphosphate that is not in the form treated above, as anhydrous sodium tripolyphosphate with a high content of the phase II form, sodium tripolyphosphate hydrated or some combination of the two.

The total amount of sodium tripolyphosphate, in all forms, present in the tablet composition of a textile washing tablet will generally be in a range of up to 70% by weight of the tablet. This one can also be the case for an automatic dishwasher tablet, although a range of up to 60% by weight of the tablet is preferred for This type of pill. Therefore it will be appreciated that the amount global sodium tripolyphosphate can be provided at least partially by another material besides said particles.

Salts that are fully hydrated

These salts are those that are at their maximum hydration state thermodynamically stable at temperature environment. This state of maximum hydration may be the highest possible for salt, or it may be less than the greatest possible for salt, but when the highest states of hydration are thermodynamically unstable at room temperature. These salts Fully hydrated include perborates, citrates, acetates, sulfates, carbonates and thiosulfates. Preferably salt Fully hydrated is a salt or persal of sodium.

Perborates can exist in a range of hydration states, and have at least one hydrogen peroxide present instead of, or in addition to, hydration water. For example, there is sodium perborate in a monohydrate or tetrahydrate form both being suitable for use in detergent formulations. By therefore it can be seen that sodium perborate tetrahydrate is a fully hydrated salt Perborates are used as bleach in detergent tablets (see below).

Many carbonates naturally show a range of hydration states. For example, carbonate sodium can be anhydrous, or it can have one, seven or ten molecules of water present as hydration water. Potassium carbonates and magnesium also have both several states of hydration. From this way, while there is some carbonate present at its maximum thermodynamically stable hydration state, the salt will be fully hydrated Carbonates (particularly carbonates sodium and potassium) are often included in the tablets detergent to control the pH of the composition when dissolves They also work, to some extent, as additives of detergency, particularly in dishwasher tablets automatic.

Sulfates can have different states of hydration. Sodium sulfate can be anhydrous, be heptahydrate or decahydrate, while magnesium sulfate It can be anhydrous or heptahydrated. Sulfates can be include in the detergent tablets as fillers. The Sodium thiosulfate can be anhydrous or be pentahydrated.

Sodium acetate may exist in a range of hydration states between 0 (anhydrous) and 3 (trihydrate). The sodium acetate trihydrate may be present as an adjuvant of disintegration (see below).

Sodium citrate has two states of hydration, 2 (dihydrate) and 5 (pentahydrate). However the Pentahydrate state is not thermodynamically stable at temperatures between 20 ° C and 60 ° C, and therefore sodium citrate dihydrate is a fully hydrated salt Sodium citrate also works as a disintegration adjuvant (see below).

It is preferred that the salts completely hydrates have a solubility at 20 ° C of at least 50 g per 100 g of water.

Discrete regions

Discrete regions may be in the form of layers, and a tablet with two layers is a preferred embodiment of the present invention. One layer of this two layer pill Contains phase-rich sodium tripolyphosphate granules I and also partially hydrated, while the other layer Contains fully hydrated salts and / or persalts and optionally Another disintegrant.

Each layer of said tablet is preferably substantially homogeneous, that is, it is the product of compaction of a single particulate composition, although that composition particulate may have been prepared by mixing several components and all its particles will not necessarily be identical. Normally, said two-layer tablet is manufactured in a press to make pills by partially filling the die with the composition of the first layer, pressing this layer, and adding then the composition of the second layer before pressing the tablet for the second time. It is preferable that the two layers of this tablet are not the same size - a range of weight ratio from 10:90 to 40:60, and an interval is more preferable from 20:80 to 30:70, the most preferable being a relationship from 25:75. A discrete region normally has a minimum weight of 5 g.

It is preferred that the layer or layers containing the sodium tripolyphosphate particles comprise at least 50% in weight of the tablet, and that the layer (or layers) containing the salts fully hydrated and / or persales comprise at least 15% in weight of the whole pill.

A preferred alternative embodiment of the invention is a pill that has a pair of opposite faces spaced apart and joined by a peripheral surface of the tablet, in which the tablet is subdivided into at least two regions that are each visible on said face. That pill is one that has a central core that passes through all the tablet. A particular process of manufacturing such Pills described in the joint processing application WO-00/44869.

Other forms of discrete regions are known for detergent tablets and are included herein invention, and include cores that do not pass through the entire tablet and a central region completely enclosed by a region Exterior.

Active detergent compounds

In laundry detergent tablets, active detergent compounds are suitably present in a amount between 2% or 5% up to 50% by weight, more preferably between 5% or 8% up to 40% by weight of the entire tablet. These will be more frequently anionic and non-ionic surfactants and mixtures of two. Amphoteric detergents (including ions can also be used bipolar) and less commonly cationic.

Anionic surfactant compounds

Synthetic anionic surfactants (i.e. not soapy) are well known to those skilled in the art. The anionic surfactant may comprise, in its entirety or predominantly benzene linear alkyl sulfonate of the formula

one

where R is linear alkyl of 8 to 15 atoms of carbon and M + is a solubilization cation, especially sodium.

Having the primary alkyl sulfate the formula

ROSO_ {3} {} - M +

in which R is an alkyl or alkenyl chain from 8 to 18 carbon atoms especially from 10 to 14 atoms of carbon and M + is a solubilization cation, it is also commercially significant since an anionic surfactant is can use in this invention.

Frequently, such linear alkyl sulfonate benzene or primary alkyl sulfate of the above formula, or a mixture of these will be the desired non-soap anionic surfactant and can provide 75 to 100% by weight of any non-surfactant anionic soap in the composition.

Examples of other anionic surfactants do not Soaps include olefin sulphonates; alkane sulfonates; dialkyl sulfosuccinates; and acid ester sulfonates fatty.

One or more soaps may also be included. fatty acids in addition to the non-soap anionic surfactant required. Examples are sodium soaps derived from acids fatty coconut oil, beef tallow, sunflower oil or hardened rapeseed.

Nonionic surfactant compounds

Nonionic surfactant compounds include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with oxides of alkylene, especially ethylene oxide.

Nonionic surfactant compounds specific are alkyl condensates (C 8-22) phenol-ethylene oxide, alcohol condensation products C 8-20 aliphatic primary or secondary linear or branched with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.

Especially preferred are the ethoxylates of primary and secondary alcohol, especially primary alcohols and secondary C_ {9-11} and C 12-15 ethoxylates with an average of 3 to 20 moles of ethylene oxide per mole of alcohol.

Amphoteric surfactants

Amphoteric surfactants that can be used in conjunction with anionic or non-ionic surfactants or both include amphipropionates of the formula:

\uelm{C}{\uelm{\dpara}{O}}

---NH---CH_{2}CH_{2}---

\uelm{N}{\uelm{\para}{CH _{2} CH _{2} OH}}

---CH_{2}CH_{2}CO_{2}Na

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- NH --- CH2 {CH2} ---

 \ uelm {N} {\ uelm {\ para} {CH2CH2OH}} 

--- CH 2 CH 2 CO 2 Na

where RCO is an acyl group of 8 to 18 atoms of carbon, especially acyl of coconut.

The category of amphoteric surfactants also includes amine oxides and bipolar ion surfactants, notably betaines of the general formula

two

where R_ {4} is a hydrocarbon chain aliphatic containing from 7 to 17 carbon atoms, R2 and R 3 are independently hydrogen, alkyl of 1 to 4 atoms of carbon or hydroxyalkyl of 1 to 4 carbon atoms such as CH 2 OH, Y is CH2 or CONHCH2CH2CH2CH2 (amidopropyl betaine); Z is a COO - (carboxybetaine), or of the CHOHCH2SO3 form (sulfobetaine or hydroxy sultaine)

Another example of amphoteric surfactant is an oxide of formula amine

\delm{N}{\delm{\para}{R _{4} }}

(CH_{2})_{n}---

\melm{\delm{\para}{R _{3} }}{N}{\uelm{\para}{R _{2} }}

\rightarrowOR_ {1} --- CO

 \ delm {N} {\ delm {\ para} {R 4}} 

(CH 2) n ---

 \ melm {\ delm {\ para} {R 3}} {N} {\ uelm {\ para} {R 2}} 

\ rightarrowO

where R 1 is C 10 alkyl or alkenyl C_ {20}.

R 2, R 3 and R 4 are each hydrogen or C 1 to C 4 alkyl while n is 1 to 5.

In automatic dishwasher tablets, active detergent compounds are preferably present is an amount of 5% by weight of the total composition or less.

Normally the active detergent compound is a little or no foam non-ionic surfactant, which can be an alkoxylated nonionic surfactant in which the moieties alkoxy are selected from the group consisting of ethylene oxide, oxide of propylene and mixtures thereof. This nonionic surfactant is used to improve detergency without excessive foaming, however, an excessive proportion of the surfactant should be avoided nonionic Preferably the level of non-ionic surfactant is at minus 0.1% by weight, more preferably at least 0.5% by weight.

Examples of nonionic surfactants suitable for use in automatic dishwasher tablets invention are ethoxylated linear chain alcohols that form little or no foam Preferred non-ionic surfactants are the BASF Plurafac LF series, ICI Synperonic series; Serie Lutensol® LF, from BASF Company and the Triton® DF series, from Rohm & Haas Company

Other surfactants such as anionic surfactants can be used but may require the additional presence of a antifoaming agent to prevent foaming. If a anionic surfactant is advantageously present at 2% levels by weight or less.

Detergency adjuvant

The detergent tablets of the invention contain one or more detergency builders, in addition to the additive of sodium tripolyphosphate of the invention. These adjuvants can be water soluble or water insoluble, and also includes a mixing of the two within the scope of the present invention.

Water insoluble adjuvants

Alkali metal aluminosilicates are strongly favored as water insoluble adjuvants Environmentally acceptable for washing textile material. Alkali metal aluminosilicates (preferably sodium) they can be crystalline or amorphous or mixtures of these, which have the General Formula:

0.8 - 1.5 Na_ {2} O \ cdotAl_ {2} O_ {3} \ cdot 0.8 - 6 SiO2 { xH_ {2} O

These materials contain some bound water (indicated as "xH_ {2} O") and are required to have a Calcium ion exchange capacity of at least 50 mg CaO / g. The Preferred sodium aluminosilicates contain 1.5-3.5 units of SiO_ {2} (in the previous formula). Both amorphous materials as crystals can be easily prepared by reaction between sodium silicate and sodium aluminate, as described extensively in the bibliography.

Exchange detergency adjuvants of Suitable crystalline sodium aluminosilicate ions are described, for example, in GB-1429143 (Procter & Gamble). Preferred sodium aluminosilicates of this type they are commercially available and well-known zeolites A and X, the zeolite P described and claimed in EP 384070 (Unilever) which is also called MAP zeolite, and mixtures thereof. MAP zeolite is available from Crosfields under its designation Zeolite A24.

Conceivably, the water-insoluble detergency builder could be a layered sodium silicate as described in US 4664839. NaSKS-6 is the registered trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated as "SKS-6 "). NaSKS-6 has the morphology form of
delta-Na2 SiO5 silica layered. It can be prepared by procedures such as those described in DE-A-3,417,649 and DE-A-3,742,043. Other such layered silicates, which can be used have the general formula NaMSi {O} {2x + 1} • 2 O in which M is sodium or hydrogen, x is a number between 1.9 and 4 , preferably 2, and y is a number between 0 and 20, preferably 0.

Crystalline layered silicate can be used in form of granules that also contain citric acid.

Water soluble adjuvants

Suitable organic adjuvants include the carboxylate or polycarboxylate additives containing between one and four carboxy groups, particularly selected from monomeric polycarboxylates or their acidic, acidic forms homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylate comprises at least two carboxylic radicals selected from each other by no more than two carbon atoms. The Preferred carboxylates include polycarboxylate materials described in the document US-A-2,264,103, including salts Water-soluble alkaline metal of melitic acid and citric acid (citrate), gluconic acid, dipicolinic acid, oxidisucinic acid and alkenyl succinates, glycerol mono-di-trisuccinates, carboxymethyloxysuccinates, carboxymethylximalonates, dipicolinates and hydroxyethyliminodiacetates.

Water soluble salts of polymers and polycarboxylate copolymers, such as those described herein US-A-3,308,067 are also suitable for use with the invention. Of the adjuvant materials listed In the previous paragraph, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, especially citric acid or its salt, particularly sodium citrate

Soluble detergency adjuvant salts Additional that can be used with the present invention are polyvalent inorganic and polyvalent organic adjuvants, or mixtures of these. Non-limiting examples of adjuvant salts water-soluble inorganic alkaline detergency agents include carbonates (see above), bicarbonates, borates, phosphates and polyphosphates, phosphono alkali metal carboxylates (generally sodium). Specific examples of such salts include the tetraborates, carbonates, bicarbonates, orthophosphates and sodium and potassium hexametaphosphates.

Other suitable detergency builders include organic alkaline compounds such as amino polyacetates water soluble, for example nitrilotriacetates and N- (2-hydroxyethyl) nitrilodiacetates; and you go out water soluble phytic acid, for example sodium phytates and potassium

Preferably, the total amount of adjuvants in the composition that includes the particles that contain sodium tripolyphosphate (which has a hydration water in a amount between 1% and 5% by weight and in which at least 50% by weight of the sodium tripolyphosphate inside the particles is in a way of phase I) for tablets for washing textile material is between 5 or 30 and 70% by weight, while for dishwasher tablets Automatic is between 5 or 40 and 80% by weight.

Bleaching material

The bleaching material can be incorporated preferably in the composition for use in processes according to The present invention. These materials can be incorporated into solid or encapsulated form and less preferably in dissolved form.

The bleaching material may be an agent of release of chlorine or bromine or a peroxygen compound. Without however, bleaching materials based on peroxygen for use in detergent tablets of the invention.

Inorganic peroxygen bleach

Compounds that generate inorganic peroxygen they are more preferably used as bleaching material of the present invention, and the salts (especially sodium salts) of monohydrate of perborate and carbonate tetrahydrate have been mentioned previously, and of these, sodium perborate tetrahydrate is a fully hydrated salt

Organic peroxyacids

Organic peroxyacids can be used as bleaching material. Peroxyacids suitable for use in The present invention are solid compounds and preferably substantially insoluble in water. By "substantially insoluble in water "is meant here descriptive a water solubility of less than about 1% by weight at room temperature. In general, peroxyacids organic containing at least 7 carbon atoms are what water insoluble enough to use herein descriptive

The monoperoxyacids useful herein Descriptive report include alkyl peroxyacids and peroxyacids of aryl such as peroxybenzoic acid and peroxybenzoic acids ring-substituted (for example acid peroxy-alpha-naphthoic); substituted aliphatic and aliphatic monoperoxy acids (for example peroxylauric acid and peroxystearic acid); and phthaloyl amido acid peroxy caproic (PAP).

Typical diperoxyacids useful herein Descriptive report include alkyl diperoxy acids and aryl diperoxy acids, such as acid 1,12-di-peroxy-dodecanedioic (DPDA); 1,9-diperoxyazelaic acid, acid diperoxibrasilic, diperoxisebacic acid and acid diperoxy-isophthalic; and acid 2-decyldiperoxybutane-1,4-dioic.

Chlorine and bromine bleach

Among the oxidizing materials of chlorine or bromine suitable reagents are N-bromine and N-chloro heterocyclic imides as acids trichloroisocyanuric, tribromoisocyanuric, dibromoisocyanuric and dichloroisocyanuric, and salts thereof with the cations of Water solubilization such as potassium and sodium. The compounds of hindantoin like 1,3-dichloro-5,5-dimethyl-hindantoin They are also quite suitable. Anhydrous inorganic salts water soluble and particulate are also suitable for use in the Present description as hypochlorite and hypobromite of lithium, sodium or calcium. Phosphate and trisodium chloroisocyanurates Chlorinated are also suitable bleaching materials.

Encapsulation techniques are known for both peroxygen bleach and chlorine bleach, for example as described in documents US-A-4,126,573, US-A-4,327,151, US-A-3,983,254, US-A-4,279,764, US-A-3,036,013 Y EP-A-0.436.971 and EP-A-0.510.761. However, the encapsulation techniques are particularly useful when used halogen bleaching systems.

For chlorine bleach, the compositions of the invention may comprise between 0.5% and 3% of AvCl (chlorine available). For peroxygen bleaching agents a range Suitable is between 0.5% and 3% of AvOx (oxygen available). Preferably the amount of bleaching material in the solution wash is at least 12.5 x 10-4% and at most 0.03% AvOx by weight of the solution.

Bleach activator

The detergent tablets of the present invention containing a peroxygen bleach material inorganic as sodium percarbonate or sodium perborate preferably they also contain a bleach activator. The bleach activators have been described extensively in the technique. Preferred examples include acid precursors peracetic, for example tetraacetylethylene diamine (TAED), and perbenzoic acid precursors. Bleach activators quaternary ammonium and phosphonium described in the documents US-4751015 and US-4818426 (Lever Brothers Company) are also of interest. Other type of activator bleach that can be used, but which is not a precursor to bleach, is a transition metal catalyst as it described in the documents EP-A-458397, EP-A-458398 and EP-A-549272.

It is preferred that the bleach activator be present in a different region of the tablet than the bleach, and in particular percarbonate monohydrate / metal perborate alkaline (if present). In this way you can be present in the region that contains the sodium tripolyphosphate particles which is rich in the phase I form, especially if the pill only It has two discrete regions, for example layers.

In terms of tablet composition, the bleach activator is normally present in an amount between 1 and 10% by weight of the tablet, possibly less in the case of a transition metal catalyst that can be used as 0.1% or more by weight of the tablet.

Heavy metal chelating agent

A detergent tablet of the invention It can also include a heavy metal chelating agent, which It can also act as a bleach stabilizer. Such components will also complex non-heavy metals up to a certain grade, and similarly adjuvants such as tripolyphosphate will complex heavy metals to a certain degree.

Preferred chelating agents include organic phosphonates, amino carboxylates, compounds polyfunctionally substituted, and mixtures thereof.

Particularly preferred chelating agents they are organic phosphonates such as tetramethylene phosphonate of ethylenediamine; diphosphonate hydroxy-2-phenylethyl; diphosphonate methylene; ethylene diphosphonate; hydroxy-1,1-hexylidene; 1,1-vinylidene diphosphonate; 1,1-diphosphonate 1,2-dihydroxyethane; Y 1,1-hydroxyethylene diphosphonate. Most preferred is 1,1-diphosphonate of hydroxy ethylene; acid 2-phosphono-1,2,4-butanetricarboxylic or you leave them.

Another possible chelating agent is disuccinate from ethylenediamine (EDDS).

If present, it is preferable if the level of chelating agent is between 0.5 and 3% by weight of the entire composition.
such.

Disintegrating systems

As mentioned earlier, the region of the tablet that does not include sodium tripolyphosphate rich in the form of Phase I may contain an additional disintegrating system. This is particularly preferred in discrete regions that contain more than 5% active detergent compounds, which is generally the case for detergent tablets to wash textile material. The system additional disintegrant helps these regions to disperse quickly, which opposes the binder effect of the compound of active detergent

Fully hydrated salt may in fact be a disintegrant itself, or be part of a disintegrating system.
tea.

Suitable disintegrants may be preferably present in the region as at least 15 or 20% in weight of the region, possibly at least 25% up to 50 or 60%.

Suitable disintegrants can be grouped into the following classes: swelling disintegrants (physical); effervescent disintegrants; and high solubility materials.

Swelling disintegrants

Swelling disintegrants include organic materials such as starches, for example corn starches, rice and potato and starch derivatives, such as Primojel ™, starch of carboxymethyl and Explotab?, sodium starch glycolate; celluloses, for example, Arbocel®-B and Arbocel®-BC (beech cellulose), Arbocel®-BE (beech sulphite cellulose), Arbocel®-B-SCH (cotton cellulose), Arbocel®-FIC (pine cellulose) as well as more Arbocel® types (Arbocel®-TF-30-HG) by Messrs Rettenmaier and cellulose derivatives, for example Courlose? And Nymcel ™, sodium carboxymethyl cellulose, Ac-di-Sol ™, cellulose crosslinked modified, and Hanfloc ™, cellulosic fibers microcrystalline; and various synthetic organic polymers, notably cross-linked polyethylene glycol and polyvinyl pyrrolidone, for example Polyplasdone?, XL or Kollidon? CL.

Inorganic swelling disintegrants They include bentonite clay.

Effervescent disintegrants

Effervescent disintegrants include acids weak or acid salts, for example, citric acid (preferred), malic acid or tartaric acid, in combination with carbonate or alkali metal bicarbonate; these can be used properly in an amount between 1 and 25% by weight, preferably between 5 and 15% in weight. Additional examples of sources of acid and carbonate and Other effervescent systems can be found in Pharmaceutical Dosage Forms: Tablets, Volume 1, 1989, pages 287-291 (Marcel Dekker Inc, ISBN 0-8247-8044-2).

Highly soluble materials

Very water soluble materials, which are a of the two possibilities are compounds, especially salts, with a solubility at 20 ° C of at least 50 grams per 100 grams of Water.

A solubility of at least 50 grams per 100 grams of water at 20 ° C is an exceptionally high solubility: many materials that are classified as water soluble are less soluble than this.

Some very water soluble materials that they can use are listed below, with their solubilities expressed as grams of solid to form a saturated solution in 100 grams of water at 20 ° C.

       \ newpage
    

Material Solubility in water (g / 100 g) Sodium Citrate Dihydrate 72 Potassium carbonate 112 Urea > 100 Sodium Acetate Trihydrate 76 7H2 O magnesium sulfate 71 Potassium acetate > 200

Particularly preferred materials are sodium acetate trihydrate and sodium citrate dihydrate. As different disintegrants are found in different regions of the pills, the pills can maintain the sequential release of the components of the tablet in the washing solution. By putting different types of component in different regions, said pill may be able to first provide assets of detergent, and then fabric softeners.

Additional examples of disintegrants that they fall into the previous categories, particularly swelling disintegrants, are known for use in tablets Pharmacists

Silica material for automatic dishwasher tablet

Dishwasher tablets may contain preferably silica material. The appropriate forms of silica include amorphous silica, such as precipitated silica, pyrogenic silica and silica gels, such as hydrogels, xerogels and aerogels, or pure crystal forms of quartz, tridymite or cristobalite, but it They prefer amorphous forms of silica. The right silicas are They can easily get commercially. They are marketed, by example under the registered trademark Gasil 200 (of Crossfield, United Kingdom).

Preferably, the silica is in the product in such a form that can be dissolved when added to the solution washing Therefore, the addition of silica by means of adding silica and oil antifoaming particles of sylicon.

The particle size of the silica material of the present invention may be of importance, especially if believe that any silica material that remains undissolved During the washing procedure, it can be deposited on the glass at a later stage. Therefore, it is preferred that the material of silica that is used has a particle size (as determined with a Malvern Laser, ie "particle size aggregates ") of at most 40 µm, more preferably as maximum 30 µm, more preferably maximum 20 µm Provides better washing results. In view of the incorporation into a cleaning composition, it is preferred that the particle size of the silica material is at least 1 µm, more preferably at least 2 µm, and most preferably at minus 5 µm.

Preferably, the main particle size of the silica is generally less than about 30 nm, in particular is less than about 25 nm. Preferably, the elementary particle size is less than 20 nm or even 10 nm. There is no critical lower limit of particle size elementals; the lower limit is governed by other factors As the manufacturing mode. In general the available silicas commercially they have elementary particle sizes of 1 nm or plus.

Preferably the silica material is present in the wash solution at a level of at least 2.5 x 10-4%, more preferably at least 12.5 x 10-4%, more preferably at least 2.5 x 10-3% by weight of the solution of washing and preferably at most 1 x 10 -1%, more preferably at most 8 x 10 -2%, more preferably as maximum 5 x 10 -2% by weight of the wash solution.

Preferably, the level of silica material dissolved in the solution is at least 80 ppm, more preferably at at least 100 ppm, most preferably at least 120 ppm and preferably at most 1,000 ppm. Be warned that so that the silica material be effective, the lower level of material dissolved silica depends on the pH value, that is, at pH 6.5, the level is preferably at least 100 ppm; at pH 7.0 preferably at least 110 ppm; at pH 7.5 preferably at least 120 ppm; at pH 9.5 preferably at least 200 ppm; at pH 10 preferably at least 300 ppm; at pH 10.5 preferably at least 400 ppm

Preferably, the silica material is present in the cleaning composition at a level of at least 0.1%, more preferably at least 0.5%, most preferably at least 1% by weight of the cleaning composition and preferably as maximum 10%, more preferably maximum 8%, most preferably at most 5% by weight of the composition cleaner.

Silicates

The composition of the invention comprises optionally alkali metal silicates. Metal silicate alkaline has some detergency adjuvant properties, and in Particular for automatic dishwasher can provide a ability to adjust pH and corrosion protection of metals and against attack on dishes, including advantages for delicate glassware and porcelain. The presence of such silicates Alkali metal in detergent tablets can be advantageous by providing corrosion protection of the parts of metal in washing machines, and also in helping the detergency adjuvant and in adjusting the alkalinity of the wash solution.

If there are silicates present in the tablets for automatic dishwasher, are preferably included in one level between 1 and 30%, preferably between 2% and 20%, more preferably between 3% and 10%, depending on the weight of the composition.

In tablets for washing textile material, the Preferred amounts of silicate are between 1 and 6% by weight, which is can be achieved by base powder or by dosing later.

The ratio of SiO2 to metal oxide alkaline (M 2 O, where M = alkali metal) is normally between 1 and 3.5, preferably between 1.6 and 3, more preferably between 2 and 2.8. Preferably, the alkali metal silicate is hydrated, having between 15% and 25% water, more preferably, between 17% and 20%.

Generally, metasilicates can be used very alkaline, although alkali metal silicates hydrated less alkalines having a SiO2: M2O ratio between 2.0 and 2.4 are, as indicated, greatly preferred. The forms anhydrous alkali metal silicates with a ratio of SiO 2: M 2 O of 2.0 or more are also less preferred because tend to be significantly less soluble than silicates of Hydrated alkali metal that have the same relationship.

Sodium and potassium silicates are preferred, especially sodium. An alkali metal silicate Particularly preferred is a granular hydrated sodium silicate. which has a SiO2: Na2O ratio between 2.0 and 2.4 available from Ak30 PQ Corporation, it is especially preferred Britesil H20 and Britresil H24. The most preferred is a silicate of granular hydrated sodium that has a ratio of SiO2: Na2O of 2.0. While the typical forms, it is say powder and granular, of the particles of hydrated silicate they are suitable, the preferred silicate particles have a average particle size between 300 and 900 micrometers and less than 40% less than 150 micrometers and less than 5% greater than 1700 micrometers. I know particularly preferred a silicate particle with a size of average particle between 400 and 700 micrometers with less than 20% lower 150 micrometers and less than 1% greater than 1700 micrometers. The compositions of the present invention having a pH of 9 or less they will preferably be free of alkali metal silicate.

Water soluble polymeric polycarboxylic compounds

A polycarboxylic compound may be present. Water soluble in the composition, and is advantageously present in A dishwasher composition. They inhibit unwanted depositions of the cleaning solution in the material being washed, both in textile material such as crockery, and also in the parts of the machine.

These compounds are preferably homo- or co-polymers of polycarboxylic compounds, especially co-polymeric compounds in which the acidic monomer comprises two or more carboxyl groups separated by no more than two carbon atoms. You can also use the salts of these materials

The polymeric polycarboxylates particularly Preferred are copolymers derived from acrylic acid monomers and maleic acid. The average molecular weight of these polymers in the Acid form preferably varies between 4,000 and 70,000.

Other type of polycarboxylic compounds Polymers suitable for use in the composition of the invention are Polymeric polycarboxylic acid compounds with acrylic acid as the monomer unit. The average weight of such homo-polymers in the acid form varies preferably between 1,000 and 100,000 particularly between 3,000 and 10,000

Sulfonated polymers are also suitable Acrylics as described in the document EP-851022 (Unilever).

Preferably, this polymeric material is present at a level of at least 0.1%, more preferably in levels between 1% by weight and 7% by weight of the total composition.

Polymer binder

The tablets of this invention, and in particular tablets for washing textile material, may include a polymer soluble in organic water, which serves as a binder when particles are compacted into pills. This polymer can be a polycarboxylate included as a complementary binder, as mentioned above. It can be applied as a coating to some or all constituent particles before the compaction

As shown in the document EP-A-522766, said polymers can take effect to improve the disintegration of the tablet in the time of use, as well as to act as a binder for Improve the strength of the tablet before use.

It is preferred that said binder material, if is present, it must melt at a temperature of at least 35 ° C, better at 40 ° C or higher, which is above the temperature atmosphere in many temperate countries. For use in warmer countries it will be preferred that the melting temperature is somewhat higher than 40 ° C, so that it is above room temperature.

For convenience the melting temperature of binder material must be less than 80 ° C.

Preferred binder materials are synthetic organic polymers of appropriate melting temperature, especially polyethylene glycol. Weight polyethylene glycol Medium molecular 1500 (PEG 1500) melts at 45 ° C and has been shown suitable. You can also find higher weight polyethylene glycol molecular, notably 4000 or 6000. Other possibilities are polyvinylpyrrolidone, and acrylate polyacrylates and copolymers water soluble.

The binder can be applied properly on the particles by spraying, for example as a solution or dispersion. It can be applied to particles that contain an organic surfactant. As an alternative, the binder will it can provide in a powdered form, and it can be dispersed in the composition to make pills. If used, the binder is used preferably in an amount within the range between 0.1 and 10% by weight of the tablet composition, more preferably the amount is at least 1% or even at least 3% by weight of the pills Preferably the amount is not more than 8% or even 6% by weight unless the binder serves any other function.

Enzymes

The detergent tablets of the invention they can also contain one of the detergency enzymes very known in the art for their ability to degrade and help in the removal of several spots. Suitable enzymes include the various proteases, cellulases, lipases, amylases, and mixtures of these, which are designed to remove various spots of textile materials and dishes. Examples of proteases Suitable are Maxatase (registered trademark), supplied by Gist-Brocades N. V., Delft, Holland, and Alcalase (registered trademark), and Savinase (registered trademark), supplied by Novo Industri A / S, Copenhagen, Denmark. Detergency enzymes they are commonly used in the form of granules, optionally with a protective coating, in an amount between 0.1% and 3.0% by weight of the composition; and these granules have no problems with regarding compaction to form a pill.

Other laundry detergent ingredients

Detergent tablets for washing material Textiles of the invention may also contain a fluorescent (optical brightener), for example, Tinopal (registered trademark) DMS or Tinopal CBS available from Ciba-Geigy AG, Basel, Switzerland. Tinopal SMS is disulfonate of 4,4'bis- (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disodium and Tinopal CBS is disulfonate 2,2'-bis- (phenyl-styryl) disodium

An antifoam material is included advantageously, especially if it is intended primarily a detergent tablet for use in automatic type washers drum with front load. Antifoam materials in form Granular are described in EP-266863A (Unilever). Such antifoam granules normally comprise a mixture of silicone oil, petrolatum, hydrophobic silica and phosphate of alkyl as an antifoam active material, absorbed on a carbonate-based, water-soluble inorganic carrier material, absorbed and porous. Antifoam granules may be present in an amount of up to 5% by weight of the composition.

Additional ingredients that can be optionally use in the detergent tablet for washing textile material of the invention include agents of anti-redeposition as carboxymethyl cellulose of sodium, linear chain polyvinyl pyrrolidone and ethers of cellulose such as methyl cellulose and ethyl hydroxyethyl cellulose agents fabric softeners; heavy metal inhibitors like EDTA; perfumes; and colored dyes or cues.

Other dishwashing detergent ingredients

Anti-stain agents such as benzotriazole and those described in the document EP-723577 (Unilever) can be included in tablets of dishwashing detergent of the present invention.

The optional ingredients in the pills dishwashing detergent are, for example, buffers, agents reducers, for example, borates, alkali metal hydroxide and well-known enzyme stabilizers such as polyalcohols, for example glycerol and borax; descaling agents; inhibitors of crystal growth, threshold agents; thickening agents; Perfumes and dyes.

The reducing agents can be used, for example, to avoid the appearance of a deactivating concentration of oxidizing bleaching compound enzyme. The right agents include sulfur-oxy reducing acids and salts of these. Most preferred for reasons of availability, low cost and great performance are the alkali metal and ammonium salts of sulfuroxy acids that include ammonium sulphite ((NH 4) 2 SO 3), sodium sulphite (Na 2 SO 3), sodium bisulfite (NaHSO 3), metabisulfite sodium (Na 2 S 2 O 3), potassium metabisulfite (K 2 S 2 O 5), lithium hydrosulfite (Li 2 S 2 O 4), sulfite being particularly preferred sodium Another useful reducing agent, although not particularly Preferred for reasons of cost, it is ascorbic acid. The amount of reducing agents to use may vary from case to case depending the type of bleach and the way it is, but usually a range of 0.01% and 1.0% by weight will suffice, preferably between 0.02% and 0.5% by weight.

Particle size and distribution

The discrete regions of a pill of detergent of this invention are each a matrix of particles compacted Preferably the particulate composition has a average particle size in the range between 200 and 2000 µm, more preferably between 250 and 1400 µm. Fine particles, less than 180 µm or 200 µm can be removed by screening before tablet formation, if desired, although We have observed that this is not always essential.

While the particulate composition of heading may in principle have any apparent density, the present invention is especially relevant for tablets manufactured in the compaction of powders of apparent density relatively high, due to its greater tendency to show problems of disintegration and dispersion. Such pills have the advantage that, compared to a tablet derived from a low powder apparent density, a given dose of composition as in a smaller pill.

Thus the particulate composition of heading can adequately have an apparent density of at least 400 g / liter, preferably at least 500 g / liter, and perhaps at least 700 g / liter

Granular detergent compositions of great bulk density prepared by granulation and densification in a high speed mixer / granulator, as described and claims in documents EP-340013A (Unilever), EP-352135A (Unilever), and EP-425277A (Unilever), or through the procedures of continuous granulation / densification described and claimed in the EP-367339A (Unilever) and EP-390251A (Unilever), are inherently suitable for use in the present invention.

You can also use a base powder dried by spray, and this results in a dust that can be given form of tablets that have an apparent density between 600 and 700 g / liter

Porosity

The particle compaction stage reduces The porosity of the composition. Porosity is expressed conveniently as a percentage of volume that is air.

The air content of a tablet or region of tablet can be calculated from the volume and weight of the tablet or region, provided that the free air density of the content solid be known. The latter can be measured by compressing a empty material sample with a very large applied force, then measuring the weight and volume of the resulting solid.

The percentage of air content of the tablet or region of a tablet varies inversely with the pressure applied to compact the tablet composition while the resistance of the tablet or region varies with the pressure applied to cause compaction In this way the higher the pressure of compaction, the stronger the pill or region will be but it will be smaller the volume of air inside them.

The invention can be applied when compacted. a particulate detergent composition to provide Pills with a wide range of porosities. Specifically included among the possible porosities is a porosity of up to 38% air volume, for example between 10 or 15 better than 25% up to 35% air by volume in the tablet.

Density and size of the tablet

The size of a pill will vary appropriately between 10 and 160 grams, preferably between 15 and 60 g, depending of the conditions of preferred use, and if it represents a dose for a medium load in a washing of textile or dishwasher automatic or a fractional part of such dose. In particular, a Automatic dishwasher tablet is preferably 15 to 30 g. The pills can be any way. However, for packing them more easily are preferably section blocks substantially uniform transverse, such as cylinders or cuboids. The overall density of a tablet is preferably in a range between 1040 or 1050 g / liter, possibly 1100 g / liter, up to 1450 g / liter or 1700 g / liter, or more. The density of the tablet can be in a range of up to between 1350 and 1400 g / liter for a tablet for washing textile material and in an interval between 1300 and 1600 g / liter for an automatic dishwasher tablet.

The embodiments of the present invention will be they will now describe by way of example only.

Example 1

42 g of detergent tablets were prepared cylindrical having the following formulations in a machine to make Fette rotary table pads. They were manufactured two tablets of the invention with two layers, containing the most thick of them Rhodiaphos HPA 3.5, the other tetrahydrate of sodium perborate or sodium acetate trihydrate. The thickest layer it was 75% of the tablets (31.5 g), the thinnest layer 25% (9.2 g). Two comparative tablets were made that have only one layer, but they have the same composition as the two tablets layers. All the pills contained the same base powder, which had The following formulation.

Component % in weigh Na-LAS 23.55 Non-ionic surfactant 10.42 Soap 0.72 AA / AM Copolymer (70:30) 3.22 Sodium Tripolyphosphate (adjuvant) 40.63 Sodium silicate 8.63 Methyl cellulose carboxy from sodium 0.67 Humidity 12.15 Total 100.00

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

(Table goes to page next)

3

The resistance of the pills, in their condition dry, as manufactured in the press, was determined as the strength, expressed in Newtons, which is needed to break the pill, measured using an Instron type universal test instrument to apply a compressive force on a diameter (i.e. perpendicular to the axis of the cylindrical pad).

The speed of disintegration of the tablet detergent was evaluated by means of the "water grid test Quiet ": the pill is placed on a metal rack of 10 x 9 cm with a mesh size of 1.2 x 1.2 cm and placed in a glass of precipitates containing 1 liter of calm water at 20 ° C. The disintegration time was taken when 10% residue was left in the grid. The test was repeated 3 times. The results are shown. in the following table:

Tablet TO I B II Resistance (N) 35 35 35 35 Disintegration time (s) 289 ± 56 457 ± 33 117 ± 6 173 ± 2

Example 2

25 g of cuboid tablets of dishwashing detergent in a machine for making tablets Fette rotary table. Two tablets of the invention with two layers, containing the thickest Rhodiaphos HPA 3.5 and a minor part of sodium perborate tetrahydrate, the rest the largest proportion (or all) of your salt. The thickest layer was 75% of the tablet, the thinnest layer 25%.

A comparative tablet was made that has a only layer, but it has the same composition as the tablets two respective layers.

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

(Table goes to page next)

4

Claims (15)

1. A detergent tablet of compressed particulate composition comprising an active detergent compound, a detergency builder, particles containing sodium tripolyphosphate with a phase I form content that is more than 40% by weight of sodium tripolyphosphate in said particles, at least one salt that is completely hydrated, and optionally other detergent ingredients, wherein the tablet comprises a plurality of discrete regions, characterized in that in one or more of the discrete regions containing said particles containing sodium tripolyphosphate there are less than 10% by weight of that region of fully hydrated salts, and there is at least one discrete region that contains at least 10% by weight of that region of fully hydrated salts. 2. A detergent composition according to the claim 1, wherein the fully hydrated salt is select from a carbonate, perborate, sulfate, thiosulfate, acetate or citrate, or a mixture of these. 3. A detergent tablet according to the claim 2, wherein the fully hydrated salt is select between a salt or persal of sodium. 4. A detergent tablet according to a any of the preceding claims, wherein the salt fully hydrated has a solubility at 20 ° C of at least 50 g per 100 g of water. 5. A detergent tablet according to a any of the preceding claims, wherein the sodium tripolyphosphate in said particles contains water of hydration in an amount between 1% and 5% by weight of that sodium tripolyphosphate. 6. A detergent tablet according to a any of the preceding claims, wherein said regions containing said particles containing sodium tripolyphosphate do not contain salts completely hydrated 7. A detergent tablet according to a any of the preceding claims, wherein the sodium tripolyphosphate in said particles has a content of the phase I form which is at least 50% by weight of the tripolyphosphate of sodium in said particles. 8. A detergent tablet according to a any of the preceding claims wherein the amount of hydration water in sodium tripolyphosphate particles is in a range between 2% and 4% by weight of the tripolyphosphate of sodium in those particles. 9. A detergent tablet according to a any of the preceding claims wherein the amount of sodium tripolyphosphate is less than 70% by weight of the composition global. 10. A detergent tablet according to a any of the preceding claims, wherein the region which contains at least 10% by weight of the salts completely hydrated contains a disintegration system that does not incorporate said particles containing said sodium tripolyphosphate. 11. A detergent tablet according to the claim 10, wherein the disintegrant is a disintegrant of swelling 12. A detergent tablet according to the claim 10, wherein the disintegrant is a disintegrant effervescent. 13. A detergent tablet according to the claim 10, wherein the disintegrant is a material of great water solubility. 14. A detergent tablet according to a any of the preceding claims wherein the particle contains between 2 and 40% by weight of detergent compound active and between 5 and 70% by weight of detergency adjuvant. 15. A detergent tablet according to a any one of claims 1 to 13, wherein the particle Contains less than 5% by weight of active detergent compound and between 5 and 70% by weight of detergency adjuvant.