DE60224007T2 - CLEANING COMPOSITIONS - Google Patents

Description

Field of the invention

These This invention relates to cleaning compositions in the form of Tablets. Such tablets are said to dissolve when incorporated into water are and are therefore for the individual consumption provided. The tablets can be used for Use in dishwashing, when washing fabrics or other cleaning applications be.

Background of the invention

Products in tablet form have opposite powdered products have several advantages: for example, you have to do not measure and are therefore easier to handle and in the wash load to distribute, and they are more compact, allowing economic storage facilitated.

Detergent compositions in tablet form intended for laundering have been described in a variety of patent documents, e.g. GB 911,204 ; EP-A-711827 . WO-98/42817 ; US 5,360,567 and WO-99/20730 (all Unilever), US 3,953,350 (Kao) DE 19 637 606 (Henkel) and are currently being sold commercially. The tablets of a composition suitable for dishwashing are, for example, in EP-A-318204 . WO-96/23530 and US-A-5691293 and sold commercially.

The Tablets from a cleaning composition will generally by compressing or compacting a composition in particulate Mold made. Although it is desirable that the Tablets an adequate Have firmness when dry, and they spread quickly and dissolve should, when contacted with water, it can be difficult to achieve both properties at the same time.

Tablets formed using a low compaction pressure could crumble or disintegrate during handling and packaging; while tablets compressed with more force may be sufficiently cohesive, but then disintegrate or disperse to an adequate extent in the wash. Tableting is often done with enough pressure to compromise these desirable but conflicting properties. However, there remains a desire to improve either of these properties without adversely affecting the other in order to improve the overall compromise between them. US-A-3018267 (Procter & Gamble) taught that the force, and therefore the pressure, of compressing a composition into tablets should be limited or else the tablets take too long to disintegrate.

If a tablet may contain an organic surfactant this act as a binder that softens the tablet. However, it may also delay disintegration of the tablet by: It forms a viscous gel when the tablet is in contact with water comes. Therefore, the presence of a surfactant may be more difficult make both a good strength and disintegration speed to achieve: it has been proven that this problem in particular for tablets formed by compression of powders, the one surface-active Contain funds and with non-soluble Builders such as sodium aluminosilicate (zeolite) have been built, is acute.

It is known to include materials whose function is to increase the disintegration of the tablets when they are introduced into wash water. Some tablets that are sold commercially contain urea for this purpose. EP-A-711827 (Unilever) teaches for this purpose the use of sodium citrate and EP-A-838519 (Unilever) teaches the use of sodium acetate trihydrate for this purpose. A variety of documents have taught that the disintegration of tablets from a cleaning composition can be accelerated by the inclusion of a quantity of a water-insoluble but water-swellable material in the tablet which serves to disintegrate the tablet when placed in water at the time of use , Such documents include WO-98/40462 (Rettenmaier), WO-98/55583 (Unilever) and WO-98/40463 (Handle).

typical water swellable agents acting as potential tablet disintegrating agents have been disclosed are strengths, Cellulose and cellulose derivatives, alginates, dextrans, cross-linked polyvinylpyrrolidones, Gelatins and Formaldehydkasein as well as numerous minerals and certain ion exchange resins.

These water-swellable agents often have no function in laundry washing except to promote tablet disintegration. Furthermore, due to their insolubility and relatively large particle size, they usually settle on the fabric during the wash. Several attempts have been made to minimize the deposition problem, for example by combining the water-swellable, water-insoluble disintegrator with a second, very soluble disintegration aid ( WO-98/55582 ). Other attempts included the use of a preferred particle size of the disintegrator. WO-98/55583 (Unilever) claims the use of such a material having a particle size of at least 400 microns to achieve more efficient disintegration. WO-98/55575 and DE 199 01 063 (both handles) teach the use of cellulose disintegration aids having a particle size of less than 100 microns to minimize deposition. For DE 199 01 063 For example, the cellulosic material is mixed with a material having a given oil absorption capacity containing some zeolites.

We found out that two different dimensions the tablet strength for relevant to a consumer's characteristics are. The power to break is a direct assessment of Strength and shows the resistance of the tablet against the Breaking down when viewed by a consumer at the time of use is used. The amount of energy (or mechanical work) that before fracture is a measure of tablet deformability and is relevant for the resistance of the tablet against breaking during the Transport. Both properties are for consumer perceptions relevant to the tablet: for Consumers need Keep pills firmly enough to handle them, stay whole and yourself fast and complete disintegrate at the time of use.

It the need remains for a cleaning composition in the form of a Tablet, which has adequate strength has when it is dry (so that it resists handling) and which disperses / dissolves in an acceptable time if it is contacted with a washing medium such as water. It There is a special need for a tablet, which further no undesirable residues on the cleaned substrate and in particular one, which retains good disintegration properties even during storage.

Summary of the invention

We have a surprise found out that a Cleaning composition in the form of a tablet containing one or more to address several of the aforementioned problems can, if disintegrator grains, the a co-granulated mixture of a swelling clay, a water-insoluble comprising inorganic material and a water-swellable agent, be added to a cleaning composition before they a tablet is formed. It has been found that this too acceptable low levels of residues on the substrate, the treated with the tablet and / or with the tablets, resulting in good disintegration properties are retained during storage.

DE 199 15 321 (Henkel) and EP 1 048 719 (Procter & Gamble) disclose disintegrator or plasticizer grains of compressed clay. JP 10110199 (Kao) discloses detergent tablets comprising porous silica and kaolin clay material as separately added ingredients.

Therefore The present invention provides a tablet of a compressed, particulate A detergent composition comprising a non-soap surfactant Agent and a builder, wherein the tablet or a single Range of disintegrator grains, comprising water-swellable clay, a water-insoluble inorganic material and a water-swellable agent.

Especially preferred water-insoluble inorganic materials are silica or crystalline aluminosilicates.

A particularly preferred embodiment In the present invention, a tablet is made from a compressed, particulate A detergent composition comprising a non-soap surfactant and a builder, wherein the tablet or a single area of which disintegrator grains, comprising water-swellable clay, a water-insoluble inorganic material and a water-swellable agent, that in its anhydrous Condition not more than 20 wt .-% of the combined weight of the water-swellable Clay, the water-insoluble inorganic material and the water-swellable agent.

The present invention also provides a method of making a tablet from a compressed particulate detergent composition comprising a non-soap surfactant and a detergency builder, the process comprising mixing disintegrator grains comprising a water-swellable clay, a water-insoluble inorganic material and a water-swellable agent with other ingredients of the detergent composition to make a particulate detergent composition, placing a certain amount of the resulting particulate detergent composition in a mold, and compressing the composition in the mold to make the tablet.

By the inclusion of a Disintegrator grain produced by the cogranulation of a water-swellable clay, a water-insoluble inorganic material and a water-swellable agent formed into a detergent tablet comprising a non-soap surfactant Medium and a builder, is a surprisingly good disintegration after storage of the tablets and / or acceptable residue obtained on a substrate. It is believed that if the water-swellable clay, the water-insoluble, inorganic material and the water-swellable agent is used in this cogranulated form be, this in the promotion The disintegration of the tablet is more efficient than if the components added separately to the composition.

Provided Unless otherwise specified, all amounts are based on the weight.

Full description

to shape of this invention, including preferred and optional features, and materials used can be will now be more detailed discussed.

A Tablet of the present invention may be either homogeneous or heterogeneous be. In the present specification, the term "homogeneous" is intended to refer to a tablet suggest by compressing a single particulate composition However, it does not imply that all particles of the composition to have the same composition. The term "heterogeneous" is intended to refer to a tablet indicate that from a variety of individual areas, for example Layers, inserts or coatings, consists of compressing each one out a particular Composition were obtained. In a heterogeneous tablet according to the present invention Invention, each individual area of the tablet is preferred Have a weight of at least 5 g.

Provided unless otherwise stated, all references refer to percentages herein by weight, based on the total weight of the Tablet or area of it.

disintegrant

A Detergent (cleaning) tablet of a compressed, particulate detergent composition, comprising a non-soap surfactant Agent and a builder, according to the present invention comprises a disintegrator in the form of granules, the disintegrator grains having a swelling tone, a water-insoluble inorganic material and a water swellable agent.

By "water-insoluble" as used herein is a compound with respect to the inorganic material solubility in water at 25 ° C less than 5 grams per 100 grams of water, preferably less than 1 gram per 100 grams of water, to understand.

A Variety of clays is known as swelling clay. The term "swelling" as used herein refers to the ability the layered clay structure to swell on contact with water or to expand, that is, the particle size of a Clay particle increased significant when in contact with water. Swelling clay for use in this invention, three-layered ones include Quelltone, which are materials that geologically classified as smectites become.

There are two different classes of smectite clays. In the first, alumina is present in the silicate crystal lattice; in the second class, magnesium oxide is present in the silicate crystal lattice. The general formulas of these smectites are Al ₂ (Si ₂ O ₅ ) ₂ (OH) ₂ and Mg ₃ (Si ₂ O ₅ ) (OH) ₂ for the aluminum and magnesium oxide clays, respectively.

The range of water of hydration in the clay may vary with the processing to which it is subjected. Such processing does not significantly affect the source characteristics of the hydrated clays, as this is dictated by the silicate lattice structure. Further, atomic substitution by iron and magnesium may occur in the crystal lattice of the smectites, while metal cations such as Na ⁺ , Ca ²⁺ and H ^{+ may} also occur in water of hydration may be present to provide electrical neutrality.

The three-layer aluminosilicate source clays useful in the invention are further characterized by a dioctahedral crystal lattice, while three-layered magnesium source silicates a trioctahedral crystal lattice to have.

The Clays used in the invention may contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions and magnesium ions contain. Usually Clays are based on a predominantly or exclusively absorbed Cation differentiated. For example, a sodium tone is one in the absorbed cation is predominantly sodium. Such absorbed Cations can in exchange reactions with cations present in aqueous solutions be.

Especially Suitable smectite clays include montmorillonite and hectorite clays. A class of naturally occurring ones Montmorillonite clay is known as the bentonite clay, and it is found out that these are particularly useful in the present invention. They are different Forms of bentonite clays are known in which the inherent negative Charge the clay matrix balanced by different cations becomes. The course occurring forms, where the cation is predominantly either sodium (sodium) or Calcium (calcium) is suitable as the material passes through the Treatment of calcium bentonite with a sodium compound and with other cations is produced.

The smectite clays used in the present invention are commercially available. Such clays include, in addition to the above-mentioned saponite, wolchonskoite, nontronite and sauconite. Suitable clays are available under various trade names, such as GELWHITE ^™ GP, Bentonite L, H and MB, all from Southern Clay, USA; Clays available under the brand name VOLCAY ^™ from American Colloid Co., USA. Other suitable clays are commercially available. The smectite minerals available from these commercial and brand names may include mixtures of various individual mineral elements. Such mixtures of the smectite minerals are suitable for use in the invention.

A preferred bentonite clay is a bentonite clay in calcium form which has been treated with a sodium compound. An example is a calcium form of bentonite clay which has been treated with sodium carbonate and sold under the trade names BREBENT ^™ and FLUGEL ^™ (ex Laporte PLC). The weight average particle size of these clays is between 5 and 25 microns when measured with a Malvern Mastersizer using the method described hereinafter. These clays contain relatively high levels of sodium, for which reason they are called "calcium-form" clays. It has been found that calcium clays according to the present invention are particularly suitable.

It has been found to be smaller Particle sizes in terms to arrears to cause less problems on the substrate.

The weight average particle size of the materials used in this invention is determined using a Malvern Mastersizer Model X, with a lens range of up to 300 mm RE and an MS 17 sample presentation unit. This device, manufactured by Malvern Instruments, Malvern, England, utilizes the principle of Mie scattering using a low-energy HE / NE laser. Prior to measurement, the sample is initially dispersed with ultrasound in water for seven minutes to form an aqueous suspension. This suspension is stirred before being measured using the 300 mm RF lens in the detector system as described in the operating manual for the instrument. The Malvern Mastersizer measures the weight average particle size distribution of the inorganic or reference material. The weight average particle size (d ₅₀ ) or 50 percentile is readily available from the data generated by the instrument.

Smectite clays with neutral or white Color are to form the Desintegratorkorns, especially for neutral colored Detergent tablets preferred.

It has been found that clays having a Na ₂ O content of less than about 4% by weight and a Ca ₂ O content of less than about 1.5% by weight are effective according to the present invention.

Suitable water-insoluble inorganic materials include silica, aluminosilicates, aluminas, calcium carbonate, barium sulfate, titanium dioxide and pigments. Preferred water-insoluble materials are silica, materials consisting of at least 70% by weight of silica, and alumosi silicates.

The Alumosilicate is preferably a crystalline aluminosilicate, usually a zeolite, especially a zeolite, suitable for use in a detergent formulation suitable is. helpful Zeolites include zeolite P, A, X and Y and mixtures thereof, wherein Zeolite P and zeolite A are preferred. Zeolite P is particularly preferred. It has been found that one type of zeolite P, known as maximum aluminum zeolite P (eg DOUCIL A24 from Ineos Silicas, UK), is particularly effective, and it is referred to herein as zeolite MAP designated.

In general, the empirical formula of a zeolite is: M 2 / n O. Al 2 O 3 .xSiO 2 yH 2 O, where M represents a metallic cation of valency n, x indicates the ratio of atoms of silica to atoms of aluminum, and y indicates the ratio of molecules of water to atoms of aluminum. Many different types of zeolite with varying ratios of silica to alumina are known. Usually, M is an alkali metal.

zeolites for use in this invention, the structure of any have known zeolite. The structure and features of many Zeolites are used in the standard work "zeolite Molecular Sieves" by Donald W. Brock, published by Robert E. Krieger Publishing Company. Usually lies the value of x in the above empirical formula is in the range of 1.5 to 10. The value of y, which represents the amount of water in the cavities of the zeolite can vary in a wide range. In an anhydrous material y = 0 and in a fully hydrated Material can be up to 5 y.

Zeolites useful in this invention can be based on naturally occurring or synthetic aluminosilicates and the preferred forms of zeolite have the structure known as zeolite P, zeolite X or zeolite A. Particularly preferred forms of zeolite are those described in U.S. Pat EP-A-0 384 070 . EP-A-565,364 . EP-A-0 697 010 . EP-A-0 742 780 . WO 96/34828 and WO 97/06102 be revealed. The zeolite P, which is in EP-A-0 384 070 has the empirical formula given above, wherein M represents an alkali metal cation and x has a value of up to 2.66, preferably in the range of 1.8 to 2.66 and has a structure which is particularly useful according to the invention and is known as maximum aluminum zeolite P as described above.

It It has been found that granular disintegrators of the invention are more effective when the zeolites used to make them used to contain relatively little water. The preferred Amount of water in the zeolite depends from the type of zeolite used. For the zeolites A and P is the amount of water is preferably less than 21% by weight of the zeolite, stronger preferably less than 15 wt .-%, in particular 8 to 13 wt .-%, such as 9 to 12 wt .-%. A particularly useful form of zeolite P, containing about 9 to about 12% by weight of water is zeolite MAP. If the Water content in zeolite P over As this range increases, its effectiveness diminishes as a disintegrator with the rising water content. It has been found that fully hydrated Zeolite P is less effective compared to zeolite MAP as a disintegrator is.

According to the invention For example, the zeolite used as the inorganic carrier preferably has one Volume increase upon contact with water at 20 ° C.

The relative amount of water-swellable clay and water-insoluble, inorganic material, in particular the crystalline aluminosilicate, in the granular Desintegrator is preferably in a weight ratio of 9: 1 to 1 : 9, stronger preferably 6: 1 to 1: 5, such as 2: 1 to 1: 4, based on the Weight of the clay: inorganic material. Good results are with circumstances in the range of 1.5: 1 to 1: 3, based on the weight of water-swellable Clay: inorganic material, obtained.

Of the water-swellable clay is preferred in the disintegrator grain in one Amount of 10 to 50 wt .-%, preferably 20 or 25 to 45 wt .-%, such as 30 to 40 weight percent, based on the weight of the disintegrator grain, available. The water-insoluble, Inorganic material is preferably in an amount of 35 to 80 Wt .-%, preferably 45 to 70 wt .-%, such as 50 to 60 wt .-%, based present on the weight of the disintegrator grain. The water-swellable Agent is preferably in an amount of 1 to 10 wt .-%, preferably From 3 to 9% by weight, such as 5 to 9% by weight, based on the weight of the Desintegrator grain available.

Alkali metal, especially zeolites, are commonly used in detergency compositions as detergency builders, such as further described hereinafter. If a composition according to the invention an alkali metal aluminosilicate is used as a builder preferably at least a portion of the detergency builder of the cleaning composition used as the aluminosilicate material in the disintegrator grains. As indicated below the detergency builder, for example the aluminosilicate component, is typically 10 to 60% by weight of the total composition. When zeolite in the disintegrator grains and is used as a builder in the composition, preferably comprises at least 1% by weight of the total weight of the composition Zeolite component used in the form of disintegrator grains becomes.

Prefers have the water-insoluble, inorganic materials have a primary average particle size below 10 μm and stronger preferably, the average particle size is less than 5 μm, as using measured by a Malvern Mastersizer (brand name).

Especially Preferably, the disintegrator grains comprise a water-swellable agent, in its anhydrous state, not more than 15% by weight, more preferably not more than 10% by weight, most preferably not more than 8% by weight, such as 7.5% or less of the combined Weight of swelling clay, water-insoluble, inorganic material and the water-swellable agent in the granular disintegrator. In general comprises at least 1% of the combined weight of the swelling clay, of the inorganic material and the water-swellable agent in the granular disintegrator water-swellable Medium. Preferably comprises the water-swellable agent is 1-8% by weight of the combined weight of swelling clay, inorganic material and water swellable Agent.

Surprisingly may be a relatively small amount of the water-swellable agent in the tabletted composition of the invention may be used while still always acceptable properties in the tabletted composition to be provided. For usually is the amount of water swellable agent in the tableted composition, based on the total weight of the tabletted composition less than 2% by weight, preferably less than 1% of the composition. They are usually however, at least 0.2% by weight of the water-swellable agent, based on the total weight of the tabletted composition.

Typically, the water-swellable agent comprises a polymer, often a wholly or partially crosslinked polymer, e.g. Natural cellulose, cross-linked cellulose, (sodium) carboxymethylcellulose, cross-linked sodium carboxymethylcellulose, swellable starch, cross-linked starch or cross-linked polyvinylpyrrolidone. Currently preferred are Aquasorb A500 (from Hercules) and Ac-Di-Sol ^™ and Nilyn ^™ XL 90 (from FMC Corporation, USA).

The water-swellable agent in the disintegrant grain is preferably a crosslinked carboxymethyl cellulose such as Aquasorb ^™ A500 and Ac-Di-Sol ^™ and Nilyn ^™ XL 90, as mentioned above. Crosslinked sodium carboxymethyl cellulose is particularly preferred. It is believed that these crosslinked carboxymethylcelluloses for use in the present invention have particularly suitable levels of crosslinking and / or degree of substitution.

in the In general, the compositions of the invention will be 1 to 20 % By weight of the disintegrator grains, based on the total weight of the compositions, preferred 1 or 2 to 15 wt .-%, such as 3 to 10 wt .-%, z. B. 4 to 8 wt .-% the disintegrator grains contain. If the grains rather to promote the resolution The tablets can be introduced as disintegration, the amount the grains in the tablets then 1 wt .-% amount.

The Water-swellable agent preferably has an average primary particle size of up to to 600 μm, Conveniently however, an average primary particle size of not more than 200 μm, preferably not more than 100 microns.

The water-swellable agent preferably has a water swelling capacity of at least 5 cm ³ / g, preferably 10 cm ³ / g and more preferably 20 cm ³ / g as in the test described below determined.

The disintegrant preferably have an average particle size in the range of 250 to 1500 Micrometer, stronger preferably 500 to 1200 microns, most preferably 700 to 1200 Micrometers.

The grains of the swelling clay, the water-insoluble inorganic material and the water-swellable Agents are produced in a preferred embodiment by a dry granulation process. A typical known method for producing inorganic material grains involves mixing the inorganic material with water or an aqueous liquid, stirring the wet mixture until grains form and then removing water from the grains. In the dry granulation process of the present invention, the granules are prepared without the use of water or an aqueous liquid. The dry granulation process may be any process known to those skilled in the art, for example mixing the dry ingredients in a blender (such as a Pek mixer, available from George Tweedy & Co of Preston-281b SA Machine) and compressing on a roller compactor (Alexanderwerk WP50 - manufactured by Alexanderwerk AG, D 5630 Remscheid 1, Germany) and a Lodige mixer, available from Gebr. Lodige Maschinenbau, Paderborn, Germany, as well as low- / medium-shear mixers such as the circular screw nautamixer, available from Vrleco-Nauta, Holland or a ribbon blender such as supplied by Morton, Motherwell, Scotland. Suitable roller compactors include the Alexanderwerk WP50, manufactured by Alexanderwerk AG, Remscheid, Germany, the IR520 Chilsonator, available from the Fitzpatrick Company, Illinois, USA, and a roller compactor from Hosokawa Bepex of Minneapolis, USA.

One typical small scale Manufacturing method will now be described in detail. The swelling sound, the inorganic material and the particles from the water-swellable Means are in appropriate parts in a pek mixer for 30 minutes mixed together. A minimum of 2 kg of mixed material, produced in this way is obtained by feeding it into an Alexanderwerk roller compactor, equipped with a sinter block vacuum deaeration system, compressed. The roller pressure is selected according to the desired grain strength, wherein higher pressures to firmer grains to lead. In general, the roller pressure is between 8 and 25 MPa and a typical roller pressure is 10 MPa. The compressed material from the compressor is in a Fed granulator, which forms part of the machine, and pressed through a sieve, and the resulting grains are then set to the desired one using standard laboratory sieves particle size sieved, for example an average particle size of 250 up to 3000 μm. Preferably, the particles have a particle size of 700 to 1500 microns. The manufactured Grains include but an intimate mixture of particles of swelling clay, inorganic Material and water-swellable agent.

It has been found that a particularly effective disintegrator grain must be one that Mixture, preferably cogranulated, made from a bentonite clay by treating the bentonite in calcium form with a sodium compound, Zeolite MAP and a crosslinked sodium carboxymethylcellulose.

Surface-active compounds

The Compositions of this invention contain one or more non-soap surfactants. In a fabric washing composition, these preferably make up 5 to 50% by weight of the composition of the tablet or a portion thereof, stronger preferably 8 or 9% by weight of the composition up to 35 or 40 Wt .-% off. If the tablet consists of more than one single area, can these preferred amounts of surfactant then on Apply the tablet as a whole.

The organic surface-active Agent can act as a component in granulated particles in an amount between 10 and 70% by weight of the particles, more preferably 15 to 50% by weight, based on the total weight of the granulated particles. The whole surface-active Composition in the composition may be contained in these particles be. The surface active Agent may be anionic (soap or non-soap), cationic, zwitterionic, amphoteric, non-ionic or a combination of these.

In A tissue wash tablet may be anionic surfactant Agent in an amount of 0.5 to 50 wt .-%, preferably 2 or 4 up to 30 or 35 or 40% by weight of the tablet or range be present of it.

In a dishwashing composition can be organic surface active Average 0.5 to 8, more preferred 0.5 to 5% of the composition of the tablet or range this form and may be non-ionic surface active Agent, either alone or in a mixture with anionic surfactant Means to exist.

Synthetic (ie, non-soap) anionic surfactants are well known to one skilled in the art. Examples include alkylbenzenesulfonates, especially linear sodium alkylbenzenesulfonates with egg an alkyl chain length of C ₈ -C ₁₅ ; olefin; alkane; Dialkyl sulfosuccinates and fatty acid ester sulfonates.

Primary alkyl sulfate with the formula ROSO ₃ ^- M ⁺ wherein R is an alkyl or alkenyl chain of 8 to 18 carbon atoms, more preferably 10 to 14 carbon atoms, and M ^{+ is} a solubilizing cation is commercially important as an anionic surfactant.

worin R lineares Alkyl aus 8 bis 15 Kohlenstoffatomen ist und M⁺ ein löslichmachendes Kation ist, insbesondere Natrium, ist ebenso ein kommerziell bedeutsames anionisches oberflächenaktives Mittel.Linear alkylbenzenesulfonate of the formula

wherein R is linear alkyl of 8 to 15 carbon atoms and M ^{+ is} a solubilizing cation, especially sodium, is also a commercially important anionic surfactant.

Such a linear alkyl benzene sulfonate or primary alkyl sulfate of the above Formula, or a mixture thereof, often becomes the desired anionic surfactants May be 75 to 100% by weight of each anionic non-soap surfactant Make up in the composition. In some forms of this Invention is the amount of non-soap anionic surfactant Mean in the range of 5 to 20 or 25% by weight of the tablet or an area of it.

It may be equally desirable be to include one or more soaps of fatty acids. These are prefers sodium soaps derived from naturally occurring fatty acids, for example the fatty acids from coconut oil, beef tallow, Sunflower or hardened Rapeseed oil.

suitable nonionic surfactant In particular, compounds which can be used include the reaction products of compounds with a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, Amides or alkylphenols with alkylene oxides, in particular ethylene oxide.

Specific nonionic surfactant compounds are alkyl (C _8-22) phenol-ethylene oxide condensates, the condensation products of linear or branched, aliphatic, primary or secondary C _8-20 alcohols with ethylene oxide, and products made with by the condensation of ethylene oxide the reaction products of propylene oxide and ethylene diamine were prepared.

Particularly preferred are the primary and secondary alcohol ethoxylates, especially the primary and secondary C _9-11 and C _12-15 alcohols which are ethoxylated with an average of 5 to 20 moles of ethylene oxide per mole of alcohol.

In In certain forms of this invention, the amount of non-ionic surfactant Average in the range of 4 to 40 wt .-%, preferably 4 or 5 wt .-% to 30% by weight of the composition of the tablet or range from that. Many nonionic surfactants are liquids. these can on particles of the composition before compression into tablets be absorbed.

worin RCO eine Acylgruppe mit 8 bis 18 Kohlenstoffatomen, insbesondere Kokosnußacyl ist.Amphoteric surfactants which may be used in conjunction with the anionic or nonionic surfactants, or both, include amphopropionates of the formula:

wherein RCO is an acyl group having 8 to 18 carbon atoms, especially coconut acyl.

worin R₄ eine aliphatische Kohlenwasserstoffkette ist, die 7 bis 17 Kohlenstoffatome enthält, R₂ und R₃ unabhängig Wasserstoff, Alkyl mit 1 bis 4 Kohlenstoffatomen oder Hydroxyalkyl mit 1 bis 4 Kohlenstoffatomen, wie CH₂OH, ist, Y CH₂ oder -CONHCH₂CH₂CH₂ (Amidopropylbetain) ist; Z entweder COO- (Carboxybetain) oder CHOHCH₂SO₃- (Sulfobetain oder Hydroxysultain) ist.The category of amphoteric surfactants also includes amine oxides and also zwitterionic surfactants, especially betaines of the general formula:

wherein R _{4 is} an aliphatic hydrocarbon chain containing 7 to 17 carbon atoms, R ₂ and R _{3 are} independently hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms such as CH ₂ OH, Y is CH ₂ or -CONHCH _{2 is} CH ₂ CH ₂ (amidopropylbetaine); Z is either COO- (carboxybetaine) or CHOHCH ₂ SO ₃ - (sulfobetaine or hydroxysultaine).

worin R₁ C₁₀- bis C₂₀-Alkyl oder -Alkenyl ist; R₂, R₃ und R₄ jeweils Wasserstoff oder C₁- bis C₄-Alkyl sind, während n 1 bis 5 ist.Another example of an amphoteric surfactant is amine oxide of the formula:

wherein R _{1 is} C ₁₀ to C ₂₀ alkyl or alkenyl; R ₂ , R ₃ and R _{4 are} each hydrogen or C ₁ to C ₄ alkyl, while n is 1 to 5.

worin jeder R unabhängig eine Alkylgruppe oder eine Hydroxyalkylgruppe mit 1 bis 3 Kohlenstoffatomen kennzeichnet, und R_h eine aromatische, aliphatische oder gemischte aromatische und aliphatische Gruppe mit 6 bis 24 Kohlenstoffatomen kennzeichnet, bevorzugt eine Alkyl- oder Alkenylgruppe mit 8 bis 22 Kohlenstoffatomen und X ein Gegenion ist.Cationic surfactants may possibly be used. These often have a quaternary nitrogen atom in a polar head group and an attached hydrocarbon group of sufficient length to be hydrophobic. A general formula for a category of cationic surfactants is:

wherein each R independently denotes an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and R _h denotes an aromatic, aliphatic or mixed aromatic and aliphatic group having 6 to 24 carbon atoms, preferably an alkyl or alkenyl group having 8 to 22 carbon atoms and X. Counterion is.

The Amount of amphoteric surfactant Agent, if present, may be 3 to 20 or 30% by weight of the tablet or a portion of a tablet; the amount of cationic surfactant Agent, if present, may be 1 to 10 or 20% by weight of the tablet or a portion of a tablet.

builder

A Composition used to form tablets or tablet areas is compressed contains typically a detergency builder that serves calcium and / or To remove or mask magnesium ions in the water. Therefore The builder acts as a water softener. In detergent tablets can the amount of builder is 5 to 80% by weight, more preferably 10 or 15 to 40 wt .-%, 55 or 60 wt .-% of the tablet.

Of the Builder can in granulated particles in an amount of 20 up to 80% by weight, stronger preferably 20, 25 or 30 to 60 wt .-% be present.

construction materials can Completely by water-soluble Materials are provided, or may be largely or even completely a water-insoluble Material provided with water softening properties become.

Alkali metal aluminosilicates are highly preferred as environmentally acceptable detergency builders for fabric washing and are preferred in this invention. Alkali metal (preferably sodium) aluminosilicates may be either crystalline or amorphous, or mixtures thereof, having the general formula: 0.8-1.5 Na ₂ O. Al ₂ O _3. 0.8-6 SiO ₂ .xH ₂ O

These materials contain some bound water (indicated as xH ₂ O) and must have a calcium ion exchange capacity of at least 50 mg CaO / g. The preferred sodium aluminosilicates contain from 1.5 to 3.5 SiO ₂ units (in the above formula). Both the amorphous and crystalline materials can be readily prepared by the reaction of sodium silicate and sodium aluminate, as well-described in the literature.

Suitable crystalline sodium aluminosilicate ion exchange materials are described, for example, in US Pat GB 1 429 143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, the newer zeolite P disclosed in U.S. Pat EP 384,070 (Unilever), and mixtures thereof. The novel zeolite P is also referred to as "zeolite MAP" as indicated hereinbefore.

A builder may possibly be a layered sodium silicate, as in US Pat US 4,664,839 described. NaSKS-6 is the brand name for a crystalline layered silicate marketed by Hoechst (commonly abbreviated to "SKS-6") .NaSKS-6 has the delta-Na ₂ SiO ₅ morphology form of layered silicate in DE-A-3,417,649 and DE-A-3,742,043 be prepared.

Other such phyllosilicates, such as those with the general formula NaMSi _x O _2x + 1 · yH ₂ O wherein M represents sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can be used.

The less preferred category of water-soluble phosphorus-containing inorganic plasticizer the alkali metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.

Water-soluble non-phosphorus builders can be organic or inorganic. Inorganic building materials that can be present include alkali metal (generally sodium) carbonate; while organic Builders Polycarboxylate polymers such as polyacrylates, acrylic / maleic copolymers and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, Oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, Carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates include.

tablet compositions preferably include polycarboxylate polymers, more specifically, polyacrylates and acrylic / maleic copolymers, which have a certain function as a water softener and also the unwanted separation on the fabric from the washing liquid inhibit.

Contains the tablet a water-soluble Builder, this is preferably in an amount of 10 to 80 wt .-%, based on the total weight of the tablet or area this, available. Contains the Tablet a water-insoluble Builder, this is preferably in an amount of 5 to 80 wt .-%, based on the total weight of the tablet or a portion of this, available.

tablets, the 4 to 50 wt .-% surface-active Compositions and 5 to 80% by weight of detergency builder are for fabric washing tablets particularly preferred. Tablets containing 1 to 5 wt .-% surface-active Means and 50 to 98% detergency builder are for dishwasher tablets particularly preferred.

to Avoiding doubts, if a tablet is heterogeneous, the Percentage ranges for the components herein are based on the overall composition of the tablet and apply to at least one area of the tablet.

Water-soluble, the disintegration promotional particle

The compositions of the invention may contain water soluble disintegration promoting particles in addition to disintegrant grains either in the whole tablet or in a range thereof. Preferably, such disintegration promoting particles make 2, 3, 5, 8 or 10 up to 15, 20, 25 or 30 wt .-% of the composition of the tablet or a range of these. More preferably, such disintegration promoting particles comprise from 5 to 25 percent by weight of the composition based on the total weight of the composition.

Such soluble Particles typically contain at least 40% (of their own Weight) on one or more materials that are not soap or an organic surface-active Means are, and the one solubility in deionized water of at least 30 g / 100 g at 20 ° C.

Prefers will be at least part of the water-soluble, the disintegration promoting Particles to a vorgranulierten part of the composition, the used for the preparation of the tablet added. A little Part of such a soluble Material can also be made into granulated particles that have an organic content surfactant Means and / or a builder included in an amount of preferably from 1 to 25% by weight, stronger preferably 3 or 5 to 10 or 15% by weight of these granulated particles, introduced become.

More preferred This becomes water soluble Material selected from compounds, the at least 40% (based on the weight of the particles) of one or more materials selected from the group consisting from: compounds with a water solubility of 50 grams / 100 Grams in water at 20 ° C; or sodium tripolyphosphate, which is at least 50% of its own weight on the anhydrous phase I form; or sodium tripolyphosphate, partially hydrated so that it contains water of hydration in an amount at least 0.5% by weight of the sodium tripolyphosphate in the particles is.

As further explained below will, can these promoting disintegration Particles also other forms of tripolyphosphate or other salts contained in the rest of their composition.

If the material in such water-soluble, promoting disintegration Particles can act as a builder (as with sodium tripolyphosphate the case is), then wear it goes without saying to the total amount of detergency builder in the tablet composition at.

A solubility of at least 50 g / 100 g of deionized water at 20 ° C is one unexpectedly high solubility: many materials that are classified as water-soluble, are less soluble as this.

Some highly water-soluble materials that can be used are listed below, with their solubilities expressed as grams of solid to form a saturated solution in 100 grams of deionized water at 20 ° C: material Water solubility (grams / 100 grams of water) sodium citrate dihydrate 72 potassium carbonate 112 urea > 100 sodium 119 sodium acetate trihydrate 76 Magnesium sulfate 7H ₂ O 71

In contrast, the solubilities of some other common materials at 20 ° C are as follows: material Water solubility (g / 100 g) sodium chloride 36 decahydrate 21.5 Sodium carbonate, anhydrous 8.0 Sodium percarbonate, anhydrous 12 Sodium perborate, anhydrous 3.7 Sodium tripolyphosphate, anhydrous 15

Prefers this becomes very water-soluble Material as particles of the material in essentially pure form introduced (i.e., each particle contains over 95% by weight) of the material). The particles can however, a material having such a solubility in a mixture with a different material included, provided the material with the special solubility provides at least 50% by weight of these particles.

Preferred water-soluble materials having a solubility exceeding 50 grams / 100 grams of deionized water at 20 ° C are sodium citrate dihydrate, urea and sodium acetate, which may be partially dissolved or fully hydrated form (trihydrate). Sodium acetate trihydrate is particularly preferred.

Prefers is the very water-soluble Material a salt that dissolves in water in ionized form. If such a salt dissolves, fünhrt this to a temporary local increase the ionic strength, the can promote the disintegration of the tablet by preventing that will nonionic surfactant Medium swells and the dissolution the other materials is inhibited.

More accurate can said the tablets of this invention a water-soluble salt having a solubility which 50 g / 100 g deionized water at 20 ° C, both as a small percentage in the granulated particles as well as separate Contain particles mixed with this.

In the granulated particles containing a surfactant and / or may contain a builder, can be such a very water-soluble Salt in an amount of 0 to 30 wt .-% of these particles, preferably 3 to 10 or 15% of it, while the materials, the be added to these particles before tableting, such very soluble Salts in an amount of 2 or 5% up to 15% of the total tablet formulation could be.

A different possibility, which is less preferred is that the particles that cause the disintegration promote, Particles are the sodium tripolyphosphate with more than 50% (relative on the weight of the particles) of the anhydrous phase I form, and that is partially hydrated to allow water of hydration in one Contains quantity, which is at least 1% by weight of the sodium tripolyphosphate.

sodium tripolyphosphate is as a masking builder in detergent compositions very famous. It exists in a hydrated form and two crystalline anhydrous forms. These are the normal crystalline ones anhydrous form, known as Phase II, which is the low-temperature form and Phase I, which is stable at high temperature. The transformation from phase II to phase I takes place when heated above the transition temperature, which is about 420 ° C, pretty much fast, but the reverse reaction is slow. As a result, is sodium tripolyphosphate as a phase I form at ambient temperature metastable.

A process for the preparation of particles containing a high proportion of the phase I form of sodium tripolyphosphate by spray drying below 420 ° C is disclosed in U.S. Pat US-A-4 536 377 specified. These particles should also contain sodium tripolyphosphate which is partially hydrated. The extent of hydration should be at least 1% by weight of the sodium tripolyphosphate in the particles. It can be in the range of 1 to 4% or it can be higher. In fact, fully hydrated sodium tripolyphosphate can be used to provide these particles.

Of the Remainder of the tablet composition used to form the tablet or an area thereof may be additional Include sodium tripolyphosphate. This can be in any form including Sodium tripolyphosphate with a high content of the anhydrous phase II form. A suitable material is commercially available. Include suppliers Rhone-Poulenc, France and Rhodia, UK.

Some countries demand that phosphate not used. For such countries For example, a zero phosphate tablet according to this invention may be suitable Quantity, e.g. B. 15 wt .-% or more of a disintegration promoting Material with a solubility of at least 50 g / 100 g at 20 ° C, deploy. Other countries approve the use or at least a limited use of phosphates, indicating the use of some sodium tripolyphosphate allows.

Optional water-soluble, organic polymer

The Tablets of the present invention may be a water-soluble, organic polymer which is solid at 25 ° C and as a binder for the particulate Composition used in the compression. This can be granulated Particles containing an organic surfactant and / or a builder included.

Of the The term "solid" is used herein used to mark materials that at 25 ° C like a immobilized solid appear and are handled as solids can. They are in contrast to liquids, which, even when viscous, can flow. Organic polymers are In general, amorphous materials strictly as supercooled liquids however, be classified with such high viscosity that they are practical Purposes are fixed.

Of the Expression water-soluble is used herein with respect to this organic polymer to indicate that if the polymer is placed in water, it will be closer dissolves. Whether the solution now a true isotropic solution is or has a somewhat colloidal nature is not important to this invention.

The Polymeric material should preferably be at a temperature of at least 35 ° C, better 40 ° C or above, what in many countries in a temperate climate above the Ambient temperature is, melt. For use in hotter countries the melting temperature preferably slightly above 40 ° C, so that it is above ambient temperature.

Some Polymers that can be used are solid at temperatures up to 100 ° C, that is, they they seem to be stuck, although they are in an amorphous state are located. Upon further heating can they soften and melt to a mobile liquid, or they can decompose without melting if heated sufficiently above 100 ° C. Such polymers are generally as a powder during added to the granulation. Another possibility could be the addition as a solution in a fleeting one organic solvents But that is not preferable.

Other Polymers that can be used Melt at temperatures not exceeding 80 ° C in a liquid form and can as a molten liquid on the mixture of surface-active Agent and builder during the granulation sprayed become.

organic Polymers are generally amorphous solids. A significant Parameter characterizing amorphous solids is their glass transition temperature. When an amorphous hydrophilic polymer absorbs moisture, it acts the moisture as a plasticizer and reduces the glass transition temperature of the polymer. Suitable polymers can, if they are anhydrous, a glass transition temperature of 300 to 500K (i.e. 25 ° C to 225 ° C), can but be introduced in a moisture-containing state so that theirs Glass transition temperature is lower.

One preferred polymer is polyethylene glycol. Preferred polymeric materials are synthetic organic polymers, in particular polyethylene glycol. Polyethylene glycol of average molecular weight 1500 (PEG 1500) melts at 45 ° C and is considered suitable. Polyethylene glycol with a higher Molecular weight can also be used (PEG 4000 melts at 56 ° C and PEG 6000 at 58 ° C). Other options are polyvinylpyrrolidone and polyacrylate and water-soluble acrylate copolymers.

The Amount of water-soluble Polymer introduced into particles which is also an organic surfactant and a Building material contained, is preferably between 0.2 or 0.5 or 1 and 15% by weight of the particles, possibly at least 1.5 or 3% by weight. Preferably, the amount is not above 7 or 10% by weight. Alternatively, the amount of water-soluble Polymer in terms of the overall composition of the tablet or the range thereof, in which case it is desirable in an amount of 0.5 and 5% by weight, more preferably 0.5 to 4% by weight is present. It has been found that in some cases the Addition of the polymer easily prevents the disintegration of the tablet. Therefore, the level of the water-soluble polymer is for some Formulations preferably in the range of 0.5 to 2 wt .-%.

Optional bleaching system

The Tablet compositions according to the invention can contain a bleach system. This preferably comprises one or more Peroxy bleach compounds, for example to organic persalts or organic peroxyacids which can be used in conjunction with activators to to improve the bleaching action at low washing temperatures. If there is a peroxy compound, the amount is likely in the range of 10 to 25% by weight of the composition of the tablet or an area of it.

Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, which is advantageously used in conjunction with an activator. Bleach activators, also referred to as bleach precursors, have been widely disclosed in the art. Preferred examples include peracetic acid precursors, for example tetraacetylethylenediamine (TAED), currently in widespread use in conjunction with sodium perborate and percarbonate; and perbenzoic acid precursor. The quaternary ammonium and phosphonium bleach activators known in US 4,751,015 and U.S. 4,818,426 (Lever Brothers Company) are also of interest. Another type of bleach activator which can be used, but which is not a bleach precursor, is a transition metal catalyst, as in EP-A-458,397 . EP-A-458,398 and EP-A-549 272 disclosed. A bleach system may also include a bleach stabilizer (heavy metal masking agent) tel) such as ethylenediamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate.

enzymes

 The Tablets according to the invention can include one or more purification enzymes. The enzyme is preferred selected from amylase, protease, cellulase, lipase and mixtures thereof. The The aforementioned enzymes are said to have different soils and stains remove from the tissues.

cleaning enzymes are in the art for that she's known various contaminants and stains decomposed and theirs Contribute to removal. Examples of suitable proteases are Maxatase (trade name) as described by Gist-Brocades N.V., Delft, Holland supplied, and Alcalase (brand name), and Savinase (brand name), as supplied by Novo Industri A / S, Copenhagen, Denmark. cleaning enzymes become common in the form of grains or granules, optionally with a protective layer, in quantity from about 0.1 to about 3.0% by weight of the composition of the tablet or an area thereof; and these grains or Granules prepare to form a tablet during compression no problem.

Optional other ingredients

The Tablets of the invention can as well a fluorescent substance (optical brightener), for example, Tinopal (trade name) DMS or Tinopal CBS, available from Ciba-Geigy AG, Basel, Switzerland, included. Tinopal DMS is disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulfonate; and Tinopal CBS is disodium 2,2'-bis (phenyl-styryl) disulphonate.

An antifoam material is advantageously included when an organic surfactant is present, especially when a detergent tablet is primarily intended for use in automatic front loading drum washing machines. Suitable antifoam materials are usually in granular form, such as those described in U.S. Pat EP 266 863A (Unilever). Such antifoam grains typically comprise a blend of silicone oil, petrolatum, hydrophobic silica, and alkyl phosphate as an antifoaming material sorbed on a porous absorbed water-soluble carbonate-based inorganic support material. Antifoaming agents may be present in an amount of up to 5% by weight of the composition of the tablet or a portion thereof.

It may be equally desirable be that one Tablet of the invention a certain amount of alkali metal silicate, especially sodium ortho, meta or disilicate. The Presence of such alkali metal silicates in levels, for example from 0.1 to 10 wt .-%, can for the provision of protection against corrosion of metal parts be beneficial in washing machines, in addition to providing a certain degree of Construction and the provision of processing advantages in the Production of the particulate Material that is compressed into tablets. A composition for the fabric washing will generally contain no more than 15% by weight of silicate. A tablet for wash the dishes will often contain at least 20% by weight silicate.

bulk density of an uncompressed detergent powder & granulation process While the particulate Starting composition from which the tablets are made, in principle, any bulk density may have, the present invention in particular for tablets be relevant from a cleaning composition, which by the Compressing powders with a relatively high bulk density because they have more disintegration and distribution problems show. Such tablets have the advantage that, in comparison to a tablet made from a powder with a low bulk density is a predetermined dose of the composition as a smaller Tablet can be displayed.

Therefore can the particulate Starting composition suitably has a bulk density of at least 400 g / l, preferably at least 500 g / l and if possible at least 600 g / l exhibit.

Granular detergent compositions having a high bulk density prepared by granulation and densification in a high speed mixer / granulator as in EP-A-340 013 (Unilever) EP-A-352 135 (Unilever) and EP-A-425 277 (Unilever) and claimed, or by the continuous granulation / densification processes as in EP-A-367,339 (Unilever) and EP-A-390 251 (Unilever) are naturally suitable for use in the present invention.

Another particularly suitable method for producing a detergent powder with a high bulk density is in WO-A-98/11193 (Unilever). In this document, a raw substrate from the starting acid to produce the anionic surfactant is partially neutralized, for example by sodium hydroxide, before being fed to a high speed mixer (e.g. Lodige CB 30 recycler) where the partially neutralized acid raw substrate is completely neutralized while is mixed with most of the other components of the detergent base powder granules. This powder can be further densified by treatment in a medium speed mixer (for example, Lodige KM 300 Mixer), whereby further builder can be added beforehand. The water-soluble polymer material is preferably added prior to the further densification step, although it may be added to the first mixer. The water-soluble polymer material may be heated to a temperature significantly above its melting point to obtain a free-flowing liquid. The resulting powder can be cooled and dried using a fluidized bed, after which any desired particle size control can be performed.

All separate particles containing further components of the final formulation can contain be mixed with the base powder before compression.

particle size control

The Particle sizes can be in the method of preparation of the particles contained in the composition are controlled. Oversized particles are usually at the end of the manufacturing process by sieving removed (for example, by a Mogensensieb), followed by grinding and recycling the removed oversized fraction. Too small particles can also be removed by sieving, or if the manufacturing process a fluidized bed can use too small particles are introduced into the air stream and subsequently from it for the recycling in the granulation be recovered.

It is preferred that the average particle size of the granulated Particles that are the particulate Form the composition of which the tablet is formed between 400 and 1100 microns, preferably between 500 and 1000 microns, lies. Preferably, not more than 5% of these particles are smaller than 200 microns while not more than 5% larger than 1,400 microns are.

Materials, which are mixed with the granulated particles, these can Meet requirements in view of the particle size as well. These Materials (postdosed) typically make up 5 to 60 wt% of the total weight of the final composition, more usually 35 to 55% by weight.

tableting

The Tableting brings the compression of a particulate composition with himself. A variety of Tablettiermaschinerie is known and can be used. In general, it is made by pressing a certain amount of particulate Composition enclosed in a mold will work. The tableting may be at ambient temperature or at a temperature above ambient be performed, what makes it possible an adequate one To achieve firmness with little applied pressure during compression. To carry out the tableting at a temperature above ambient lies, becomes the particular Preferably transferred composition at elevated temperature to the tabletting machine. this will cause the release of heat to the tabletting machine, however The machine can also be heated in a different way. Will heat applied, it should be remembered that this in a conventional way supplied as by passing the particulate composition through a Oven, rather than by application of microwave energy.

The Size of the tablet is suitably in the range of 10 to 160 grams, preferred 15 to 60 g, depending on the conditions of the intended application and whether or not she has a dose for an average load in a washing machine or dishwasher or a fractional part of such a dose depends. The Tablets can have any shape. For However, they are preferably blocks with the lighter packaging a substantially uniform cross-section, such as cylinders or Cube.

The Total density of one tablet for the fabric wash is preferably in the range of 1040 or 1050 g / liter, preferably at least 1100 g / liter up to 1400 g / liter. The tablet density can also be in the range of up to no more than 1350 or even 1250 g / liter. The total density of a tablet of some others Cleaning compositions, such as a tablet for dishwashing or as a bleaching additive, may be in the range of up to 1700 g / liter and will often be in the range of 1300 to 1550 g / liter.

The Detergent tablet can be prepared by methods that mixing the disintegrator grains with the other components of the composition, the placing a certain amount of the resulting particulate composition in one Mold and compressing the composition in the mold for manufacture of the tablet.

Tablet test - disintegration

The Disintegration rate of the tablets in the examples was measured by a test method under static conditions, by using a previously weighed tablet on a metal grid 1 × 1 cm mesh was placed, and then the tablet and the grid immersed in a suitable amount of tap water at 15 ° FH (French Hardness) at 10 or 20 ° C were so that the Tablet when submerged 2 cm covered with water. After 60 seconds The metal grid was carefully removed from the water and the wet tablet residue was weighed. If the tablet completely disintegrates during this time was the tent for recorded a 100% disintegration.

The Tablets preferably show 70% or more disintegration in the above test, stronger preferably 75% or more, the strongest preferably 80% or more.

tablet strength

worin DBB die diametrale Bruchbelastung in Pascal ist, F_max die angewandte Last in Newton zur Herbeiführung eines Bruches ist, D der Tablettendurchmesser in Meter ist und t die Tablettendicke in Metern ist. Der Test wird unter Verwendung eines Instron Universaltestgerätes durchgeführt, um eine Kompressionskraft auf den Tablettendurchmesser auszuüben (d. h. senkrecht zur Achse einer zylindrischen Tablette). Die Tabletten haben bevorzugt eine DBB von zumindest 20 kPa, stärker bevorzugt mindestens 25 kPa, wie 30 kPa oder darüber.The strength of tablets in their dry state, as prepared on the compacting press, can be determined according to their diametrical breaking load, DBB, which is calculated from the equation:

where DBB is the diametric breaking load in Pascals, F _{max is} the load applied in Newton to cause breakage, D is the tablet diameter in meters, and t is the tablet thickness in meters. The test is performed using an Instron universal tester to apply compressive force to the tablet diameter (ie perpendicular to the axis of a cylindrical tablet). The tablets preferably have a DBB of at least 20 kPa, more preferably at least 25 kPa, such as 30 kPa or above.

Determination of the water swelling capacity of the water swellable through

To illustrate the water swell capacity of the water swellable agent, 19.6 grams of the agent was mixed with 0.4 grams of ultramarine pigment and compressed into a tablet using a laboratory tablet press at about 250 MPa to obtain a 32 mm diameter tablet. This was crushed and sieved to obtain grains having a particle size of 500 to 1000 μm. A glass tube, 33 mm inside diameter and about 30 cm long with a sintered, porous glass (porosity 1), which was attached to one end was immersed vertically with one end at the bottom in a large beaker of water (at 25 ° C), so that the water level rose to about 14 cm above the sintered glass. One gram of the grains was added to the tube and they were allowed to settle on the sintered glass. With this arrangement, the water can reach the grains from both above and below. The grains immediately begin to swell, forming a jelly-like mass. The ultramarine pigment gave the mass a blue color, making the end easier to recognize and record its height. The height of the swelling mass was recorded at intervals and showed an initial rapid increase, followed by flattening after about 20 to 30 minutes. From the diameter of the tube, the volume of the swollen mass can be calculated. The result was expressed after about 20 minutes as cm ³ / g of water-swellable agent.

The Tablets are intended to be used as tissue washing tablets when in use an automatic washing machine either in the powder dispenser or can be placed directly in the washing drum. This can be done either manually or take place automatically.

The detergent / cleansing tablets of the invention are suitable for use, as known in the art, in "home" applications, that is, detergent tablets suitable for use in cleaning and maintenance procedures typically performed around the home. It does not include any methods that are performed directly on a human or an animal body known as personal care applications Examples of household detergent tablets include: laundry tablets, (machine) dishwashing tablets, hard surface cleaning tablets, toilet bowls tablets, bleaching tablets, water softener tablets, etc.

Examples

The Invention will be further described by the following examples. Other examples within the scope of the present invention will become Be professional.

Preparation of a granular starting powder

One granular Detergent starting powder was added by granulating the ingredients over the post-dosed Ingredients "under High shear followed by compression under reduced shear for producing a granulated component.

• ^*1 „DOUCIL^TM A24", ein Maximum-Aluminium-Zeolith P (MAP) von Ineos Silcas, UK.
• ^*2 NDOM ist kein Waschmittel auf organischer Basis.
• ^*3 SOKALAN^TM HP23 ist ein gepfropftes Co-polymer von Polyethylenoxid und Polyvinylacetat von BASF, Deutschland.
• ^*4 beschichtetes Percarbonat von Interox
• ^*5 DEQUEST^TM 2047 ist Ethylendiamintetramethylenphosphonat von Monsanto
• ^*6 DEQUEST^TM 2016 ist Ethylenhydroxydiphosphonat von Monsanto.

The post-dosed ingredients were then added as described above under the heading "Granulation Procedure" to produce a detergent powder having the overall composition shown in Table 1. Table 1: Detergent powder starting composition ingredient Wt .-% Linear sodium alkylbenzenesulfonate 12.34 C _13-15 fatty alcohol, 7EO, branched 3.53 C _13-15 fatty alcohol, 3EO, branched 1.89 Soap 0.94 Zeolite ^{* 1} (anhydrous) 27.60 Sodium acetate trihydrate / zeolite mixture (99: 1, weight mixture) 3.53 sodium 4.10 Sodium carboxymethylcellulose (69% active) 0.55 Salts, moisture and NDOM ^{* 2} postdosed ingredients 4.97 Fluorescent additive 2.17 Sokalan ^TM HP23 additive ^{* 3} 1.45 sodium citrate dihydrate 5.07 Tetraacetylethylenediamine (TAED) grains (83% active) 5.44 Sodium percarbonate (coated) ^{* 4} 20,30 Sodium silicate granules (80% active) 4.35 EDTMP granules (Dequest ^™ 2047) ^{* 5} 1.04 EHDP granules (Dequest ^™ 2016) ^{* 6} 0.73 total 100% by weight

• ^{* 1} "DOUCIL ^™ A24", a maximum aluminum zeolite P (MAP) from Ineos Silcas, UK.
• ^{* 2} NDOM is not an organic based laundry detergent.
• ^{* 3} SOKALAN ^™ HP23 is a grafted co-polymer of polyethylene oxide and polyvinyl acetate from BASF, Germany.
• ^{* 4} coated Percarbonate from Interox
• ^{* 5} DEQUEST ^™ 2047 is ethylene diamine tetra methylene phosphonate from Monsanto
• ^{* 6} DEQUEST ^TM 2016 is ethylene hydroxydiphosphonate from Monsanto.

Desintegrator grains A to F

Six desintegrator grains were prepared by the typical preparation method described above under the heading "Desintegrator grains." The grains had the composition shown in Table 2 and were sieved to collect the fraction having a particle size of 500 to 1200 μm, as far as The amounts given in Table 2 are percentages of each ingredient by weight in the disintegrant grain and are 100 weight percent based on the total weight of the grain Ac-Di-Sol ^™ is the water swellable agent Table 2: Desintegrator Grain Compositions A B C D e F Wt .-% Wt .-% Wt .-% Wt .-% Wt .-% Wt .-% Zeolite P ^{* 1} 46,25 82.5 72,25 59,25 33.25 20.25 water-swellable clay ^{* 7} 46,25 10 20.25 33.25 59,25 72,25 Ac-Di-Sol ^{TM * 8} 7.5 7.5 7.5 7.5 7.5 7.5

• ^{* 7} Brebent clay, a water-swellable calcium bentonite clay treated with sodium carbonate sold under the name BREBENT by Laporte PLC.
• ^{* 8} Crosslinked carboxymethylcellulose from FMC Corporation, USA.

Comparative Examples C1 to C5

Comparative Examples C1 to C5 were prepared with the composition shown in Table 3. Table 3: Comparative Examples C1 to C5 C1 C2 C3 C4 C5 Wt .-% Wt .-% Wt .-% Wt .-% Wt .-% Starting composition from Table 1 100 90 90 90 90 Granular, water-swellable clay ^{* 7} - - 10 - - Granular zeolite ^{* 1} - 10 - - - Granules: 92.5 parts; Clay ^{* 7} : 7.5 parts, Ac-Di-Sol ^{TM * 8} - - - - 10 Granules: 92.5 parts; Zeolite ^{* 1} : 7.5 parts; Ac-Di-Sol ^{TM * 8} - - - 10 -

shares 40 g of each comparative composition became too cylindrical Tablets with a diameter of 44.5 mm and a height of 18 up to 22 mm using a Graseby Specac laboratory tableting machine processed. The compression pressure used for each tablet was set so that the Tablets all with the same diametral breaking load of 30 kPa were compressed. The strength of the tablets in their dry Condition, as produced on the press, was called their diametral breaking load, DBB, by the procedure above was carried out in the description of the invention determined.

Examples 1 and 2

The detergent starting powder of Table 1 was mixed with the disintegrator grains A and B of Table 2 to prepare Examples 1 and 2 which are examples according to the invention as set forth in Table 4. Table 4: Preparation of Examples 1 and 2. 1 2 Wt .-% Wt .-% Starting composition from Table 1 90 90 Desintegrator grains A 10 - Desintegrator grains B - 10

These Compositions were as described above for Comparative Examples C1 executed compressed.

disintegration results Comparative Examples C1 to C5 and Examples 1 and 2.

The rate of disintegration of the tablets was measured under static conditions as described above under the heading "Tablet Test Disintegration." The disintegration results are reported in Table 5. The "output" result is the disintegration result obtained for tablets which were the same Tag were made and tested. The "storage" result is the disintegration result obtained for tablets which were prepared and stored at 20 ° C in a closed container for 14 days before being tested for disintegration Table 5: Disintegration results for Comparative Examples C1 to C5 and Examples 1 and 2. example % Output disintegration; 60 s, 20 ° C % Storage disintegration; 60 s; 20 ° C C1 10% 8th % C2 49% 49% C3 27% 43% C4 81% 48% C5 28% 44% 1 65% 96% 2 63% not measured

The The above examples show that the Tablets, the disintegrator grains, comprising the swelling clay, the crystalline aluminosilicate and the water-swellable Means include good disintegration properties both initially also show during storage. A comparison with C1 and C2 illustrates This point. C4 shows a good initial disintegration, this one is not preserved during storage.

Comparative Example C6

Comparative Example C6 was prepared as shown in Table 6. The disintegrator grain components are expressed as parts by weight. Table 6: Comparative Example C6 Wt .-% Starting composition from Table 1 74 Granules: 92.5 parts clay ^{* 7} : 7.5 parts Ac-Di-Sol ™ ⁸ 5 Na-acetate · 3H ₂ O / zeolite mixture (99: 1 weight mixture) 21

shares of 40 g of the compositions were as above for Comparative Example C1 executed, processed into cylindrical tablets.

Examples 3 to 6

The detergent starting powder of Table 1 was additionally blended with the disintegrant grain A of Table 2 and, where indicated in Table 7, with a sodium acetate / zeolite mixture to produce Examples 3-6. These are examples according to the invention. Table 7: Preparation of Examples 3 to 6 3 4 5 6 Wt .-% Wt .-% Wt .-% Wt .-% Starting composition from Table 1 90 90 85 85 Desintegrator Grain A - 10 - 10 Na-acetate · 3H ₂ O / zeolite mixture (99: 1 weight mixture) - - 5 5

These Compositions were compressed as outlined above for Comparative Example C1.

disintegration results of Comparative Example C6 and Examples 3 to 6.

The rate of disintegration of the tablets was measured under static conditions as described above under the heading "Tablet Test Disintegration." The disintegration results are given in Table 8. Table 8: Disintegration Results for Comparative Example C6 and Examples 3 to 6 Example% Output disintegration; 60 s, 20 ° C C6 100% 3 57% 4 73% 5 84% 6 91%

C6 shows excellent disintegration but requires 21% by weight of one promoting disintegration Material plus 5 wt .-% of a Desintegratorkorns. The tablets according to the invention also show acceptable disintegration, but at much lower levels Overall levels of disintegration promoting material and disintegrator grain. Thereby can larger amounts in the tablets the "starting" composition used become. The additional Improvement of disintegration by the inclusion of a promoting disintegration Material in the composition in addition to the disintegrator grain is by comparing the results of Examples 3, 5, 4 and 8 to recognize.

Comparative Example C7

Comparative Example C7 was prepared as shown in Table 9. The grain components are expressed in parts by weight. Table 9: Comparative Example C7 Wt .-% Starting composition from Table 1 90 Granules: 92.5 parts zeolite ^{* 1} : 7.5 parts Ac-Di-Sol ™ ⁸ 5 Na-acetate · 3H ₂ O / zeolite mixture (99: 1 weight mixture) 5

shares of 40 g of the composition were as in the above examples executed compressed.

Examples 7 to 14

The detergent starting powder of Table 1 was mixed with the disintegrator granules A and C through F and, where indicated, additionally with a sodium acetate / zeolite mixture to prepare Examples 7-14, which are examples according to the invention as set forth in Table 10. Table 10: Preparation of Examples 7 to 14. 7 8th 9 10 11 12 13 14 Wt .-% Wt .-% Wt .-% Wt .-% Wt .-% Wt .-% Wt .-% Wt .-% Starting composition from Table 1 90 90 90 90 90 85 77 70 Desintegrator Grain A 5 - - - - - - - Disintegrator grain C - 5 - - - - - - Desintegrator Grain D - - 5 - - 5 5 5 Desintegrator grain E - - - 5 - - - - Disintegrator grain F - - - - 5 - - - Na-acetate · 3H ₂ O / zeolite mixture (99: 1 weight mixture) 5 5 5 5 5 10 18 25

These Compositions were compressed as outlined above for Comparative Example C1.

disintegration results of Comparative Example C7 and Examples 7 to 14.

The rate of disintegration of the tablets was measured under static conditions as described above under the heading "Tablet Test Disintegration." The disintegration results are given in Table II. Table 11: Disintegration results for Comparative Example C7 and Examples 7 to 14 example % Output disintegration; 60 s, 20 ° C C7 42% 7 67% 8th 74% 9 79% 10 63% 11 50% 12 90% 13 100% in 45 s 14 100% in 32 s

The Tablets according to the invention show in comparison to a tablet comprising a Desintegratorkorn, the Zeolite but no clay contained, good disintegration.

Examples 15 to 17

The detergent starting powder from Table 1 was mixed with disintegrant grain B and additionally with a sodium acetate / zeolite mixture to prepare Examples 15-17 which are examples according to the invention as set forth in Table 12. Table 12: Preparation of Examples 15 to 17. 15 16 17 Wt .-% Wt .-% Wt .-% Starting composition from Table 1 90 90 90 Disintegrator bead B; Particle size 500-1200 μm 5 - - Disintegrator bead B; Particle size 500-710 μm - 5 - Disintegrator bead B; Particle size 710-1200 μm - - 5 Na-acetate-3H ₂ O / zeolite mixture (99: 1 weight mixture) 5 5 5

These Compositions were compressed as outlined above for Comparative Example C1.

Disintegration results of the examples 15 to 17

The rate of disintegration of the tablets was measured under static conditions as described above under the heading "Tablet Test Disintegration." The disintegration results are given in Table 13. TABLE 13 Disintegration results of Examples 15-17 example % Output disintegration; 60 s, 20 ° C 15 80% 16 43% 17 62%

The Results show that the Particle size of the disintegrator grain the disintegration result obtained for the tablet can influence.

Examples 18 and 19

Two examples were prepared which additionally contained minor ingredients normally found in detergent tablets. The detergent starting powder from Table 1 was mixed with disintegrant grain A and additionally with a sodium acetate / zeolite mixture to prepare Examples 18 and 19, which are examples according to the invention as set forth in Table 14. Table 14: Preparation of Examples 18 and 19. 18 19 Wt .-% Wt .-% Starting composition from Table 1 85.78 82,40 Desintegrator Grain A 4.90 5.00 defoamers 1.96 2.00 Lipolase 100T - 0.1 Savinase 12T - 0.5 PEG 1500 powder 1.96 - perfume 0.49 - Na-acetate 3H ₂ O / zeolite mixture (99: 1 weight mixture) 4.90 10.00

These Compositions were compressed as outlined above for Comparative Example C1.

Disintegration results of the examples 18 and 19

The rate of disintegration of the tablets was measured under static conditions as described above under the heading "Tablet Test Disintegration." The disintegration results are given in Table 15. Table 15: Disintegration Results of Examples 18 and 19 example % Output disintegration; 60 s, 20 ° C 18 46% 19 86%

Claims (27)

Tablet of a compressed, particulate detergent composition, comprising a non-soap surfactant Agent and a builder, wherein the tablet or a single Range of disintegrator grains, comprising water-swellable clay, a water-insoluble inorganic material and a water-swellable agent. A tablet according to claim 1, wherein the water-swellable Agent in its anhydrous state not more than 20 wt .-% of united weight of water-swellable clay, water-insoluble inorganic material and the water-swellable agent. A tablet according to any one of claims 1 or 2, wherein the water-swellable Sound a smectite tone is. A tablet according to claim 3, wherein the smectite clay is a Bentonite clay is. A tablet according to claim 4, wherein the bentonite clay by the treatment of bentonite in calcium form with a sodium compound will be produced. A tablet according to any one of the preceding claims, wherein the water-insoluble inorganic material silicon dioxide, a material that is at least Contains 70% by weight of silica, or an aluminosilicate. The tablet of claim 6, wherein the aluminosilicate is a zeolite having the empirical formula: M _{2 / n} O · Al ₂ O ₃ · xSiO ₂ · yH ₂ O where M is a metallic cation having a valency of n, x is the ratio of the atoms of silica to atoms of aluminum, and y is the ratio of molecules of water to atoms of aluminum. A tablet according to claim 7, wherein the zeolite is a zeolite P or zeolite A is. A tablet according to claim 8 wherein the zeolite is zeolite P is where M is an alkali metal cation and x is a value in the range from 1.8 to 2.66. A tablet according to any one of claims 7 to 9, wherein the zeolite a zeolite P with a water content in the range of 9 to 12% by weight is. A tablet according to any one of claims 7 to 10, wherein the zeolite P is a maximum aluminum zeolite P is. A tablet according to any one of the preceding claims, wherein the relative amount of water-swellable clay and water-insoluble clay inorganic material in the disintegrator grain in the weight ratio range from 2: 1 to 1: 4 by weight of water swellable clay: water-insoluble inorganic material. A tablet according to any one of the preceding claims, wherein the water-swellable agent from the group consisting of cellulose, crosslinked cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crosslinked Sodium carboxymethylcellulose, swellable starch, crosslinked starch and crosslinked polyvinylpyrrolidone. A tablet according to claim 13, wherein the water-swellable Agent is a cross-linked sodium carboxymethylcellulose. A tablet according to any one of the preceding claims, wherein the water-swellable agent in its anhydrous state 1 to 8% by weight of the combined weight of the swelling clay, the water-insoluble one inorganic material and the water-swellable agent. A tablet according to any one of the preceding claims, wherein the water-swellable agent in the disintegrator grain in an amount less than 2% by weight, based on the total weight of the tablet composition, is present. A tablet according to any one of the preceding claims, wherein the water-swellable agent has an average primary particle size of up to to 600 μm Has. A tablet according to any one of the preceding claims, wherein the water-swellable agent has a water swelling capacity of at least 5 cm ³ / g. A tablet according to any one of the preceding claims, wherein the tablet 1 to 15% by weight of the disintegrator grains based on the total weight the tablet composition. A tablet according to any one of the preceding claims, wherein the disintegrator grains an average particle size in the range from 700 to 1200 microns. A tablet according to any one of the preceding claims, comprising disintegrant, comprising a bentonite clay obtained by the treatment of a bentonite prepared in calcium form with a sodium compound, maximum aluminum zeolite P and cross-linked sodium carboxymethylcellulose. A tablet according to any one of the preceding claims, wherein the disintegrator grain 20 to 45% by weight of water-swellable clay, 45 to 70 wt .-% water-insoluble inorganic material and 3 to 9% by weight of water-swellable agent, based on the weight of the disintegrator grain. A tablet according to any one of the preceding claims, further comprising water-soluble disintegration promoting particles containing at least 40%, by weight of the particles, of one or more materials selected from the group consisting of i) compounds having a water solubility 50 g per 100 g of water at 20 ° C, and ii) sodium tripolyphosphate containing at least 50% of its own weight of anhydrous Phase I form, and iii) sodium tripolyphosphate partially hydrated to contain water of hydration in an amount of at least 0.5% by weight of the sodium tripolyphosphate in the particles , A tablet according to claim 23, wherein the compounds with a water solubility, which exceeds 50 g per 100 g of water at 20 ° C, selected from sodium acetate, sodium citrate dihydrate or urea. A tablet according to claim 24, wherein the sodium acetate Sodium acetate trihydrate. A tablet according to any one of claims 23 to 25, wherein the water-soluble, promoting disintegration Particles in an amount of 5 to 25 wt .-%, based on the total weight of the composition. Process for producing a tablet from a compressed, particulate A detergent composition comprising a non-soap surfactant Agent and a builder, the method comprising mixing disintegrant granules, comprising a water-swellable clay, a water-insoluble clay inorganic material and a water swellable agent, with others Components of the detergent composition for the preparation of a particulate Detergent composition, placing a certain amount of resulting particulate Detergent composition in a mold and compressing the Composition in the form for the preparation of the tablet.