DE10026334A1 - Detergent tablets with graft copolymer coating - Google Patents

Abstract

Coated detergent tablets in which the coating both protects the tablets against mechanical stress and is an active substance in the washing or cleaning process are coated with a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture being selected from graft copolymers which can be obtained by grafting (a) polyalkylene oxides with (b) vinyl acetate.

Description

The present invention is in the field of compact moldings, the washing and have cleaning-active properties. Such detergent tablets include, for example, detergent tablets for washing textiles, Detergent tablets for automatic dishwashing or hard cleaning Surfaces, bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets. In particular, the invention relates Detergent tablets which are used for washing textiles in a household washing machine used and briefly referred to as detergent tablets.

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and to use and because of their compact size Structure advantages in storage and transportation. In the patent literature too, washing and detergent tablets consequently described comprehensively. A problem with the Use of washing and cleaning active moldings occurs again and again, that is too low rate of disintegration and dissolution of the moldings under conditions of use. There sufficiently stable, d. H. Shaped and unbreakable molded articles only by relatively high Press prints can be produced, there is a strong compression of the Molded parts and a resulting delayed disintegration of the Shaped body in the aqueous liquor and thus to a slow release of the Active substances in the washing or cleaning process. The delayed disintegration of the  Shaped body has the further disadvantage that conventional washing and Detergent tablets not through the detergent dispenser of household washing machines Allow to be flushed in, as the tablets do not quickly become secondary particles disintegrate, which are small enough to be washed into the washing drum from the dispensing chamber become. Another problem, particularly in the case of detergent tablets occurs, the friability of the moldings or their often insufficient stability against Abrasion. So can be sufficiently stable, d. H. hard washing and Detergent tablets are produced, but these are often the loads Packaging, transport and handling, d. H. Falling and rubbing stresses, not grown sufficiently so that edge breakage and abrasion appearances of the molded body or even completely destroy the molded body structure to lead.

To overcome the dichotomy between hardness, i. H. Transport and handling stability, and easy disintegration of the moldings, many solutions have been developed in the prior art been. A well known in particular from pharmacy and in the field of washing and Detergent tablets extensive approach is the incorporation of certain Disintegration aids that make it easier to access water or when accessing water swell or develop gas or disintegrate in another form. Other Proposed solutions from the patent literature describe the compression of premixes certain particle sizes, the separation of individual ingredients from certain others Ingredients and the coating of individual ingredients or the entire molded body with binders.

The coating of detergent tablets, also in German Language usage is increasingly referred to as "coating" is the subject of some Patent applications.

The European patent applications EP 846 754, EP 846 755 and EP 846 756 (Procter & Gamble) coated detergent tablets that have a "core" of compressed, Particulate detergents and cleaning agents and a "coating" include, where as Coating materials dicarboxylic acids, especially adipic acid, are used optionally contain other ingredients such as disintegration aids.  

Coated detergent tablets are also the subject of European patent application EP 716 144 (Unilever). According to the information in this document, the hardness of the tablets can be measured reinforce a "coating" without affecting the disintegration and dissolving times. As Coating agents become film-forming substances, in particular copolymers of Acrylic acid and maleic acid or sugar and polyethylene glycols called.

The proposed solutions disclosed in the prior art make use of this Coating materials that have no effect in the later washing or cleaning process unfold. A certain proportion by weight of the moldings is thus attributable to auxiliaries that Don't let consumers benefit directly, but in product costs must be taken into account in the calculation.

The present invention was based on the object, coated washing and Provide detergent tablets in which the advantageous properties of higher hardness without impairing the short disintegration times with small amounts Coating agents can be achieved, using such substances as coating materials should be provided in addition to the mechanical protection of the molded body in the future Washing or cleaning also have an effect. The resistance of the molded body against falling and friction loads should be achieved compared to the known moldings or be further improved. Ideally, the coated moldings should be with minimized packaging effort, d. H. with a cheaper individual packaging or can even be delivered to retailers without any individual packaging without the Storage stability of the molded body suffers from this. An easy to carry out and universal to provide an applicable process for the production of such coated moldings another object of the present invention.

It has now been found that certain water-soluble polymers, known as Graying inhibitors for textile detergents are known, also for coating laundry detergents. and detergent tablets are suitable and give them advantageous properties.

The invention therefore relates to detergent tablets compacted particulate detergent and cleaning agent containing builders (e) and if necessary, further detergent and cleaning agent components, which with a polymer or  Are polymer mixture coated, the polymer or at least 50 wt .-% of The polymer mixture is selected from graft copolymers which are obtainable by grafting of (a) polyalkylene oxides with (b) vinyl acetate.

The detergent tablets according to the invention are with a polymer or Coated polymer mixture, the polymer (and accordingly the entire Coating) or at least 50% by weight of the polymer mixture (and thus at least 50% the coating) is selected from certain polymers. The coating is there all or at least 50% of their weight from graft copolymers that are available by grafting (a) polyalkylene oxides with (b) vinyl acetate. These polymers will described in more detail below.

The coating materials used in the context of the present invention Graft copolymers are described in European patent application EP 219 048 A (BASF) described. They are available by grafting a polyalkylene oxide with vinyl acetate, whereby the acetate groups of the vinyl acetate can be partially saponified. As polyalkylene oxides come especially polymers with ethylene oxide, propylene oxide and butylene oxide units into consideration, with polyethylene oxide being preferred.

The graft copolymers can be prepared, for example, by dissolving the Polyalkylene oxides in vinyl acetate and continuous or batch polymerization after Addition of a polymerization initiator, or by semi-continuous polymerization, in which part of the polymerization mixture of polyalkylene oxide, vinyl acetate and Polymerization initiator is heated to polymerization temperature, after which the rest of the polymerizing mixture is added. The graft copolymers can also do this are obtained by introducing polyalkylene oxide, heated to the polymerization temperature and vinyl acetate and polymerization initiator either at once, batchwise or preferably adds continuously.

Preferred detergent tablets in the context of the present invention are characterized in that the coating consists of at least 50% by weight of graft copolymers which can be obtained by grafting (a) polyalkylene oxides with a molecular weight of 1500 to 70,000 gmol ^-1 with (b ) Vinyl acetate in the weight ratio of (a): (b) from 100: 1 to 1: 5, the acetate groups optionally being saponified up to 15%.

In addition to the graft copolymers, the coating can include other coating materials such as for example other polymers or ingredients of washing or cleaning agents, such as Dyes, fragrances, etc. included. With the exception of the moldings that are in the coating contain further active substance (see below), here are washing or Preferred detergent tablets, the coating of which is at least 70% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular entirely from graft copolymers of (a) polyalkylene oxides with (b) Vinyl acetate exists.

In preferred embodiments of the present invention, the molecular weight of the polyalkylene oxides contained in the graft copolymers is 2000 to 50,000 gmol ^-1 , preferably 2500 to 40,000 gmol ^-1 , particularly preferably 3000 to 20,000 gmol ^-1 and in particular 4000 to 10,000 gmol ^-1 . Corresponding detergent tablets are preferred according to the invention.

Depending on the desired properties of the coating, the proportion of individual monomers vary. Detergent tablets are preferred, in which the vinyl acetate content in the graft copolymers is 1 to 60% by weight, preferably 2 up to 50% by weight, particularly preferably 3 to 40% by weight and in particular 5 to 25% by weight, each based on the graft copolymer.

A graft copolymer which is particularly preferred in the context of the present invention is based on a polyethylene oxide with an average molecular weight of 6000 gmol ^-1 (corresponding to 136 ethylene oxide units) which contains about 3 parts by weight of vinyl acetate per part by weight of polyethylene oxide. This polymer, which has an average molecular weight of approx. 24000 gmol ^-1 , is sold commercially by BASF under the name Sokalan® HP22.

The detergent tablets coated according to the invention also have Small amounts of coating material already have significantly improved properties. It is  preferred in the context of the present invention that the amount of coating material less than 5% by weight, preferably less than 2.5% by weight and in particular less than 1% by weight of the total weight of the coated molded body. Washing and Detergent tablets in which the weight ratio of uncoated Shaped body for coating greater than 10 to 1, preferably greater than 25 to 1 and is particularly larger than 50 to 1, are therefore preferred embodiments of the present Invention.

Due to the small amounts in which the aforementioned polymers are already high resilient and advantageous coating of the previously pressed washing and Detergent tablets cause coating thicknesses that can be realized in the Compared to the dimensions of the moldings are small. In preferred washing and Detergent tablets, the thickness of the coating on the tablet is 0.1 to 500 µm, preferably 0.5 to 250 µm and in particular 5 to 100 µm.

To make the coating even more resistant to mechanical stress, Polyurethanes can be incorporated into the coating. These give the coating Elasticity and stability and can vary according to the amount specified above make up water-soluble polymers up to 50% by weight of the coating.

The polyurethanes consist of at least two different types of monomers,

• - A compound (A) with at least 2 active hydrogen atoms per molecule and
• - a di- or polyisocyanate (B).

The compounds (A) can be, for example, diols, triols, diamines, triamines, Trade polyetherols and polyesterols. The connections with more than 2 active Hydrogen atoms usually only in small amounts in combination with a large one Excess of compounds with 2 active hydrogen atoms used.

Examples of compounds (A) are ethylene glycol, 1,2- and 1,3-propylene glycol, Butylene glycols, di, tri, tetra and poly ethylene and propylene glycols, copolymers of lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, ethylenediamine,  Propylene diamine, 1,4-diaminobutane, hexamethylene diamine and α, ω-diamines based on long chain alkanes or polyalkylene oxides.

Polyurethanes in which the compounds (A) are diols, triols and polyetherols can be preferred according to the invention. In particular with polyethylene glycols and polypropylene glycols Molar masses between 200 and 3000, in particular between 1600 and 2500, have become proved to be particularly suitable in individual cases. Polyesterols are usually made by Modification of the compound (A) with dicarboxylic acids such as phthalic acid, isophthalic acid and Obtained adipic acid.

The compounds (B) used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluenediisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate. These compounds can be described by the general formula I:

O = C = NR ¹ -N = C = O (I),

in which R ^{1 represents} a linking group of carbon atoms, for example a methylene-ethylene-propylene, butylene, pentylene, hexylene, etc. group. In the above-mentioned, most widely used hexamethylene diisocyanate (HMDI), R ¹ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluenediisocyanate (TDI) R ^{1 is} C ₆ H ₃ -CH ₃ ) , in 4,4'-methylenedi (phenyl isocyanate) (MDI) for C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) and in isophorone diisocyanate R ^{4 represents} the isophorone residue (3,5,5-trimethyl-2-cyclohexenone) .

Furthermore, the polyurethanes used according to the invention can also contain building blocks such as for example, diamines as chain extenders and hydroxycarboxylic acids. Dialkylolcarboxylic acids such as dimethylolpropionic acid are particularly suitable Hydroxy carboxylic acids. With regard to the other building blocks, there is no fundamental one Restriction on whether it is non-ionic, anionic or cationic building blocks acts.

For more information on the structure and manufacture of the polyurethanes expressly to the articles in the relevant overviews such as Römpps Chemie- Lexicon and Ullmann's encyclopedia of technical chemistry referenced.  

Polyurethanes, which can be characterized as follows, have proven particularly suitable according to the invention in many cases:

• - only aliphatic groups in the molecule
• - No free isocyanate groups in the molecule
• - Polyether and polyester polyurethanes
• - anionic groups in the molecule.

Furthermore, it has proven to be suitable for the production of the coated washing and Detergent tablets have proven to be advantageous if the polyurethanes are not directly with the mixed other components, but introduced in the form of aqueous dispersions were. Such dispersions usually have a solids content of approx. 20-50%, in particular about 35-45%, and are also commercially available.

Detergent tablets in which the coating is in addition to mentioned polymers polyurethane in amounts of 5 to 50 wt .-%, preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the coating, contains are preferred according to the invention.

In addition to the polymers from the group of graft copolymers and optionally others The coated moldings according to the invention can also polymers in the coating contain further ingredients, in particular further ingredients of washing and Have proven cleaning agents. These substances are discussed in detail below In general, detergent tablets according to the invention are described preferred, in which the coating additionally one or more substances from the groups disintegration aids, dyes, optical brighteners, fragrances, enzymes, Bleaching agents, bleach activators, silver protection agents, complexing agents, surfactants, Graying inhibitors and mixtures thereof in amounts of 0.5 to 30% by weight, preferably from 1 to 20% by weight and in particular from 2.5 to 10% by weight, in each case based on the weight the coating.

According to the invention, it is particularly advantageous to use readily soluble substances, so-called Solution mediator to work into the coating. Particularly preferred solubilizers  have solubilities above 200 grams of solubilizer in one liter of deionized Water at 20 ° C. As such preferred solubilizers for incorporation into the A whole series of coatings are suitable for the purposes of the present invention Compounds that are both from the group of covalent compounds and from the group the salts can come from. It is preferred if the solubilizers are even higher Have solubilities, so that solubilizers are preferred as an additive to the coating, which have a solubility of more than 250 g per liter of water at 20 ° C, preferably of more than 300 g per liter of water at 20 ° C and in particular of more than 350 g per liter of water at 20 ° C exhibit. An overview of the solubilities of within the scope of the present invention The following list provides suitable solubilizers. The ones in this table The solubility values given relate - unless other temperatures are explicit are mentioned - on the solubility at 20 ° C.

The amount in which the substances mentioned in the coating according to the invention can be incorporated are advantageously in the above range, i. H. at Amounts from 0.5 to 30% by weight, preferably from 1 to 20% by weight and in particular from 2.5 up to 10 wt .-%, each based on the weight of the coating.

The following substances are preferred finely divided solubilizers in the context of the present invention:

The components of the coating of the moldings according to the invention were explained in more detail above described. In the following, the components of the moldings themselves, i.e. H. the uncoated moldings described. These moldings are in part as "Basic molded article" refers to a verbal delimitation against the term "molded article" or “tablet” for the detergent tablets coated according to the invention  to achieve, but sometimes the general term "molded body" is used. Since the The present invention relates to base moldings provided with a coating, The information given below for the basic molded body naturally also applies to Detergent tablets according to the invention, which have the corresponding Meet conditions, and vice versa.

The basic moldings contain builders (e) as essential components. In the Base moldings according to the invention can all usually be found in washing and Builders used in cleaning agents may be included, in particular thus zeolites, silicates, Carbonates, organic cobuilders and - where there are no ecological prejudices against their use exist - also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + i} . H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for × 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ . yH ₂ O preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

n Na ₂ O. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular Compound used, as well as a kind of "powdering" of the whole to be pressed Mixture are used, usually both ways to incorporate the zeolite in the premix can be used. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and contain preferably 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Among the variety of commercially available phosphates are the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or Potassium tripolyphosphate) in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogenphosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3) . Both salts are white, water-soluble powders which, when heated lose the water of crystallization and at 200 ° C change into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature into sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below) ₂ PO _{4 is} acidic, it is formed when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed in. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ is a white salt the density 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate.

Despite the higher price, in the detergent industry, the more soluble, therefore highly effective, potassium phosphates compared to corresponding sodium compounds in many cases prefers.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or 6H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n - Na with n = 3. In 100 g of water about 17 g of the crystal water-free salt dissolve at room temperature, about 20 g at 60 ° and about 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O).

The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or Mixtures of these two can be used; also mixtures of sodium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and Potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Polycarboxylates / poly in particular can be used as organic cobuilders in the base moldings carboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, others organic cobuilders (see below) and phosphonates are used. These substance classes are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.  

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven suitable % Acrylic acid and 50 to 10 wt .-% maleic acid. Your molecular weight, based on free acids, is generally from 2000 to 70,000 g / mol, preferably 20,000 up to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The amount of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.  

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of acrylic acid as monomers and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which are preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives, which in addition to cobuilder properties also a have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates obtained by partial hydrolysis of starches can. The hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molar masses in the range from 400 to 500000 g / mol. A polysaccharide is included a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a poly saccharids compared to dextrose, which has a DE of 100. Both are usable Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher ones Molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. An oxidized oligosaccharide is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and are also preferred in this context Glycerol trisuccinate. Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and a maximum of two Acid groups included.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly special Meaning as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The Aminoalkanephosphonates also have a strong ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it may be preferred Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.

In addition, all compounds that are capable of complexing with alkaline earth ions train as cobuilders.  

The amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. The amount of Builder used is dependent on the intended use, so bleach tablets may have higher amounts of builders (for example between 20 and 70% by weight %, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), as, for example, detergent tablets (usually 10 to 50% by weight, preferably 12.5 up to 45% by weight and in particular between 17.5 and 37.5% by weight).

Preferred base tablets furthermore contain one or more surfactant (s). In the Base moldings can be anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. Are preferred from application technology point of view mixtures of anionic and nonionic surfactants. The The total surfactant content of the moldings is 5 to 60% by weight, based on the Molded body weight, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins having an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, as in the preparation by esterification of a monoglycerol with 1 to 3 mol Obtained fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated ten fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.  

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearin acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The given degrees of ethoxylation are statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl ester.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than that Half of it.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II),

in which RCO stands for an aliphatic acyl radical having 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups . The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N- Alkoxy- or N-aryloxy-substituted compounds can then be reacted with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In the context of the present invention, preference is given to base moldings which are anionic and contain non-ionic (s) surfactant (s), with application advantages from certain Ratios in which the individual classes of surfactants are used result can.

For example, base moldings in which the ratio of Anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Washing or Detergent tablets which contain anionic (s) and / or nonionic (s) surfactant (s) and Total surfactant contents above 2.5% by weight, preferably above 5% by weight and in particular above 10% by weight, based in each case on the molding weight. Detergent tablets, the surfactant (s), are particularly preferred anionic and / or nonionic surfactant (s), in amounts of 5 to 40% by weight,  preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight us in particular from 12.5 to 25% by weight, based in each case on the molding weight.

From an application point of view, it can have advantages if certain classes of surfactants are used some phases of the base tablets or in the entire tablet, d. H. in all phases, not are included. Therefore, see another important embodiment of the present invention before that at least one phase of the shaped body is free of nonionic surfactants.

Conversely, however, the content of individual phases or the entire molded body, d. H. all phases, certain surfactants have a positive effect. The bringing in the alkyl polyglycosides described above have proven to be advantageous, so that Base moldings are preferred in which at least one phase of the moldings Contains alkyl polyglycosides.

Similar to nonionic surfactants can also be left out of anionic Surfactants result from individual or all phases of basic shaped bodies which are suitable for certain Areas of application are better suited. It is therefore also within the scope of the present invention Detergent tablets in which at least one phase of the Shaped body is free of anionic surfactants.

In order to facilitate the disintegration of highly compressed moldings, it is possible to Disintegration aids, so-called tablet disintegrants, to be incorporated into them in order to Shorten disintegration times. Under tablet disintegrants or disintegrators according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical Technologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances necessary for the rapid disintegration of tablets in water or gastric juice and for the release of pharmaceuticals in absorbable Shape.

These substances, which are also known as "explosives" due to their effectiveness, increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand a pressure can also be generated via the release of gases, which breaks the tablet into smaller particles. Well-known disintegration aids are for example carbonate / citric acid systems, with other organic acids  can be used. Swelling disintegration aids are, for example, synthetic Polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred base agent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, in each case based on the weight of the molded article.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred base moldings such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not in finely divided form Form, but before mixing into the premixes to be pressed into a transferred coarser form, for example granulated or compacted. Washing and  Detergent tablets, the disintegrants in granular or optionally co-granulated Form contained, are in the German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO 98/40463 (Henkel) described. These documents also contain more information on the production of granulated, compacted or cogranulated cellulose disintegrant. The particle sizes such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular at least 90% by weight between 400 and 1200 µm. The aforementioned and described in more detail in the cited documents Coarser disintegration aids based on cellulose are within the scope of the present Invention preferably used as a disintegration aid and commercially, for example available under the name Arbocel® TF-30-HG from Rettenmaier.

As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial hydrolysis of celluloses obtained under such conditions that only the amorphous Attack areas (approx. 30% of the total cellulose mass) of the celluloses and completely dissolve, but leave the crystalline areas (approx. 70%) undamaged. A subsequent one The disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses with primary particle sizes of approx. 5 µm and for example, can be compacted into granules with an average particle size of 200 μm.

Preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in Quantities from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, each based on the weight of the shaped body, preferred Disintegration agent average particle sizes above 300 microns, preferably above of 400 microns and especially above 500 microns.

In addition to the ingredients mentioned builder, surfactant and disintegration aid, the Detergent tablets according to the invention further in detergent and Common detergent ingredients from the group of bleaching agents, bleach activators, Dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils,  Anti-redeposition agents, graying inhibitors, color transfer inhibitors and Corrosion inhibitors included.

To develop the desired bleaching performance, the washing and Detergent tablets of the present invention contain bleach. Have here the usual bleaches from the group sodium perborate monohydrate, Sodium perborate tetrahydrate and sodium percarbonate have proven themselves, the latter clearly is preferred.

"Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a solution obtained from sodium carbonate in hydrogen peroxide, but mistakenly as peroxy carbonate viewed. It was not until 1909 that the compound was used as a hydrogen peroxide addition compound recognized, nevertheless the historical name "sodium percarbonate" has been used in practice enforced.

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried at 90 ° C. in fluid bed dryers. The bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and substances used for coating are widely described in the patent literature.

In principle, all commercially available percarbonate types can be used according to the invention as for example from the companies Solvay Interox, Degussa, Kemira or Akzo Tobe offered.

In the bleaching agents used, the content of the moldings in these substances is from Depending on the intended use of the molded body. While common universal detergents in Tablet form between 5 and 30 wt .-%, preferably between 7.5 and 25 wt .-% and contain in particular between 12.5 and 22.5% by weight of bleach, the contents are Bleach or bleach booster tablets between 15 and 50 wt .-%, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.

In addition to the bleaching agents used, the washing and Detergent tablets contain bleach activator (s), which is within the scope of the present Invention is preferred. Bleach activators are used in detergents and cleaning agents incorporated to improve when washing at temperatures of 60 ° C and below To achieve bleaching effect. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C- Atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used. Substances containing the O- and / or N-acyl groups are suitable mentioned number of carbon atoms and / or optionally substituted benzoyl groups. Prefers are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the moldings. With these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also  Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

If the moldings according to the invention contain bleach activators, they contain, in each case based on the entire molded body, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or more Bleach activators or bleach catalysts. Depending on the intended use of the manufactured Shaped bodies can vary these amounts. So are in typical universal detergent tablets Bleach activator contents between 0.5 and 10% by weight, preferably between 2 and 8% by weight and especially between 4 and 6% by weight, while bleach tablets are quite common higher contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular can have between 10 and 20% by weight. The specialist is is not restricted in its freedom of formulation and can be stronger or weaker bleaching detergent tablets, detergent tablets or Manufacture bleach tablets by reducing the levels of bleach activator and bleach varies.

A particularly preferably used bleach activator is the N, N, N ', N'- Tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred detergent tablets are thereby characterized in that as a bleach activator tetraacetylethylenediamine in the above Amounts are used.

In addition to the ingredients mentioned, bleach, bleach activator, builder, surfactant and Disintegration aids, the washing and Detergent tablets from other ingredients common in detergents and cleaning agents the group of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, Silicone oils, anti-redeposition agents, graying inhibitors, color transfer inhibitors and Corrosion inhibitors included.

The aesthetic impression of the detergent tablets according to the invention To improve, they can be colored with suitable dyes. Preferred dyes, the selection of which is no problem for the expert has a high degree  Storage stability and insensitivity to the other ingredients of the agent and against light as well as no pronounced substantivity towards textile fibers stain.

Preferred for use in the detergent tablets according to the invention are all colorants that can be oxidatively destroyed in the washing process, as well as mixtures the same with suitable blue dyes, so-called blue toners. It has proven to be beneficial proven to use colorants in water or at room temperature in liquid organic substances are soluble. For example, anionic colorants, e.g. B. anionic nitroso dyes. A possible colorant is, for example, naphthol green (color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a commercial product, for example as Basacid® Green 970 is available from BASF, Ludwigshafen, and mixtures of these with suitable blue dyes. Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blau (CI Acid Blue 182, CAS 12219-26-0) for use.

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in detergents or cleaning agents, however, is typically some 10 ^-3 to 10 ^-4 wt .-%.

The moldings can be optical brighteners of the derivative type of the diaminostilbene contain sulfonic acid or its alkali metal salts. Are suitable for. B. 4,4'-bis (2- anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like built-up compounds that instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. B. the Alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can be used. The optical brighteners are used in the washing and detergent tablets in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight, each based on the entire molded body used.

Fragrances are added to the agents according to the invention in order to give the aesthetic impression of Improve products and provide consumers with a visual and visual performance to provide sensory "typical and distinctive" product. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products from Type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p- tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. B. the linear alkanals with 8-18 C atoms, citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, among the Ketones e.g. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol Hydrocarbons mainly belong to the terpenes like limonene and pinene. Prefers however, mixtures of different odoriferous substances are used, which together form a generate an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil,  Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The content of the detergent tablets according to the invention is usually in the range of fragrances up to 2% by weight of the total formulation. The fragrances can be directly in the agents according to the invention can be incorporated, but it can also be advantageous that Apply fragrances to carriers that increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. As such Carrier materials have proven themselves, for example, cyclodextrins, the cyclodextrin Perfume complexes can also be coated with other auxiliaries.

Enzymes include, in particular, those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases wear in the laundry to remove stains such as protein, fat or starchy Stains and graying. Cellulases and other glycosyl hydrolases can furthermore by removing pilling and microfibrils for color preservation and Contribute to increasing the softness of the textile. To bleach or inhibit the Color transfer can also be used with oxidoreductases. Are particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified Variants of enzymatic active ingredients obtained. Proteases are preferably from Subtilisin type and in particular proteases obtained from Bacillus lentus, used. Enzyme mixtures, for example of protease and amylase or Protease and lipase or lipolytic enzymes or protease and cellulase or from Cellulase and lipase or lipolytic enzymes or from protease, amylase and Lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases or Oxidases have been found to be suitable in some cases. To the suitable amylases count in particular alpha-amylases, iso-amylases, pullulanases and pectinases. As Cellulases are preferably cellobiohydrolases, endoglucanases and glucosidases that also called cello bias, or mixtures of these are used. Because there are different  Can distinguish cellulase types by their CMCase and avicelase activities targeted mixtures of the cellulases the desired activities can be set.

The enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect against premature decomposition. The proportion of enzymes, enzyme mixtures or Enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% be.

In addition, the detergent tablets can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile that is already soiled previously several times with a detergent according to the invention that this oil and fat-dissolving Contains component that has been washed. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxy propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, the are particularly preferred sulfonated derivatives of phthalic acid and terephthalic acid polymers.

The moldings according to the invention are produced in two steps. In the first step are known detergent tablets by pressing in a conventional manner particulate detergent and cleaner compositions made, the second Step with the coating.

Another object of the present invention is therefore a method for producing coated detergent tablets by pressing known per se a particulate detergent and detergent composition and the following Immersion in or spraying with a melt, solution or dispersion of one or several polymers from the group of graft copolymers which are obtainable by grafting of (a) polyalkylene oxides with (b) vinyl acetate.  

Analogous to the explanations for the washing and Detergent tablets are also those mentioned in the process according to the invention Polymers preferred, so that reference can be made to the above statements.

A description of the two major process steps follows.

The moldings to be coated later according to the invention are first produced by the dry mixing of the components, which are partially or completely pre-granulated can, and then bringing information, in particular compression to tablets, whereby on conventional methods can be used. For the production of the shaped body the premix in a so-called die between two stamps to a solid Compressed compressed. This process, which is briefly referred to below as tabletting, is divided into four sections: dosage, compression (elastic deformation), plastic Deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the Weight and shape of the resulting shaped body through the position of the lower stamp and the shape of the press tool can be determined. The constant dosage also with high molding throughput is preferably a volumetric dosage of Premix reached. As the tableting continues, the upper stamp touches this Premix and continues to lower towards the lower stamp. With this compression the particles of the premix are pressed closer together, the void volume within the filling between the stamps decreases continuously. From a certain Position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation in which the particles flow together and it to form the Shaped body comes. Depending on the physical properties of the premix, there will also be a Part of the premixed particles are crushed and one comes at even higher pressures Sintering the premix. With increasing press speed, i.e. high throughputs, the phase of elastic deformation is shortened further and further, so that the resulting Moldings can have more or less large cavities. In the last step the The finished molded article is tabletted by the lower die from the die pushed out and transported away by subsequent transport devices. To this Only the weight of the molded body is finally determined at the time, since the compacts  due to physical processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size.

Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure, the lower punch also moves up during the pressing process the upper stamp while the upper stamp presses down. For little ones Production quantities are preferably eccentric tablet presses, in which the or the stamps are attached to an eccentric disc, which in turn is on an axis with a certain rotational speed is mounted. The movement of this ram is with the Operation of a conventional four-stroke engine comparable. The pressing can be done with one Upper and lower stamps are made, but it is also possible to have several stamps on one Eccentric disk can be attached, the number of die holes correspondingly expanded is. The throughputs of eccentric presses vary from a few hundred to a maximum, depending on the type 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle. The number of Matrices vary between 6 and 55 depending on the model, although larger matrices are also commercially available are available. Each die on the die table is assigned an upper and lower stamp, again the pressure is active only through the upper or lower stamp, but also through both stamps can be built. The matrix table and the stamps move by one common vertical axis, the stamp with the help of rail-like Curve tracks during the circulation in the positions for filling, compression, plastic Deformation and discharge are brought. In those places where a particularly serious The stamp needs to be raised or lowered (filling, compacting, ejecting), these cam tracks are replaced by additional low pressure pieces, low tension rails and Lifting lanes supported. The matrix is filled using a rigidly arranged one Feeding device, the so-called filling shoe, which with a storage container for the Premix is connected. The pressing pressure on the premix is via the pressing paths for top and lower stamp individually adjustable, the pressure build-up by rolling the Stamp shaft heads happen on adjustable pressure rollers.

Rotary presses can also be equipped with two filling shoes to increase throughput be, only a semicircle has to be run through to produce a tablet.  

Several filling shoes are used to produce two- and multi-layer molded articles arranged one behind the other without the slightly pressed first layer before the next Filling is ejected. Appropriate process control also means that and point tablets can be produced, which have an onion-shell-like structure, whereby in the case the tablet is not covering the top of the core or core layers and thus remains visible. Rotary tablet presses are also available with single or Multiple tools can be equipped so that, for example, an outer circle with 50 and an inner one Circle with 35 holes can be used for pressing at the same time. The throughputs are more modern Rotary tablet presses are over one million tablets per hour.

When tableting with rotary presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching the filler paddle speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed

All known from the art can be used to reduce stamp caking Non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps have also proven to be advantageous proven, where possible the upper and lower stamps should be rotatable. At A rotating plastic stamp is usually not necessary. Here should the stamp surfaces must be electropolished.

It was also shown that long pressing times are advantageous. This can be done with pressure rails, several pressure rollers or low rotor speeds can be set. Since the Fluctuations in hardness of the tablet are caused by the fluctuations in the pressing forces systems should be used that limit the pressing force. Here elastic  Stamps, pneumatic compensators or spring elements are used in the force path. The pressure roller can also be designed to be resilient.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holland Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). The hydraulic double pressure press HPF, for example, is particularly suitable 630 from LAEIS, D. Tableting tools are, for example, from Adams Tableting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Toolmaking, Tamm available. Other providers are e.g. B. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can be made in a predetermined spatial shape and a predetermined size become. Practically all sensibly manageable designs come in as the spatial form Consider, for example, the formation as a board, the rod or bar shape, cubes, Cuboid and corresponding room elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section. This last one Design covers the presentation form from the tablet to compact Cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents corresponds. However, it is also possible to form compacts which have a plurality of them Connect mass units in a compact, in particular by predetermined Breaking points are intended for easy separability of portioned smaller units. For the use of textile detergents in machines of the type common in Europe with horizontal arranged mechanics can the formation of the portioned compacts as tablets, in  Cylinder or cuboid shape may be appropriate, with a diameter / height ratio in Range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, Ex Center presses or rotary presses are suitable devices especially for Production of such compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions Detergent dispenser of commercial household washing machines adapted so that the Shaped bodies can be dosed directly into the induction bowl without a dosing aid, wherever they are dissolves during the induction process. It goes without saying that the Detergent tablets easily possible via a dosing aid and within the scope of present invention preferred.

Another preferred shaped body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine. This Principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles, only on one side are connected alongside each other, can be realized.

But it is also possible that the various components do not become one Tablet are pressed, but that molded bodies are obtained that have multiple layers, ie have at least two layers. It is also possible that these different Layers have different dissolving speeds. This can be advantageous application properties of the moldings result. If, for example Components are contained in the moldings that have a mutually negative effect, so it is possible to integrate the one component in the more quickly soluble layer and the incorporate other components into a slower soluble layer so that the first Component 16721 00070 552 001000280000000200012000285911661000040 0002010026334 00004 16602e has already reacted when the second goes into solution. The layer structure of the Shaped bodies can be made in a stack-like manner, with a dissolution process of the inner one Layer (s) on the edges of the molded body already takes place when the outer layers are not yet fully resolved, but it can also completely wrap the inner  Layer (s) can be reached through the layer (s) further out, which leads to a Prevention of premature release of components of the inner layer (s) leads.

In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleaching agent, while at stack-shaped molded body, the two cover layers and the shell-shaped molded body outermost layers, however, are free of peroxy bleach. It is also possible to Peroxy bleach and any existing bleach activators and / or enzymes spatially separated from each other in a molded body. Such multilayered molded articles have the advantage that they do not have only one induction chamber or one Dosing device which is added to the wash liquor can be used; much more In such cases it is also possible to put the molded body in direct contact with the textiles the machine without bleaching and the like would be feared.

In addition to the layer structure, multiphase moldings can also be in the form of Ring-core tablets, core-coated tablets or so-called "bulleye" tablets are produced become. An overview of such embodiments of multi-phase tablets is in EP 055 100 (Jeyes Group). This document discloses blocks of toilet cleaners that a molded body from a slowly soluble detergent composition comprise, in which a bleach tablet is embedded. This document also reveals the various forms of design of multi-phase molded bodies from the simple Multi-phase tablets to complex multi-layer systems with inserts.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

Here σ stands for diametral fracture stress (DFS) in Pa, P is the force in N, which leads to the pressure exerted on the molded body, which breaks the Shaped body, D is the shaped body diameter in meters and t is the height of the Molded body.

Preferred manufacturing processes for detergent tablets are based on one Granules containing surfactants, which combine with other processing components to form one compressing particulate premix is prepared. Completely analogous to the The above statements about preferred ingredients of the washing and Detergent tablets are also the use of other ingredients in their manufacture transfer. In preferred processes, the particulate premix additionally contains Granulate (s) containing surfactant and has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

In preferred processes according to the invention, the surfactant-containing granules have particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferred between 400 and 1600 µm and in particular between 600 and 1400 µm.

The other ingredients of the washing and Detergent tablets can be introduced into the process according to the invention, for which reference is made to the above explanations. Preferred methods are thereby characterized in that the particulate premix additionally comprises one or more substances the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH Adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Contains color transfer inhibitors and corrosion inhibitors.

The second step of the method according to the invention comprises the application of the coating. Common methods of coating bodies can be used for this purpose, in particular immersing the body in or spraying the body with a Melt, solution or dispersion of the polymers mentioned.  

Since the immersion of detergent tablets in melts or solutions or dispersions only with great technical effort to the desired thin Leads coatings, it is preferred in the context of the present invention, Spraying polymer solutions or dispersions onto the shaped bodies, the solution or dispersant evaporates and leaves a coating on the molding. In the preferred method according to the invention is an aqueous solution of one or more Polymers from the group of the graft copolymers which can be obtained by grafting (a) Polyalkylene oxides with (b) vinyl acetate sprayed onto the moldings, the aqueous Solution, in each case based on the solution, 10 to 90% by weight, preferably 15 to 85% by weight and in particular 20 to 60% by weight of polymer (s) optionally up to 20% by weight, preferably up to 10 wt .-% and in particular less than 5 wt .-% of one or more water-miscible Solvent and the rest water.

To shorten the drying time, the aqueous solution can be further with water miscible volatile solvents are added. These come in particular from the group of alcohols, ethanol, n-propanol and iso-propanol being preferred. Out For reasons of cost, ethanol and isopropanol are particularly recommended.

The polymers from the group of graft copolymers which can be obtained by grafting (a) Polyalkylene oxides with (b) vinyl acetate make up 50 to 100% by weight of the coating of the Shaped body according to the invention. Accordingly, the can on the molded body solution to be sprayed on contain further ingredients, an addition of polyurethanes - as mentioned above - is preferred. If water-insoluble polyurethanes are added here, so the liquid to be sprayed on is in the form of a dispersion.

Another preferred embodiment of the method according to the invention is therefore a Process variant in which an aqueous dispersion of one or more polyurethanes additionally one or more dissolved polymers from the group of the graft copolymers which are obtainable by grafting (a) polyalkylene oxides with (b) vinyl acetate on which Molded body is sprayed, the dispersion, based in each case on the dispersion, 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight of polyurethane (s), 1 up to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight of polymer (s) from groups a) to e), optionally up to 20% by weight, preferably up to 10% by weight and  in particular below 5% by weight of one or more water-miscible solvents and the rest contains water.

For the purposes of the invention, aqueous dispersions are understood to mean those dispersions which whose outer phase consists mainly of water. The outer phase can go beyond that other water-miscible solvents such as ethanol and iso-propanol contain; these further solvents are at most in amounts of up to 20% by weight, based on all the means included. The outer phase preferably contains water as the only one Solvent; a further preferred embodiment contains, based on the outer phase on the entire agent, no more than 5% of other solvents.

The spraying of such aqueous solutions or dispersions can be done in different ways take place that are familiar to the expert. For example, the solution or dispersion can be supplied by means of a pump system to a nozzle, where the solution or dispersion passes through the high shear forces are atomized. The resulting spray mist can then on the Coating moldings are directed, which subsequently optionally with the help suitable measures (e.g. blowing with heated air) can be dried. It is but also possible to use a multi-component nozzle and the aqueous solutions or Nebulize dispersions using a gas stream through the nozzle. In the simplest case a two-component nozzle is used and compressed air is used as the carrier gas. To the dispersion if necessary to protect against oxidation or other interactions with the carrier gas, can also other carrier gases such as nitrogen, noble gases, lower alkanes or Ether are used.

It is also possible to reduce the water content of the dispersion or solution, which drying times shortened, interactions with moisture-sensitive ingredients minimized on the molding surface and lowers production costs. Here too the above-mentioned lower alcohols as solvents, being completely anhydrous Solvent mixtures are less preferred, since certain amounts of water Favor formation of an even coating layer. In preferred The method according to the invention becomes a solution or dispersion of one or more polymers from the group of graft copolymers which can be obtained by grafting (a) Polyalkylene oxides with (b) vinyl acetate in a solvent or solvent mixture  the group of water, ethanol, propanol, iso-propanol, n-heptane and their mixtures with the help inert blowing agents from the group consisting of nitrogen, nitrous oxide, propane, butane, Dimethyl ether and mixtures thereof are sprayed onto the moldings.

In such preferred process variants according to the invention, the solutions or dispersions advantageously have the following composition, the details relating in each case to the dispersion to be sprayed on:

• a) 30 to 99% by weight, preferably 40 to 90% by weight and in particular 50 to 85% by weight Ethanol, propanol, isopropanol, n-heptane or mixtures thereof,
• b) 0 to 20, preferably 1 to 15 and in particular 2 to 10% by weight of water,
• c) 1 to 50, preferably 2 to 25 and in particular 3 to 10 wt .-% of one or more Polymers from the group of graft copolymers which are obtainable by grafting of (a) polyalkylene oxides with (b) vinyl acetate.

If polyurethanes or other ingredients are to be part of the coating, they can these are the polymers from the group of graft copolymers which are obtainable by grafting of (a) polyalkylene oxides with (b) vinyl acetate in the above Frame formulation up to 50% of the replace the mentioned weight.

Other ingredients of the dispersions to be sprayed on can be, for example, color or Fragrances or pigments. Such additives improve, for example, the visual or olfactory impression of the moldings coated according to the invention. Dyes and fragrances have been described in detail above. Pigments come for example White pigments such as titanium dioxide or zinc sulfide, pearlescent pigments or color pigments in Consideration, the latter being divided into inorganic pigments and organic pigments can. If used, all of the pigments mentioned are preferably finely divided, i. H. with average particle sizes of 100 µm and well below.

In order to achieve the formation of a uniform and as thin a coating as possible, it is preferably, the solution or dispersion of the coating materials as fine as possible fog before it hits the molded body. Processes according to the invention in which the the relevant solution and / or dispersion is applied to the moldings via a nozzle,  wherein the average droplet size in the spray is less than 100 microns, preferably less than 50 µm and in particular less than 35 µm, are preferred in this way the preferred thickness of the coating mentioned above can be easily realized.

Since the polymers used according to the invention as a coating can be melted without decomposition it is advantageously possible to dispense with the use of solutions or dispersions and instead, a melt of the coating is applied to the moldings.

Processes according to the invention in which a melt of polymers from the group of Graft copolymers obtainable by grafting (a) polyalkylene oxides with (b) Vinyl acetate, which optionally contains further constituents, is applied to the moldings are therefore preferred according to the invention.

Another object of the present invention is the use of polymers or Polymer mixtures for coating detergent tablets, the Polymer or at least 50 wt .-% of the polymer mixture is selected from the group of Graft copolymers obtainable by grafting (a) polyalkylene oxides with (b) Vinyl acetate.

This inventive use of the polymers mentioned leads to coated moldings with advantageous properties, as the examples below show. Regarding preferred embodiments of the use according to the invention (ingredients, The composition of the premix, preferred polymers etc.) applies analogously to the above for the method according to the invention said.  

Examples

A was used to produce uncoated detergent tablets Granular surfactant mixed with other processing components and placed on an eccentric Tablet press pressed into shaped bodies. The composition of the surfactant granules is in the given in Table 1 below, the composition of the premix to be compressed (and thus the composition of the moldings) can be found in Table 2.

Table 1

Granular surfactant [% by weight]

Table 2

Premix [wt%]

The tablettable premix became tablets in a Korsch eccentric press (Diameter: 44 mm, height: 22 mm, weight: 37.5 g) pressed.

These tablets were divided into three series, the first series of which, untreated, served as a comparative example (V), while the second series (E1) was sprayed with a melt of a graft copolymer made from polyethylene oxide (molar mass 6000 gmol ^-1 ) and vinyl acetate in a ratio of 9: 1. The third series (E2) was sprayed with a melt of a graft copolymer made of polyethylene oxide (molar mass 6000 gmol ^-1 ) and vinyl acetate in a ratio of 9: 1. In the case of example E1, 0.82 g of the polymer was applied as a coating, corresponding to a ratio of uncoated molded article to coating of 45.7 to 1. In example E2 according to the invention, 1.53 g polymer was applied (corresponding to a ratio of uncoated molded article to Coating from 24.5 to 1).

Two tablets from each of the three series V, E1 and E2 were placed on a 4 mm sieve Mesh size laid and on a Retsch screening machine with maximum amplitude 120 seconds long shaken. After this experiment, the weight loss of the tablets was determined. The Table 3 below shows the weight loss of the shaped bodies E1, E2 and V, the Values are averages from five determinations.  

To determine tablet disintegration, the tablet was placed in a beaker with water (600 ml water, temperature 30 ° C) and the time taken for the tablet to completely disintegrate. The experimental data of the individual tablet series is shown in Table 3:

Table 3

Detergent tablets [physical data]

Claims (20)

1. laundry detergent or cleaning product tablets made of compressed particulate washing and cleaning agents, containing builders (e) and optionally further washing and cleaning agent components, characterized in that the molded articles are coated with a polymer or polymer mixture, the polymer or at least 50% by weight. % of the polymer mixture is selected from graft copolymers which can be obtained by grafting (a) polyalkylene oxides with (b) vinyl acetate. 2. Detergent tablets according to claim 1, characterized in that the coating consists of at least 50% by weight of graft copolymers which can be obtained by grafting (a) polyalkylene oxides having a molecular weight of 1500 to 70,000 gmol ^-1 with (b) Vinyl acetate in the weight ratio of (a): (b) from 100: 1 to 1: 5, the acetate groups optionally being saponified up to 15%. 3. shaped detergent or cleaning product according to one of claims 1 or 2, characterized characterized in that the coating at least 70 wt .-%, preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular completely from graft copolymers of (a) polyalkylene oxides with (b) vinyl acetate consists. 4. Detergent tablets according to one of claims 1 to 3, characterized in that the molecular weight of the polyalkylene oxides contained in the graft copolymers 2000 to 50,000 gmol ^-1 , preferably 2500 to 40,000 gmol ^-1 , particularly preferably 3000 to 20,000 gmol ^-1 and is in particular 4000 to 10000 gmol ^-1 . 5. shaped detergent or cleaning product according to one of claims 1 to 4, characterized characterized in that the vinyl acetate content in the graft copolymers 1 to 60 wt .-%, preferably 2 to 50% by weight, particularly preferably 3 to 40% by weight and in particular 5 up to 25% by weight, based in each case on the graft copolymer. 6. Detergent tablets according to one of claims 1 to 5, characterized characterized in that the weight ratio of uncoated molded body to  Coating larger than 10 to 1, preferably larger than 25 to 1 and in particular larger than 50 to 1. 7. Detergent tablets according to one of claims 1 to 6, characterized characterized in that the thickness of the coating on the molded body is 0.1 to 500 µm, preferably 0.5 to 250 microns and in particular 5 to 100 microns. 8. shaped detergent or cleaning product according to one of claims 1 to 7, characterized characterized in that the coating in addition to the polymers mentioned polyurethanes in amounts of 5 to 50% by weight, preferably of 7.5 to 40% by weight and in particular of 10 to 30 wt .-%, each based on the coating contains. 9. shaped detergent or cleaning product according to one of claims 1 to 8, characterized characterized in that the coating additionally one or more substances from the groups disintegration aids, dyes, optical brighteners, fragrances, enzymes, Bleaching agents, bleach activators, silver protection agents, complexing agents, surfactants, Graying inhibitors and their mixtures in amounts of 0.5 to 30% by weight, preferably from 1 to 20% by weight and in particular from 2.5 to 10% by weight, in each case based on the weight of the coating. 10. shaped detergent or cleaning product according to one of claims 1 to 9, characterized characterized in that they additionally contain a disintegration aid, preferably a Disintegration aid based on cellulose, preferably in granular, co-granulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the molding weight, contain, preferred disintegration aids average particle sizes above 300 microns, preferably above 400 microns and especially above 500 microns exhibit. 11. shaped detergent or cleaning product according to one of claims 1 to 10, characterized characterized in that they contain anionic (s) and / or nonionic (s) surfactant (s) and Total surfactant contents above 2.5% by weight, preferably above 5% by weight and  in particular above 10% by weight, based in each case on the molding weight, exhibit. 12. Process for the production of coated detergent tablets by known compression of a particulate washing and Detergent composition and subsequent immersion in or spraying with a melt, solution or dispersion of one or more polymers from the group of Graft copolymers obtainable by grafting (a) polyalkylene oxides with (b) Vinyl acetate. 13. The method according to claim 12, characterized in that an aqueous solution of one or several polymers from the group of graft copolymers which are obtainable by Grafting (a) polyalkylene oxides with (b) vinyl acetate sprayed onto the moldings is, the aqueous solution, in each case based on the solution, 10 to 90 wt .-%, preferably 15 to 85 wt .-% and in particular 20 to 60 wt .-% polymer (s) optionally to up to 20% by weight, preferably up to 10% by weight and in particular below 5% by weight of one or several water-miscible solvents and the rest water. 14. The method according to claim 12, characterized in that a solution or dispersion one or more polymers from the group of graft copolymers that are available by grafting (a) polyalkylene oxides with (b) vinyl acetate in a solvent or Solvent mixture from the group water, ethanol, propanol, iso-propanol, n-heptane and their mixtures with the aid of inert blowing agents from the group nitrogen, Nitrous oxide, propane, butane, dimethyl ether and their mixtures on the shaped bodies is sprayed on. 15. The method according to claim 14, characterized in that the solution or dispersion has the following composition:

• a) 30 to 99% by weight, preferably 40 to 90% by weight and in particular 50 to 85% by weight of ethanol, propanol, isopropanol, n-heptane or mixtures thereof,
• b) 0 to 20, preferably 1 to 15 and in particular 2 to 10% by weight of water,
• c) 1 to 50, preferably 2 to 25 and in particular 3 to 10% by weight of one or more polymers from the group of the graft copolymers which can be obtained by grafting (a) polyalkylene oxides with (b) vinyl acetate.

16. The method according to claim 12, characterized in that a melt of polymers from the group of graft copolymers which can be obtained by grafting (a) Polyalkylene oxides with (b) vinyl acetate, which optionally contains further constituents the molded body is applied. 17. The method according to any one of claims 12 to 16, characterized in that the to Coating moldings obtained by pressing a particulate premix containing granulate (s) containing surfactant and a bulk density of at least 500 g / l, preferably has at least 600 g / l and in particular at least 700 g / l. 18. The method according to claim 17, characterized in that the surfactant-containing granules Particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 µm. 19. The method according to any one of claims 17 or 18, characterized in that the Particulate premix additionally one or more substances from the group of Bleaching agents, bleach activators, disintegration aids, enzymes, pH adjusting agents, Fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, Contains color transfer inhibitors and corrosion inhibitors. 20. Use of polymers or polymer mixtures for coating washing and Detergent tablets, the polymer or at least 50 wt .-% of Polymer mixture is selected from the group of graft copolymers that are available are by grafting (a) polyalkylene oxides with (b) vinyl acetate.