WO2000066702A1

WO2000066702A1 - Washing method comprising detergent tablets

Info

Publication number: WO2000066702A1
Application number: PCT/EP2000/003663
Authority: WO
Inventors: Fred Schambil; Monika Böcker; Hans-Friedrich Kruse
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-05-03
Filing date: 2000-04-22
Publication date: 2000-11-09
Also published as: AU4555100A; CA2307430A1; DE19920119A1; AR023831A1

Abstract

The aim of the invention is to overcome the disadvantages of dosing detergent tablets directly into the washing drum, in particular, how to avoid the use of dosing devices whilst overcoming the problem of poor dissolution or 'spotting'. This is achieved by a washing method for washing textiles which uses detergent and cleansing-agent shaped bodies in a conventional domestic washing machine, whereby said detergent and cleansing-agent shaped bodies are added to the washing in the drum and without a dosing device before the washing process and contain sodium percarbonate.

Description

"Washing process with detergent tablets"

The present invention relates to a washing method for washing textiles in a household washing machine. In this washing process, detergent tablets, which are referred to as detergent tablets for short, are used.

Detergent and cleaning agent compositions in the form of moldings, in particular tablets, have long been known and widely described in the prior art, although this form of offer had until recently not been of outstanding importance on the market. The reason for this is that, in addition to a number of advantages, the form in which the shaped body is offered also has disadvantages which impair production and use, as well as consumer acceptance. The main advantages of moldings such as the fact that the consumer does not have to measure the required amount of product, the higher density and thus the reduced packaging and storage costs, and an aesthetic aspect that should not be underestimated are offset by disadvantages such as the dichotomy between acceptable hardness and sufficiently rapid disintegration and Dissolution of the moldings and numerous technological difficulties in production and packaging put into perspective. To solve these problems, there has recently been extensive state-of-the-art technology, and detergent tablets are now being offered as a form of supply for detergents and cleaning agents almost all over Europe. So far, only two ways of dosing the tablet-shaped detergents by the consumer have been realized: firstly, metering aids are added to the shaped articles in the sales pack, into which the shaped articles must be placed before use. The dosing device including the inserted tablet is then placed in the washing drum for washing. These mostly network-like dispensers are intended to prevent the detergent tablets from coming into direct contact with the laundry, since the sometimes longer dissolution times without the doser would lead to tablet residues coming into direct contact with the laundry, which in turn can cause discoloration or brightening to occur locally on the laundry. Another task of the dosing device is to improve the dissolving behavior of tablets in drum washing machines. Since the washing drum is slightly inclined forward, it can happen that the molded body is pressed into the gap between the sealing ring and the porthole by the moving laundry. It is hardly possible for the water to enter the molded body on this rubber sleeve, so that the tablet remains undissolved or breaks down too slowly on the rubber sleeve. On the one hand, the consumer has the annoyance of a poorer washing result, since the active substance of the undissolved molded article was not available or was only available with a long delay in the wash cycle, on the other hand, the removal of tablet residues from the rubber sleeve is also a nuisance for the consumer. This phenomenon is to be prevented by the metering devices, since the moving laundry covers part of the metering network or solid molded body and pulls the metering device along, even if it happens to be on the rubber sleeve.

On the other hand, detergent tablets are offered which, like conventional powder detergents, can be washed in via the detergent dispenser of household washing machines. Since these tablets already disintegrate in the induction chamber and are thus injected into the machine as powder, the problems mentioned above, which is referred to as "pin hole spotting" in English, do not exist in them because of the small amount of water used for induction and due to the short induction time, much greater demands are placed on such detergent tablets than on conventional tablets with dosing devices. The problem of "spotting" in the case of drum dosing occurs in particular in the case of tablets which contain bleach. The direct contact of the moistened bleach-containing tablet with the laundry locally results in a high concentration of peroxygen which can bleach dyes. Bleach-containing detergent tablets are also broadly described in the prior art:

For example, European patent application EP-A-0 481 793 (Unilever) discloses detergent tablets in which individual ingredients are present separately from others. The detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability. Information on the particle size and dosage of the finished detergent tablets cannot be found in the document.

Detergent tablets which contain sodium percarbonate are described in the older German patent application DE 198 43 778.1 (Henkel KGaA). The moldings described here are distinguished by a high hardness and disintegration speed because the sodium percarbonate contained in them consists of at least 60 percent of its weight from particles with a particle size of less than 0.8 mm. The teaching of this document according to the invention makes it possible to provide detergent tablets which can be washed in via the detergent dispenser of household washing machines.

International patent application WO98 / 42816 (Unilever) describes detergent tablets in which the bleaching agent is selected from sodium perborate tetrahydrate, sodium percarbonate or mixtures thereof. No information can be found in the writing regarding the use of these tablets.

The present invention was based on the object of avoiding the disadvantages of detergent tablets when dosing via the washing drum. In particular, a washing process should be provided in which the use of dosing devices can be dispensed with without problems with regard to the dissolving behavior or "spotting". Since the tablet is inserted into a Dosers and the closing of the doser are perceived by the consumer as additional and unnecessary steps, a washing process should be provided which enables the consumer to meter the drum without the hassle of additional work.

It has now been found that a washing process in which the detergent tablets dosed via the drum contain sodium percarbonate meets the requirements mentioned.

The invention relates to a washing process for washing textiles using detergent tablets in a household washing machine, in which the detergent tablets are added to the laundry without a metering aid before washing and contain sodium percarbonate.

It has been shown that the washing process according to the invention overcomes the disadvantages mentioned. Detergent tablets containing sodium percarbonate can be added directly to the drum as part of the washing process according to the invention, without the need for a metering aid to avoid dissolving or “spotting” problems.

To develop the desired bleaching performance, the detergent tablets used in the washing process according to the invention contain

Sodium percarbonate. Here, “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 C0 ₃ -3 HO ₂ and is therefore not peroxy carbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^"3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as peroxy carbonate. It was not until 1909 that the compound was Addition compound recognized, but the historical name "sodium percarbonate" has prevailed in practice, which is why it is also used in the context of the present application.

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 1300 g / 1 depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available types of percarbonate can be used, such as those offered by Solvay Interox, Degussa, Kemira or Akzo. According to the invention, the advantageousness of the rapid molding disintegration results from the defined particle size of the percarbonate.

The sodium percarbonate is used in varying amounts depending on the desired product performance. Usual contents are between 5 and 50% by weight, preferably between 10 and 40% by weight and in particular between 15 and 35% by weight, in each case based on the entire molded body. Washing processes according to the invention in which the detergent tablets contain sodium percarbonate in amounts of 1 to 40% by weight, preferably 5 to 30% by weight and in particular 10 to 25% by weight, based in each case on the weight of the tablet. are preferred.

The advantageousness of the use of sodium percarbonate within certain particle size ranges described in the prior art can also be applied to the process according to the invention. So washing processes are preferred in which at least 60 wt .-%, preferably at least 70 wt .-%, particularly preferred at least 80% by weight and in particular at least 90% by weight of the sodium percarbonate particles contained in the detergent tablets

Have particle size below 0.8 mm, it being particularly preferred that the sodium percarbonate contained in the shaped bodies is substantially free of particles with sizes above 1.2 mm.

In addition to sodium percarbonate, the detergent tablets used in the washing process according to the invention can contain bleach activator (s), which is preferred in the context of the present invention. Bleach activators are incorporated into detergents and cleaning agents to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacrylic alkylenediamines, in particular tetraacetylethylene diamine (TAED), acyherized triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acyherized glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acyherten phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acyherte polyhydric alcohols, especially diacetyloxy, especially triacetate, 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. 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 also be used as bleaching catalysts. The moldings used in the washing process according to the invention usually contain, based in each case on the entire mold, 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. These amounts can vary depending on the intended use of the moldings produced. For example, bleach activator contents of between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight, are common in typical universal detergent tablets, while bleach tablets contain quite high contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight. The person skilled in the art is not restricted in its freedom of formulation and can thus produce more or less bleaching detergent tablets, detergent tablets or bleach tablets by varying the bleach activator and bleach content.

Particularly preferred bleach activators used are N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaning agents, and n-nonanoyloxybenzenesulfonate (NOBS). Accordingly, preferred detergent tablets are characterized in that tetraacetylethylenediamine is used as the bleach activator in the amounts mentioned above.

In addition to the ingredients mentioned, the detergent tablets used in the washing process according to the invention can contain further ingredients, the amounts of which depend on the intended use of the tablets. For example, substances from the groups of surfactants, builders and polymers are particularly suitable for use in the detergent and cleaning agent moldings according to the invention. Here too, the person skilled in the art will have no difficulty in selecting the individual components and their amounts. For example, a universal detergent tablet will contain higher amounts of surfactant (s), while bleach tablets may even be dispensed with. The amount of builder (s) used also varies depending on the intended use. The detergent tablets used in the washing process according to the invention can contain all builders customarily used in detergents and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Suitable crystalline schichtfb ^'-shaped sodium silicates have the general formula NaMSi _x θ ₂ ₊ χ ^ι' H ₂ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred Values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. 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 disilicate Na Si ₂ O ₅ 'yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171.

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 are added

Electron diffraction experiments provide washed-out or even sharp diffraction maxima. 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, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. 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 (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O ^• (ln) 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 and can also be used for a kind of "powdering" of the entire mixture to be veφressed, usually both ways of incoφoration of the zeolite in the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance 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 PO4 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 dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ θ ₇ ) at 200 ° C, and at higher temperatures in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ Pθ _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light 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 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na P ₂ O ₇ when heated more. Disodium hydrogen phosphate is used by neutralizing phosphoric acid with soda solution Made from phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K2HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P ₂ θ ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39 ^ -0% P ₂ _O. O have a density of 2.536 like ^"3. Trisodium phosphate is readily soluble in water with an alkaline reaction and a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH is prepared by evaporation Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction when heating Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate),

exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na4P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating 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 ^"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 produces higher mol. 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 θιo (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, white, crystallizing with 6 HO, white, Water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. Approx. 17 g dissolve in 100 g water at room temperature and approx. 20 g at 60 °. at 100 ° around 32 g of the salt free from water of crystallization: after heating the solution to 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 + 2 KOH - Na ₃ K ₂ P3θι ₀ + H ₂ O

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; 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 also be used according to the invention.

Organic cobuilders which can be used in the detergent tablets used in the washing process according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, polycarboxylic acids being those Carboxylic acids are understood that carry 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), as long as such use is not objectionable for ecological reasons, and 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. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative 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 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content 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 contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

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

Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that in addition to cobuilder properties they also have a bleach-stabilizing effect. Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from 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, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both 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 molar masses in the range from 2000 to 30000 g / mol can be used.

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. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferred in the form of its sodium or magnesium salts used. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 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 contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the 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 pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

The amount of builder is usually between 10 and 70 wt .-% _0, preferably between 15 and 60 wt .-% and in particular between 20 and 50% by weight. Again, the amount of builders used is dependent on the intended use, so that bleach tablets can 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), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 up to 45% by weight> especially between 7.5 and 37.5% by weight).

In preferred washing methods according to the invention, the detergent tablets further contain one or more surfactant (s). In the washing and used in the washing process according to the invention

Detergent tablets can be anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C ₉ -i ₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from Ci ₂ -i ₈ monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from Ci ₂ -i ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fatty acids having 6 to 22 carbon atoms, for example the Capron acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the Ci ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₆ alkyl sulfates and C ₂ -C ₅ -alkyl sulfates and C] -C ₅ -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 the Shell Oil Company under the name DAN, are also suitable anionic surfactants.

Also, the Schwefelsäuremonoester with 1 to 6 moles of ethylene ethoxylated straight-chain or branched C _{_7-21} alcohols, such as 2-methyl-branched C ₉ -n alcohols containing on average 3.5 mol ethylene oxide (EO) or C ₂ - ₈ -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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -ι ₈ 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, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are special prefers. 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. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. 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 also 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, in particular 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. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. ₁₄ - - The preferred ethoxylated alcohols include, for example, ₁₂ C, alcohols containing 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, Cι ₃ -. ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci2-ι ₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ - ₁₄ - alcohol having 3 EO and C _{_2-18} - alcohol with 5 EO. The degrees of ethoxylation given represent 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 this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In addition, alkyl glycosides of the general formula RO (G) can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon 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 preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or 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 esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

R ¹

R-CO-N- [Z] (I)

in the RCO for an aliphatic acyl radical with 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 (II)

R ^ OR ²

R-CO-N- [Z] (II)

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, where Cj. ₄ - Alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[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, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In the context of the present invention, washing processes are preferred in which the detergent tablets used contain anionic (s) and nonionic (s) surfactant (s), the application-related advantages resulting from certain quantitative ratios in which the individual classes of surfactants are used can. Washing methods are particularly preferred in which the detergent tablets contain anionic and / or nonionic surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5% by weight. % and in particular above 10 wt .-%, each based on the molded body weight.

For example, washing processes are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) in the detergent tablets used is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular is between 5: 1 and 1: 2. Preference is also given to washing processes in which the detergent tablets have surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40% by weight, preferably 7.5 up to 35% by weight, particularly preferably from 10 to 30% by weight and in particular from 12.5 to 25% by weight, based in each case on the molded body weight.

From an application point of view, it can be advantageous if certain classes of surfactants are used in some phases of the detergent tablets used in the washing process according to the invention or in the entire molded article, i.e. in all phases, are not included. A further important embodiment of the present invention therefore provides that at least one phase of the molded articles used in the washing process is free of nonionic surfactants.

Conversely, the content of individual phases or the entire molded body, i.e. all phases, certain surfactants have a positive effect. The introduction of the alkyl polyglycosides described above has proven to be advantageous, so that washing processes are preferred in which at least one phase of the moldings used contains alkyl polyglycosides.

Similar to nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent tablets that are better for certain areas of application own. It is therefore also conceivable in the context of the present invention to use washing and cleaning detergent tablets in which at least one phase of the tablets is free from anionic surfactants.

The detergent tablets used in the washing process according to the invention can additionally also contain a so-called “disintegrant”. In order to facilitate the disintegration of highly compressed tablets, disintegration aids, so-called tablet disintegrants, can be incorporated into them in order to reduce the disintegration times. Accelerators of disintegration are understood according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology ^' " (6th edition, 1987, p. 182-184) auxiliary substances that are necessary for the rapid disintegration of tablets in Water or gastric juice and ensure the release of the pharmaceuticals in an absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Detergent tablets preferably to be used in the washing process according to the invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. -% o and in particular from 4 to 6 wt .-%, each based on the molded body weight.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and Reinigungsmittelformköφer such a disintegrant based on cellulose in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-%. and in particular contain 4 to 6% by weight. Pure cellulose has the formal gross composition (C ₆ HιoO ₅ ) _n and, formally speaking, is a ß-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 these mixtures of cellulose derivatives 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 disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets, which contain disintegrants in granular or, optionally, granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of 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 coarser cellulose-based disintegration auxiliaries mentioned above and described in more detail in the cited documents are preferably to be used as disintegration auxiliaries in the context of the present invention and are commercially available, for example, under the name Arbocel * TF-30-HG from the Rettenmaier company.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30%> of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

As disintegration-promoting systems are used in washing and

Shaped detergent tablets are often also used in so-called "effervescent systems". Usually, effervescent systems use oligomeric oligocarboxylic acids such as succinic acid, maleic acid and in particular citric acid in combination with carbonates or hydrogen carbonates. In preferred embodiments of the present invention, however, the detergent tablets used are not "effervescent tablets", i.e. preferred detergent tablets are free of oligomeric oligocarboxylic acids, especially citric acid.

In addition to the above-mentioned components bleach, bleach activator, builder, surfactant and disintegration aid, the detergent tablets used in the washing process according to the invention can contain further ingredients from the group of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents which are customary in detergents and cleaning agents , Graying inhibitors, color transfer inhibitors and corrosion inhibitors. In preferred washing processes, the detergent tablets additionally contain one or more substances from the group of bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Because there are different types of cellulase distinguish by their CMCase and Avicelase activities, the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-% ₀ are preferably from 0.5 to about 4.5 wt .-%.

In addition, the detergent tablets used in the washing process according to the invention may also contain components which have a positive influence on the ability to wash oil and fat out of textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the Moφholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example 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 also be used. Dyes and fragrances are added to the detergent tablets used in the washing process according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and sensorially "typical and unmistakable" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl benzylatepylpionate, allylcyclohexyl propyl pionate. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, oc-isomethylionone and methyl cedryl ketone, to the alcohols A ethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol and Teφineol, to the hydrocarbons belong mainly the Teφene like Limonen and Pinen. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example 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 dye content of the detergent tablets used in the washing process according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the entire formulation.

The fragrances can be incorporated directly into the detergents to be used in the washing process according to the invention, but it can also be advantageous to apply the fragrances to carriers which ensure that the perfume adheres to the laundry intensify and ensure a long-lasting fragrance of the textiles through a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In order to improve the aesthetic impression of the agents used according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

It has been shown that in the washing process according to the invention it is preferred to use detergent tablets which have a high specific weight. Washing processes in which the detergent tablets have a density of above 1000 ^"3 , preferably above 1050 gcm ^" and in particular above 1100 gcm ^" are preferred according to the invention.

The washing method according to the invention comprises textile washing in a household washing machine using a washing and cleaning agent shaped body which is added to the washing drum without a metering aid. The placement of the molded body (or the molded body, if several molded bodies are to be used) in the drum is freely selectable by the consumer. So first the laundry can be put into the machine and then the detergent and cleaning agent shaped body (s) can be added, which is placed on the laundry or placed in the middle of the laundry. A washing method in which the detergent tablets are placed on or in the laundry in the drum before the wash cycle is a preferred embodiment of the present invention. Of course, it is also possible to place the detergent and cleaning product body (s) in the drum first and then to put the laundry into the washing machine. Such a washing method, in which the detergent tablets are placed in the drum and the laundry is placed on the tablet before the wash cycle, is also a preferred embodiment of the present invention.

In order not to limit the consumer with regard to the possible uses of the molded articles given to him, it is preferred to also perform outstandingly in applications which do not fall under the dosage recommendation. If conventional detergent tablets are metered into the detergent dispenser by the consumer, the lack of disposability and the poor washing result due to the lack of detergent lead to frustration on the part of the consumer. It is therefore preferred in the context of the present invention that the detergent tablets can also be dispensed without residue even when metered through the dispensing chamber and the detergent is thus available to the washing process. A washing method according to the invention, in which the detergent tablets can also be metered without residue via the induction chamber, is therefore preferred according to the invention.

In the context of the present invention, “residue-free” means that a maximum of 5% by weight of the originally metered amount of detergent is in the detergent dispenser after the dispensing process, the amount remaining in the dispenser being weighed out after drying.

Examples:

For the production of detergent tablets containing sodium percarbonate, a surfactant granulate was mixed with other processing components and pressed into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g). The composition of the surfactant granules is given in Table 1 below, the composition of the premix to be treated (and thus the composition of the shaped bodies) can be found in Table 2.

Table 1: Surfactant granules [% by weight]

Table 2: Premix [% by weight]

For decay investigations, two molded bodies were tested in different washing machines. For this purpose, the machine was loaded with 3.5 kg of laundry, and two molded bodies were placed in the laundry and a 40 ° C colored washing program was started without prewashing. For comparison, commercially available molded bodies were used, which according to the dosing instructions had to be dosed over a drum using a mains dosing device. These contained sodium perborate as the bleaching agent and were metered in without a metering device analogously to the washing process according to the invention. At the end of the washing program, the residues on the rubber collar of the washing machine were assessed visually. Discoloration of the laundry was also assessed using the following scheme in both assessments:

++ no residue on the cuff / no discoloration

+ slight residues on the cuff / slight lightening of black textiles clear residues on the cuff / visible discoloration on colored ones

Textiles large residues (tablet residues) on the cuff / significant discolouration of colored laundry

The results of the two washing processes in different machines are shown in Table 3:

Table 3: Washing process (comparison)

Claims

Claims:

1. Washing method for washing textiles using washing and cleaning agent shaped bodies in a household washing machine, characterized in that the washing and cleaning agent shaped bodies are added to the laundry in the drum and contain sodium percarbonate without metering aid.

2. Washing method according to claim 1, characterized in that the washing and cleaning agent molded sodium percarbonate in amounts of 1 to 40% by weight, preferably 5 to 30% by weight o and in particular 10 to 25% by weight o, each based on the molded body weight.

3. Washing method according to one of claims 1 or 2, characterized in that at least 60 wt .-%, preferably at least 70 wt .-%, particularly preferably at least 80 wt .-% and in particular at least 90 wt .-%> of those in the Detergent shaped bodies containing sodium percarbonate particles have a particle size below 0.8 mm, it being particularly preferred that the sodium percarbonate contained in the shaped bodies is substantially free of particles with sizes above 1.2 mm.

4. Washing method according to one of claims 1 to 3, characterized in that the washing and cleaning agent form surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40 wt. %, preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight and in particular from 12.5 to 25% by weight, in each case based on the molded body weight.

5. Washing method according to one of claims 1 to 4, characterized in that the washing and cleaning agent form additionally a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight. %, preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-% o, each based on the molded body weight.

6. Washing method according to one of claims 1 to 5, characterized in that the washing and cleaning agent shaped bodies have a density above 1000 like ^"3 , preferably above 1050 like ^{" 3} and in particular above 1100 like ^"3" .

7. Washing method according to one of claims 1 to 6, characterized in that the washing and cleaning agent form additionally one or more substances from the group of bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents , optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

8. Washing method according to one of claims 1 to 7, characterized in that the washing and cleaning agent molded articles are placed on the laundry in the drum before or after the washing cycle.

9. Washing method according to one of claims 1 to 8, characterized in that the washing and cleaning agent molded articles are placed in the drum and the laundry is placed on the molded articles before the washing cycle.

10. Washing method according to one of claims 1 to 9, characterized in that the washing and cleaning agent shaped body can also be metered without residue via the induction chamber.