WO2003097785A1

WO2003097785A1 - Washing and cleaning agent-containing shaped body with an active phase

Info

Publication number: WO2003097785A1
Application number: PCT/EP2003/004712
Authority: WO
Inventors: Maren Jekel; Michael Dreja; Andreas Buhl; Arnd Kessler
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2002-05-15
Filing date: 2003-05-06
Publication date: 2003-11-27
Also published as: DE10221559A1; DE10221559B4; EP1504084A1; AU2003233237A1

Abstract

Disclosed are single-phase or multi-phase washing or cleaning agent-containing shaped bodies comprising at least one active phase which consists of one or several active washing and/or cleaning substance/s and a solid matrix enveloping said substance/s. The solid matrix has a solubility of more than 100 g/L and is provided at a proportion of at least 10 percent by weight of the total weight of the active phase. The inventive shaped bodies are characterized by an improved performance profile, particularly concerning the use of conditioning additives.

Description

Detergent tablets with active phase

The present invention is in the field of detergent tablets, such as those used for portioning and dosing universal detergents for textiles or automatic dishwashing detergents. In particular, the present invention relates to single-phase or multi-phase detergent tablets which have an active phase, which in turn enables the accelerated provision of detergent and cleaning substances, in particular caring additives, and combines this improved performance profile with improved product appearance.

In the field of detergents and cleaning agents, the detergent tablets, in particular the detergent tablets, are very popular with consumers due to their easy handling. In an effort to progressively improve these products, so-called combination products have recently been developed which, in addition to the classic cleaning action, have, for example, an additional fabric softener or rinse aid function. By integrating one or more additional functions into the conventional detergent or cleaning agent, the separate dosing of a corresponding second product (fabric softener, rinse aid, etc.) is unnecessary in an additional operation, and the entire operation is simplified. However, the time-controlled release of this additive is a prerequisite for the optimal effectiveness of the integrated additional function incorporated in the washing or cleaning agent. The agents for the assembly and controlled release of detergent or cleaning agent additives known in the prior art are generally technically complex and frequently developed for the use of special additives and therefore cannot be used universally.

For example, WO 00/51724 (Procter & Gamble Company) describes the use of molecular sieves with a pore diameter above 8 angstroms for the assembly and the controlled release of additives from textile detergents such as fabric softeners or fragrances. However, the use of the disclosed molecular sieves is technically comparatively complex. The insoluble molecular sieves can also remain as insoluble residues on the objects to be cleaned after use.

WO 00/39259 and WO 01/64823 (Reckitt Benckiser) disclose water-soluble glasses and ceramic compositions for the corrosion protection of glassware. The water-soluble glass or ceramics contain at least one active agent for the corrosion protection of glassware (e.g. Zn-oxide, Al-oxide, Ti-oxide) and are used in solid, paricular form in automatic dishwashing. The glasses and ceramics described are suitable only for glass corrosion protection. Additives for silver corrosion protection or topping inhibition cannot be integrated into the stressed glasses.

The object of the present application was therefore to provide a detergent tablet which is suitable for the assembly of the combination products mentioned above and at the same time enables the rapid release of additives contained in these combination products, in particular additives with a low proportion by weight of the overall formulation of the detergent tablets without being limited to selected additives. At the same time, the corresponding shaped detergent or cleaning agent should have an improved appearance, in particular a direct visualization of the additives contained in the combination product should be realized.

This object was achieved by providing single-phase or multi-phase detergent tablets which have at least one active phase. A first subject of the present application is therefore a single-phase or multi-phase detergent tablet which has at least one active phase, consisting of one or more washing and / or cleaning-active substance (s) and a solid matrix surrounding this substance (s) , characterized in that the solid matrix has a solubility above 100 g / L at 20 ° C and the weight fraction of the solid matrix in the total weight of the active phase is at least 10% by weight.

The active phase (s) contained in the moldings according to the invention are therefore used to assemble substances that are active in washing and / or cleaning, preferably selected additives from the field of washing and cleaning agents. The matrix structure of the active phase, based on at least 10% by weight of matrix material, combined with the high solubility of this matrix material improves the release profile of the enclosed washing and / or cleaning substances and results in an optimized effect of these substances.

Although in the context of the present application the use of matrix materials with a solubility above 100 g / L has been found to be suitable for achieving the object according to the invention, the advantageous effect of agents according to the invention is even further enhanced by the use of matrix materials with solubilities above 200 g / L further strengthened. Another preferred subject of the present application are therefore detergent tablets according to claim 1, characterized in that the solid matrix (s) have a solubility above 200 g / L at 20 ° C, preferably above 300 g / L at 20 ° C has / have. If the solid matrix is formed from more than one matrix material, all matrix materials used in the context of the present invention have a solubility above 100 g / L at 20 ° C., preferably above 200 g / L at 20 ° C., in particular above 300 g / L at 20 ° C.

A matrix structure in the context of the present application can be implemented in different ways. In a first preferred embodiment, the matrix is a homogeneous, solid phase in which the washing and / or cleaning-active substance (s) are present in a homogeneous distribution. Such a homogeneous distribution can be achieved, for example, by dissolving all the washing and / or cleaning-active substances contained in the active phase in a solution or melt of the matrix material and subsequent solidification of this solution or melt. However, the substances active in washing and cleaning can also be present in a heterogeneous distribution in the matrix according to the invention. Such heterogeneous distributions can arise, for example, if solid particles of the washing and / or cleaning-active substance (s) are mixed with a solution or melt of the matrix material or poured over without dissolving. Settling movements, for example due to different densities of the substances used, can then cause an uneven distribution of the solid particles within the matrix in the course of the solidification. As can be seen from the preceding information, the preparation of washing and / or cleaning-active additives with the aid of a melt of the matrix material is a preferred procedure within the scope of the present application. In a further preferred embodiment of the inventive washing or cleaning composition shaped body, one or more meltable substance (s) having a melting point of between 30 and 250 ° C, preferably between 35 and 200 ^{° C} C and in particular between 40 ° and 180 ° C as the matrix material, therefore, contains / included, used. In the context of the present application, particular preference is given to active phases in which all matrix materials have / have a melting point between 30 and 250 ° C., preferably between 35 and 200 ° C. and in particular between 40 and 180 ° C.

A few examples of matrix materials suitable in the context of the present invention with a solubility above 100 g / L and which have the criterion of a melting point between 30 and 250 ° C. are summarized in the following table:

Sugar, sugar acids and sugar alcohols have proven to be particularly suitable matrix materials in the context of the present invention. These substances are generally not only sufficiently soluble, but are also characterized by low costs and good processability. For example, sugar and sugar derivatives, in particular the mono- and disaccharides and their derivatives, can be processed, for example, in the form of their melts, these melts having good solvency both for dyes and for many active washing and cleaning substances. The solid bodies resulting from the solidification of the sugar melts are also distinguished by a smooth surface and an advantageous appearance such as high surface brilliance or a transparent appearance.

Preferred detergent tablets in the context of the present invention are characterized in that the matrix material is selected from the group of sugars and / or sugar acids and / or sugar alcohols, preferably from the group of sugars, particularly preferably from the group of oligosaccharides, oligosaccharide derivatives, Monosaccharides, disaccharides, monosaccharide derivatives and disaccharide derivatives and mixtures thereof, in particular from the group consisting of glucose and / or fructose and / or ribose and / or maltose and / or lactose and / or sucrose and / or maltodextrin and / or Isomalt ^® .

The group of sugars preferred as matrix material in the context of the present application includes from the group of mono- and disaccharides and derivatives of mono- and disaccharides in particular glucose, fructose, ribose, maltose, lactose, sucrose, maltodextrin and Isomalt ^® and mixtures of two, three, four or more mono- and / or disaccharides and / or the derivatives of mono- and / or disaccharides. Mixtures of Isomall ^® and glucose, Isomalt ^® and lactose, Isomalt ^® and fructose, Isomalt ^® and ribose, Isomalt ^® and maltose, glucose and sucrose, Isomall ^® and maltodextrin or Isomalt ^® and sucrose are particularly preferred as matrix materials. The weight fraction of ^{Isomalt® in} the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

Mixtures of maltodextrin and glucose, maltodextrin and lactose, maltodextrin and fructose, maltodextrin and ribose, maltodextrin and maltose or maltodextrin and sucrose are also particularly preferred as the matrix material. The proportion by weight of maltodextrin in the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

In the context of the present application, maltodextrin refers to water-soluble carbohydrates (dextrose equivalents, DE 3-20) obtained by enzymatic degradation of starch with a chain length of 5-10 anhydroglucose units and a high proportion of maltose. Maltodextrin are used to improve the rheological and food. added caloric properties, taste little sweet u. do not tend to retrogradate. Commercial products, for example from Cerestar, are generally offered as spray-dried free-flowing powders and have a water content of 3 to 5% by weight.

As Isomall ^® in the context of the present application, a mixture of _{6-O-α-D-glucopyranosyl-D-sorbitol} (1,6-GPS) and 1-O- _{α-D-glucopyranosyl-D-mannitol} (1,1 -GPM). In a preferred embodiment, the weight fraction of the 1,6-GPS in the total weight of the mixture is less than 57% by weight. Mixtures of this type can be prepared industrially, for example, by enzymatic rearrangement of sucrose into isomaltose and subsequent catalytic hydrogenation of the isomaltose obtained to form an odorless, colorless and crystalline solid. In the context of the present application, matrix materials which are particularly preferably used are also the sugar acids. Sugar acids can be used alone or in combination with other substances such as the above-mentioned sugars in an advantageous manner as a component of the active phase, with sugar acids from the group consisting of gluconic acid, galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid and 2-deoxy-ribonic acid being particularly suitable to be favoured. Particularly preferred are matrix materials which contain Isomalt ^{® in} addition to the sugar acids mentioned. The proportion by weight of Isomalt ^{® in} the total weight of these mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight, mixtures of Isomall ^® with gluconic acid, Isomalt ^® with galactonic acid, isomalt ^® with mannonic acid, isomalt ^® with Fructonsäure, isomalt ^® with arabinonic acid, xylonic acid with isomalt ^®, isomalt ^® are particularly preferred with ribonic acid and isomalt ^® with 2-deoxy-ribonic acid.

A third group of matrix materials which can be used advantageously are the sugar alcohols, of which mannitol, sorbitol, xylitol, dulcitol and arabitol are preferred in the context of the present application. The sugar alcohols can be used alone or as mixtures with one another or as a mixture with other sugars, sugar derivatives, sugar acids or sugar acid derivatives. Mixtures of sugar alcohols with Isomalt ^® are particularly preferably used, mixtures of Isomalt ^® with mannitol, Isomalt ^® with sorbitol, Isomalt ^® with xylitol, Isomalt ^® with dulcitol and Isomalt ^® with arabitol being particularly preferred. The weight fraction of ^{Isomalt® in} the total weight of these mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

As mentioned at the outset, one of the tasks on which this application is based was the preparation of additives with a low proportion by weight of the overall formulation of the detergent tablets with simultaneous direct visualization of the additional function (s) caused by these additive (s). A preferred subject of the present application are, for example, laundry detergent or cleaning product tablets, the active phases of which are washing or cleaning-active substances with a weight fraction below 5% by weight, preferably below 4% by weight and in particular below 2% by weight, in each case based on the total weight of the molded body. Since the visual perception of these low-weight formulation constituents by the consumer is hampered by their small volume, in a special embodiment of the present application preference is given to detergent tablets in which the weight fraction of the solid matrix in the total weight of the active phase is at least 20% by weight. %, preferably at least 40% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight. It should be noted, however, that the increasing proportion of the matrix material in the total weight of the active phase also changes the solution and release profile of the active phase. As a rule, the release of the enclosed washing and / or cleaning substances is delayed with increasing proportion of the matrix material in the total weight of the active phase.

With a view to improved optics, preferred shaped laundry detergents or cleaning compositions according to the invention are further characterized in that the proportion by weight of the active phase is at least 5% by weight, preferably at least 7.5% by weight and in particular at least 10% by weight of the total weight of the wash - Or detergent tablets.

In a particularly preferred embodiment of detergent tablets according to the invention, the active phase is transparent. For the purposes of this invention, transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention. Transparent active phases improve the overall appearance of molded articles according to the invention and offer a further possibility of visualizing the washing or cleaning-active substances contained in these active phases, which may be present in these transparent active phases, for example as crystals or granules, and because of the transparency of the active phases surrounding them at least partially Consumers are visible. Another possibility to improve the optics of active phases according to the invention is their coloring. The active phases of detergent tablets which are particularly preferred in the context of the present application will therefore also contain dyes in addition to matrix material and detergent and / or cleaning substances. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards dishes or textiles, in order not to stain them.

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

For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically dyestuff concentrations in the range of a few selected 10- ² to 10- ³ wt .-%. The due to their brilliance, particularly preferred but are less readily water-soluble pigment dyes, for example the above Pigmosol ^® ATTO-dyes, the appropriate concentration of the dye is in the active phase contrast, typically a few

In summary, preferred single- or multi-phase detergent tablets can be described in the context of the present application in that the active phase a) 10 to 98% by weight of matrix material, b) 1.5 to 90% by weight of one or more washes - and / or cleaning-active substance (s) and c) contains 0 to 1.0% of a dye.

The group of washing and / or cleaning-active substances which are present within the single- or multiphase detergent tablets, in particular within the active phase according to the invention, generally includes all such substances known to the person skilled in the art, in particular individual substances or substance mixtures from the group of bleaching agents, Bleach activators, polymers, builders, surfactants, enzymes, disintegration aids, electrolytes, pH regulators, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors,

Disintegration aids, anti-redeposition agents, optical brighteners,

Graying inhibitors, shrinkage preventers, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, phobing and impregnating agents, swelling and anti-slip agents, non-aqueous solvents, fabric softeners, UV hydrolysers and.

Bleaching agents and bleach activators can be included in the agents according to the invention as important components of detergents and cleaning agents. Among the compounds which serve as bleaching agents and supply H ₂ Q in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Detergent tablets for automatic dishwashing can also contain bleaches from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. More typical Organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy- _α- naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, _ε- phthaloxyhexanoic acid [phthalimidoxyhexanoic acid] (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocyseboxyacidoxy acid, diperoxyacid acid, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

If the agents according to the invention are used as automatic dishwashing agents, they can contain bleach activators in order to achieve an improved bleaching effect when cleaning 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 polyacylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetoxy and 2,5-diacetyloxy and 2,5-glycethylacetyl, ethylene glycol 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the agents. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo Salene 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.

In the context of the present application, preferred washing or cleaning agents contain one or more surfactant (s) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

Anionic surfactants in acid form are preferably one or more substances from the group of carboxylic acids, sulfuric acid half-esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylarylsulfonic acids. In order to have sufficient surface-active properties, the compounds mentioned should have longer-chain hydrocarbon radicals, that is to say they should have at least 6 carbon atoms in the alkyl or alkenyl radical. The C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.

Carboxylic acids, which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification which was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as anionic surfactants in acid form in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. The preferred compound in the context of the present compound is Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacidic acid (melotonic acid), trisonic acid (melotic acid) unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((Elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid). For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as they are accessible from the fat hydrolysis. such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6% by weight C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% C ₁₄ , 10% by weight C ₁₆ , 2% by weight C ₁₈ , 8% by weight C ₁₈ -, 1% by weight C ₁₈ ..), palm kernel oil fatty acid (approx. 4% by weight C ₈ , 5 % By weight C ₁₀ , 50% by weight C ₁₂ , 15% by weight C ₁₄ , 7% by weight C ₁₆ , 2% by weight C ₁₈ , 15% by weight C ₁₈ -, 1% by weight % C _1β ~), tallow fatty acid (approx. 3% by weight C ₁₄ , 26% by weight C _1β , 2% by weight C ₁₆ -, 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight C ₁₈ -, 3% by weight C ₁₈ -, 1% by weight C ₁₈ ...), hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight) % C _16, 2 wt .-% C ₁₇ 63 wt .-% C _18: 1 wt .-% C ₁₈ -), technical grade oleic acid (about 1 wt .-% C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6% by weight C ₁₆ -, 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C ₁₈ - , 10% by weight C _1β », 0.5% by weight C _18. ~), Technical palmitin / stearic acid (approx. 1 wt% C ₁₂ , 2 wt% C ₁₄ , 45 wt% C ₁₆ , 2 wt% C ₁₇ , 47 wt% C ₁₈ , 1 wt% C ₁₈ ) and Soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C ₁₈ -, 45% by weight C ₁₈ -, 7% by weight % C ₁₈ -).

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention. Their alkali metal, in particular sodium salts, the fatty alcohol sulfates, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. In terms of volume, the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids that can be used according to the invention are the alkyl ether sulfuric acids, the salts of which, the alkyl ether sulfates, are distinguished by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates. Like the alkyl sulfuric acids, alkyl ether sulfuric acids are synthesized from fatty alcohols which combine with ethylene oxide to form the fatty alcohol ethoxylates in question be implemented. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the alkyl ether sulfuric acids concerned.

Alkane sulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention. Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons. In Reed sulfochlorination, n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which give the alkanesulfonates directly when hydrolysed with alkalis and the alkanesulfonic acids when reacted with water. Since di- and polysulfochlorides and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually only carried out up to degrees of conversion of 30% and then terminated.

Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under irradiation with UV light. This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylpersulfonyl radicals. The reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical. The reaction of the two radicals with unreacted paraffin gives the alkyl sulfonic acids or water, which reacts with alkyl persulfonic acid and sulfur dioxide to form sulfuric acid. In order to keep the yield of the two end products alkylsulfonic acid and sulfuric acid as high as possible and to suppress side reactions, this reaction is usually carried out only up to degrees of conversion of 1% and then stopped.

Olefin sulfonates are produced industrially by the reaction of _α- olefins with sulfur trioxide. Intermediate hermaphrodites form here, which cyclize to form so-called sultons. Under suitable conditions (alkaline or acid hydrolysis) these sultones react to hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also be used as anionic surfactant acids.

Alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution. In the early 1950s, to produce alkylbenzenesulfonates, propylene was tetramerized to branched _α -dodecylene and the product was converted to tetrapropylenebenzene via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized. This economical possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced the soaps as the main surfactant in washing and cleaning agents.

Due to the lack of biodegradability of TPS, there was a need to prepare new alkylbenzenesulfonates that are characterized by improved ecological behavior. These requirements are met by linear alkylbenzenesulfonates, which today are almost exclusively alkylbenzenesulfonates and are given the abbreviation ABS or LAS.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and dehydrated to the n-olefins, resulting in both _α- and i-olefins. The resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed: when using aluminum trichloride, the content of the 2-phenyl isomers is in of the mixture with the 3, 4, 5 and other isomers at about 30% by weight, on the other hand, if hydrogen fluoride is used as a catalyst, the 2-phenyl isomer content can be reduced to about 20% by weight , Finally, the sulfonation of linear alkylbenzenes is now possible on a large industrial scale with oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the most important. For sulfonation special film or tube bundle reactors are used which deliver a 97% by weight alkylbenzenesulfonic acid (ABSS) as product which can be used as anionic surfactant acid in the context of the present invention.

By choosing the neutralizing agent, a wide variety of salts, i.e. Alkylbenzenesulfonates. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among them, the sodium salts of the ABSS. These can be described by the general formula I:

in which the sum of x and y is usually between 5 and 13. C ₈ are preferred according to the invention as anionic surfactants in acid form. ₁₆ -, preferably C _g _ ₁₃ - alkylbenzenesulfonic acids. It is further preferred in the context of the present invention, C _{8 16} -, preferably C _g . Use _13- alkylbenzenesulfonic acids which are derived from alkylbenzenes and which have a tetralin content below 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C _8.16 -, preferably C ₉ - used. _13- Alkylbenzenesulfonic acids have a content of 2-phenyl isomer below 22% by weight, based on the alkylbenzenesulfonic acid.

The above-mentioned anionic surfactants in their acid form can be used alone or in a mixture with one another. However, it is also possible and preferred that the anionic surfactant in acid form, before addition to the carrier material (s), contains further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40% by weight, preferably of 1 to 15% by weight and in particular from 2 to 10 % By weight, based in each case on the weight of the mixture to be reacted.

Suitable acidic reactants in the context of the present invention are, in addition to the “surfactant acids”, also the fatty acids, phosphonic acids, polymer acids or partially neutralized polymer acids as well as “builder acids” and “complex builder acids” (details later in the text) alone and in any mixtures. As ingredients of washing Acid detergents and cleaning agents are particularly suitable, for example phosphonic acids, which in neutralized form (phosphonates) are components of many detergents and cleaning agents as incrustation inhibitors. The use of (partially neutralized) polymer acids such as polyacrylic acids is also an option According to the invention it is also possible to mix acid-stable ingredients with the anionic surfactant acid, for example so-called small components, which would otherwise have to be added in complex further steps, for example se optical brighteners, dyes etc., whereby the acid stability must be checked in individual cases.

Of course, it is also possible to use the anionic surfactants partially or fully neutralized. These salts can then be present as a solution, suspension or emulsion in the granulating liquid, but can also be part of the solid bed as a solid. In addition to the alkali metals (in particular here according to claim and K salts), ammonium and mono-, di- or triethanolalkonium ions are suitable cations for such anionic surfactants. Instead of mono-, di- or triethanolamine, the analog representatives of mono-, di- or trimethanolamine or those of the alkanolamines of higher alcohols can also be quaternized and present as a cation.

Another group of washing-active substances are the non-ionic surfactants. 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 example. 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 _g ..., 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 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.

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 ester.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides which can be used satisfy the general formula RO (G) ₂ , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, which consist of a glucose residue and an n-alkyl chain, are preferably used.

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. 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 non-ionic 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 (II),

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

in which RCO stands 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 (III)

R ¹ -OR ²

I R-CO-N- [Z] (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 oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical, the alkyl chain of which has at least two Hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propylated 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 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 case of detergents for automatic dishwashing, all surfactants are generally suitable as surfactants. However, the nonionic surfactants described above, and above all the low-foaming nonionic surfactants, are preferred for this purpose. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as C, -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ - alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used in the context of the invention. Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants within the scope of the present invention. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here are Machine dishwashing detergents according to the invention which contain surfactants of the general formula IV as nonionic surfactant (s)

R ¹ -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CH-O) _χ - (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH-O) _z -H (IV )

I I

R ² R ³

in which R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _{6 24} -alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , r-CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another represent integers from 1 to 6.

The preferred nonionic surfactants of the formula IV can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula I above can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals being from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preferred dishwasher detergents according to the invention are those in which R ¹ in formula I for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are also suitable. Preferred automatic dishwashing agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a C _{9 15} -alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, are particularly preferred for use in the agents according to the invention.

Low-foaming nonionic surfactants are used as preferred additional surfactants. If the single-phase or multi-phase detergent tablets according to the invention are used for machine dishwashing, they preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.

Suitable, in addition to the nonionic surfactants contained in the compositions according to the invention, which have melting or softening points in the temperature range mentioned, are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 C- Atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol have resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16th ₂₀ alcohol), preferably a C ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) which consist of C ₆₂₀ monohydroxyalkanols or C _6.20 alkylphenols or C ₁₆ . ₂₀ fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the make up nonionic surfactant.

Other nonionic surfactants with melting points above room temperature that are particularly preferably used contain 40 to 70% of one

Polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blends containing 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred automatic dishwashing agent according to the invention contains nonionic surfactants of the formula

R ⁱ O [CH ₂ CH (CH ₃ ) O] _χ [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, iso-propyl, n -Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in ^the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15. As described above, each R ³ in the above formula can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the latter statements are summarized, preferred agents according to the invention with an active phase contain the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ⁱ O [CH ₂ CH (R ³ ) O] _χ [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type RO [CH ₂ CH (R) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

In connection with the surfactants mentioned, anionic, cationic and / or amphoteric surfactants can also be used, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent. The agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.

In the context of the present invention, it is preferred that when an agent according to the invention is used as the automatic dishwashing agent, surfactant (s), preferably nonionic surfactant (s), in amounts of from 0.5 to 10% by weight, preferably of 0.75 to 7.5 wt .-% and in particular from 1.0 to 5 wt .-%, each based on the total agent, are included.

Cationic surfactants can also be used with advantage as washing or cleaning substances. The delivery form of the cationic surfactant can be added directly to the mixer, or it can be sprayed onto the solid carrier in the form of a liquid to pasty form of cationic surfactant. Such cationic surfactant preparation forms can be prepared, for example, by mixing commercially available cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols. Lower alcohols such as ethanol and isopropanol can also be used, the amount of such lower alcohols in the liquid cationic surfactant preparation form being below 10% by weight for the reasons mentioned above.

All customary substances are suitable as cationic surfactants for the agents according to the invention, cationic surfactants having a fabric softening effect being clearly preferred. The agents according to the invention can contain one or more cationic, fabric softening agents of the formulas V, VI or VII as cationic active substances with fabric softening effect:

R ¹ -N < ⁺ > - (CH ₂ ) _n -TR ² (V)

I

(CH ₂ ) _n -TR ²

R ¹

I

R ¹ -N «- (CH ₂ ) _n -CH-CH ₂ (VI)

I I I

R ¹ TT

I I

R ² R ²

R ¹

R ³ -NW- (CH ₂ ) _n -TR ² (VII)

R ⁴

wherein each R ^{1 group is} independently selected from C 1-4 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8.28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R or R ² or (CH ₂ ) _n - TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In preferred embodiments of the present invention, the solid (s) additionally contain nonionic surfactant (s) as a washing or cleaning-active substance. In addition to the ingredients mentioned, bleach and bleach activator and the surfactants, builders are other important ingredients of detergents or cleaning agents. The agents according to the invention can contain all builders commonly used in cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates. The builders mentioned can of course also be used in surfactant-free compressed products.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} 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 preferred values for x 2 , 3 or 4 are. 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 Na ₂ Si ₂ O ₅ yH ₂ O are preferred.

Amorphous sodium silicates with a module Na ₂ O: SiQ, from 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. Compressed / compacted are particularly preferred amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite that can be 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 ^• (1-n) K ₂ O • AI ₂ O ₃ ^• (2 - 2.5) SiO ₂ - (3.5 - 5.5) H ₂ O

can be described. 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. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

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 dihydrogen phosphate, NaH ₂ PO ₄ , disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , Tetrasodium diphosphate (sodium pyrophosphate), Na ^ O ^ and by condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ arise higher mol. Sodium and potassium phosphates, in which one can differentiate between cyclic representatives, the sodium and potassium metaphosphates and chain-like types, the sodium and potassium polyphosphates, as well as the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) are further within the scope of the present Registration with advantage used builders.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their alkali metal and in particular sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids,

Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that 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.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates,

Alkali metal sesquicarbonates, alkali silicates, alkali metasilicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.

If the agents according to the invention are used for machine dishwashing, water-soluble builders are preferred, since they generally have less tendency to form insoluble residues on dishes and hard surfaces. Common builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of the disilicate and / or metasilicate are preferably used for the production of tablets for machine dishwashing. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system which contains a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred. Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.

In order to facilitate the disintegration of the inventive compositions, these agents can disintegration aids, so-called ^'tablet disintegrating agents. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliaries which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in 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. All of the disintegration aids mentioned can be used according to the invention. In the context of the present invention, preferred disintegration aids are cellulose-based disintegration aids, preferably in granular, cogranulated or compacted form.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O 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 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. 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. In addition to or instead of the cellulose-based disintegration aids, the agents according to the invention can contain a gas-releasing system composed of organic acids and carbonates / hydrogen carbonates.

The solid mono-, oligo- and polycarboxylic acids, for example, can be used as organic acids which release carbon dioxide from the carbonates / bicarbonates in aqueous solution. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

The acids mentioned do not have to be used stoichiometrically to the carbonates or hydrogen carbonates contained in the compressed products.

A single- or multi-phase detergent tablets preferred in the context of the present invention additionally contains a shower system.

In the agents according to the invention, the gas-developing shower system consists of carbonates and / or bicarbonates in addition to the organic acids mentioned. For reasons of cost, the alkali metal salts are clearly preferred among representatives of this class of substances. In the case of alkali metal carbonates or bicarbonates, in turn, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. Out From a manufacturing point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred.

In order to bring the pH of solutions of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 1% by weight of the total formulation. A particularly preferred pH adjusting agent in the context of the present application is citric acid, where the citric acid can be used both as a pure substance, for example as a monohydrate, or in the form of coated particles.

In the context of the present invention, 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, allyl cyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate. The ethers include, for example, benzyl ethyl 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, - isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. 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 general description of the perfumes that can be used (see above) generally represents the different substance classes of fragrance substances. In order to be perceptible, a fragrance substance must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role plays. Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, the odor impressions being described in "top note", "heart or middle note" (middle note or body ) and "base note" (end note or dry out). Since the smell is largely based on the intensity of the smell, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile, ie non-stick fragrances. When composing perfumes, more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly. In the subsequent classification of the fragrances into "more volatile" or "adherent" fragrances, nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.

A suitable selection of the named fragrances or perfume oils can influence both the smell of the agents according to the invention (product fragrance) and, after the cleaning and care process has ended, the laundry fragrance, for example. While in particular volatile fragrances can be used to influence the product fragrance, the use of more adhesive fragrances is advantageous in order to achieve a sufficient laundry fragrance. Non-stick odoriferous substances that can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champaca flower oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, geranium oil, spruce oil, spruce oil, spruce oil, spruce oil, spruce oil, spruce oil, spruce oil, gannet oil guaiac wood oil, gurjun balsam oil, Helichrysumöl, Ho oil, ginger oil, iris oil, cajeput oil, calamus oil, camomile oil, camphor oil, Kanagaöl, cardamom oil, cassia oil, pine needle oil, Kopaϊvabalsamöl, coriander oil, spearmint oil, caraway oil, Kuminöl, lavender oil, lemongrass oil, lime oil, mandarin oil, melissa oil, Musk grain oil, myrrh oil, Clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spik oil, star anise oil, turpentine oil, turpentine oil, turpentine oil, turpentine oil, turpentine oil Vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil. However, the higher-boiling or solid fragrances of natural or synthetic origin can also be used in the context of the present invention as adhesive fragrances or fragrance mixtures, that is to say fragrances. These compounds include the compounds mentioned below and mixtures of these: ambrettolide, _α -amyl cinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, boryl formate benzyl benzate, benzyl formate benzyl benzate, benzyl formate benzyl benzate, benzyl formate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzate benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzate , Bornyl acetate, _α- bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, famesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropine, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether, , Isoeugenolmethylether, Isosafrol, Jasmon, Kampfer, Karvakrol, Karvon, p- Cresolmethylether, Coumarin, p-Methoxyacetophenon, Methyl-n-amylketone, Methylanthranilsäuremethylester, p-Methylacetophenon, Methylchavikol, p-Methylquinon, Methyl-methyl-naphtholinol, Methyl-n-Methyl-methyl-naphthol -nonylacetaldehyde, methyl-n-nonyl ketone, muscon , ß-Naphtholethylether, ß-Naphtholmethylether, Nerol, Nitrobenzol, n-Nonylaldehyd, Nonylaohol, n-Octylaldehyd, p-Oxy-Acetophenon, Pentadekanolid, ß-Phenylethylalkohol, Phenylacetaldehyd-Dimethyacetal, Salicylacetic acid, Salegylacetic Acid, Salegylacetic Acid, Salegylacetic Acid, Salegylacetic Acid, Salegylacetic Acid, Salegylacetic Acid, Salegylacetic Acid, Salegylacetic Acid, Salicyl Acetic Acid, Salegyl Acetic Acid, Salicyl Acetic Acid, Salicyl Acetic Acid, Salicyl Acetic Acid, Salicyl Acetic Acid, Salicyl Acetic Acid, Salicyl Acetic Acid, Salicyl Acetic Acid, Salyl Acetic Acid, Salicyl Acetate, , Salicylic acid cyclohexyl ester, Santalol, Skatol, Terpineol, Thymen, Thymol, γ-undelactone, Vanilin, Veratrum aldehyde, Cinnamaldehyde, Zimatalkohol, Cinnamic acid, Cinnamic acid ethyl ester, Cinnamic acid benzyl ester. The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and - propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal. In order to improve the aesthetic impression of agents according to the invention, these can contain dyes. The use of dyes is not limited to the active phases according to the invention, but can also take place in one or all further phases in the case of multiphase detergent tablets. To avoid repetition, reference is made to the above explanations on the dyes that can be used.

Hydrotropes or solubilizers are substances which, by their presence, make other compounds which are practically insoluble in a certain solvent soluble or emulsifiable in this solvent (solubilization). There are solubilizers that form a molecular compound with the poorly soluble substance and those that work through micell formation. It can also be said that solubilizers only give a so-called latent solvent its solvency. With water as a (latent) solvent, one speaks mostly of hydrotropes instead of solubilizers, in certain cases better of emulsifiers.

Foam inhibitors that can be used in the agents according to the invention include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials. Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are structured according to the scheme (R ₂ SiO) x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000-150,000, and viscosities between 10 u. 1,000,000 mPa ^• s.

Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether as well as the polymers known from the prior art phthalic acid and / or terephthalic acid or derivatives thereof, 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.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids ( Flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Also usable as graying inhibitors are cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof. Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the fiber direction are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylol amides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters. A particularly suitable substance for textile finishing and care is cottonseed oil, which can be produced, for example, by pressing out the brown, cleaned cottonseed and refining it with about 10% sodium hydroxide or by extracting it with hexane at 60-70 ° C. Such cotton oils contain 40 to 55% by weight of linoleic acid, 16 to 26% by weight of oleic acid and 20 to 26% by weight of palmitic acid. Further agents which are particularly preferred for fiber smoothing and fiber care are the glycerides, in particular the monoglycerides of fatty acids such as, for example, glycerol monooleate or glycerol monostearate.

To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the inventive agents.

In order to prevent undesirable changes in the detergents and cleaning agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents according to the invention can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort of textiles can result from the additional use of antistatic agents, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect.

Phobing and impregnation processes are used to finish textiles with substances that prevent dirt from accumulating or make it easier to wash out. Preferred waterproofing and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents can also be included. The dirt-repellent finish with phobing and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agents in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. Another area of application of waterproofing and impregnating agents is the water-repellent finishing of textile goods, tents, tarpaulins, leather, etc., which, in contrast to waterproofing, does not close the fabric pores, which means that the fabric remains breathable (hydrophobic). The hydrophobizing agents used for hydrophobizing coat textiles, leather, paper, wood etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are e.g. B. paraffins, waxes, metal soaps, etc. with additives to aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organotin compounds and Glutardialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless - similar to greased substances - water drops roll off them without wetting them. So z. B. silicone-impregnated textiles a soft handle u. are water u. stain-resistant; Stains from ink, wine, fruit juices and the like are easier to remove.

The non-aqueous solvents which can be used in the agents according to the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol) ), Ether and the like Glycol ether (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ether), ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and the like. a. Nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene),

Halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, tri-, tetrachloroethene, 1, 2-dichloroethane, chlorofluorocarbons), hydrocarbons (petrol, petroleum ether, cyclohexane, methylcyclohexane, decalin, terpene solvent, benzene, toluene, xylenes). Alternatively, instead of the pure solvents, their mixtures, which for example advantageously combine the solution properties of different solvents, can also be used. Such a solvent mixture, which is particularly preferred in the context of the present application, is, for example, benzine, a mixture of various hydrocarbons suitable for chemical cleaning, preferably with a content of C12 to C14 hydrocarbons above 60% by weight, particularly preferably above 80% by weight and in particular above 90% by weight, based in each case on the total weight of the mixture, preferably with a boiling range from 81 to 110 ° C.

To care for the textiles and to improve the textile properties such as a softer "handle" (finish) and reduced electrostatic charging (increased wearing comfort), the agents according to the invention can contain fabric softeners. The active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as, for example, disteraryldimethylammonium chloride, which, however, due to its inadequate biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation. Such "esterquats" with improved biological Degradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se. Dimethylolethylene urea is also suitable as a finish.

To improve the water absorption capacity, the rewettability of the textiles treated with active phase agents according to the invention and to facilitate the ironing of these textiles, for example silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and then are amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which have, for example, polyethylene glycols, and the polyalkylene oxide-modified dimethyl polysiloxanes.

Due to their fiber-caring effect, protein hydrolyzates are further active substances preferred in the field of detergents and cleaning agents in the context of the present invention. Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins). According to the invention, protein hydrolyzates of both vegetable and animal origin can be used. Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts. According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates. Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures or individual amino acids, such as arginine, lysine, histidine or pyrroglutamic acid, which have been obtained in some other way may also be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products. Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.

Detergents for automatic dishwashing may contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents and glass corrosion inhibitors in particular being particularly important in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogenous organic redox-active compounds, such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes

[Me-TACN) Mn ^{, v} (m-0) ₃ Mn ^{, v} (Me-TACN)] ²⁺ (PF ₆ -) 2.

[Me-MeTACNJ n '^ m-O Mn' ^ Me-MeTACNJ tPFQ- ^,

[Me-TACN) Mn ^l "(m-0) (m-0Ac) ₂ Mn ^{, ll} (Me-TACN)] ²⁺ (PF ₆ -) ₂ and [Me-MeTACN) Mn ^{, ll} (m-0) (m-0Ac) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ -) ₂ , where Me-TACN is 1,4,7-trimethyl-1 , 4,7-triazacyclononane and Me-MeTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Zinc compounds can also be used to prevent corrosion on the wash ware.

In the context of the present invention, it is preferred to additionally use at least one silver protective agent selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole.

In addition to the aforementioned silver protection agents, agents according to the invention can also contain one or more substances for reducing glass corrosion. In the context of the present application, in particular additives of zinc and / or inorganic and / or organic zinc salts and / or silicates, for example the layered crystalline sodium disilicate SKS 6 from Clariant GmbH, and / or water-soluble glasses, for example glasses, which have a loss in mass of at least 0 , 5 mg under the conditions specified in DIN ISO 719, preferred to reduce glass corrosion. Particularly preferred agents contain at least one zinc salt of an organic acid, preferably selected from the group consisting of zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.

As explained at the beginning of this description, it was an object of the present application to provide a detergent tablet which can be used for packaging and optimized release of additives, in particular additives with a low proportion by weight of the total formulation of the detergent tablets. While all of the above-mentioned washing and / or cleaning-active substances can generally also be used as active substances in the active phase of detergent tablets according to the invention, in the context of the present application, the packaging, in particular the packaging of washing or cleaning-active substances from the group of enzymes, Glass corrosion protection agents, silver protection agents, deposit-inhibiting polymers and the pH adjusting agents and mixtures thereof have proven to be particularly advantageous. Another preferred subject of the present application are therefore laundry detergent or cleaning product tablets, characterized in that the washing or cleaning-active substances enclosed by the solid matrix are selected from the group of enzymes and / or the glass corrosion protection agents and / or the silver protection agents and / or the deposit-inhibiting polymers and / or the pH adjusting agent.

Particularly preferred mixtures of active substances are, in particular, mixtures of glass corrosion protection agent and silver protection agent, of glass corrosion protection agent and deposit-inhibiting polymer (s), of silver protection agent and deposit-inhibiting polymer (s) or of glass corrosion protection agent, silver protection agent and deposit-inhibiting polymer (s).

If glass corrosion protection agents or silver protection agents or scale-inhibiting polymers or their aforementioned particularly preferred mixtures are used in the active phases of detergent tablets according to the invention, the proportion by weight of these washing or cleaning-active substances in the total weight of the active phase is preferably 2 to 40% by weight, particularly preferably 3 to 30% by weight and in particular 4 to 25% by weight.

Detergent tablets according to the invention can have one or more phases. Single-phase detergent tablets in the context of the present application are, for example, tablets which have only one active phase in which the active substance (s) present are present in a homogeneous distribution. Such moldings can be produced, for example, by solidifying an active substance-containing melt, as described at the beginning.

However, active phases according to the invention are also suitable for the manufacture of formally processed washing and / or cleaning-active substances. Thus, for example, crystals, powders, granules, extrudates, compactates or castings which contain washing and / or cleaning substances can also be incorporated into the active phases according to the invention. Detergent tablets which contain the washing or cleaning-active substances in the matrix surrounding them in pre-assembled form, preferably as crystal (s) and / or powder and / or Granules (e) and / or extrudate (s) and / or compact (s) and / or castings are therefore preferred in the context of the present application. Because of their advantageous appearance, in particular in combination with transparent active phases, crystals and / or tablets are particularly preferred as a form of confection for the washing and / or cleaning substances contained in the active phase. The tablets that can be used range from the “mini-tabs” with a weight in the range from 50 to 500 mg, preferably 100 to 250 mg, to tablets with a weight above 1 g, preferably above 5 g surrounding active phase not only improves their appearance and release profile, but also increases their fracture stability.Thus, such packaged tablets can generally be tabletted at reduced stamp pressures compared to the production of commercially available washing or cleaning agent tablets and, in addition to improved disintegration properties, also have correspondingly reduced fracture hardness, whereby A distinction must be made between detergent tablets for machine dishwashing and textile detergent tablets with regard to these tablets with reduced hardness that the washing or cleaning-active substances for textile cleaning are present in the matrix surrounding them in tablet form and that these tablet (s) preferably have a breaking hardness below 30 N, particularly preferably below 25 N and in particular below 20 N. Another preferred subject matter of the present application are shaped detergent tablets for machine dishwashing, characterized in that the washing or cleaning-active substances for machine dishwashing are in tablet form in the matrix surrounding them, and these tablets preferably have a hardness below 100 N, particularly preferably have below 85 N and in particular below 70 N. (The hardness of the tablet is determined by exerting a force on the side surfaces of the tablet until the tablet breaks and determining the maximum force that the tablet can withstand.)

The detergent tablets according to the invention are, as explained in the introduction, particularly suitable for assembling combination products which, in addition to the usual constituents of detergents or cleaning agents, also contain one or more additives, in particular from the group of enzymes and / or Contain glass corrosion protection agents and / or the silver protection agents and / or the deposit-inhibiting polymers and / or the pH adjusting agents.

Shaped bodies of this type can be produced by all processes known to the person skilled in the art. However, active phases according to the invention are preferably subsequently integrated into this base body after the production of a detergent or cleaning agent base body. The base body is preferably produced by tableting and / or molding and / or extrusion, but preferably by tableting and / or molding.

Basically, such base bodies are particularly suitable for accommodating the active phase which, after the integration of the active phase, enable the active phase to be presented on the surface of the resulting shaped detergent or cleaning product, since this ensures both an advantageous solution profile and an advantageous appearance. Preferred laundry detergent or cleaning product tablets are distinguished in the context of the present application in that the phase, which consists of one or more washing and / or cleaning-active substance enclosed by a solid matrix, has at least 5%, preferably at least 7.5% and in particular makes up at least 10% of the total surface of the detergent tablet, in a further preferred embodiment, the quotient of the weight fraction of the active phase to the total weight of the detergent tablet and the fraction of the active phase on the entire surface of the detergent or The detergent tablet is at least 0.1, preferably at least 0.2, particularly preferably at least 0.4 and in particular at least 1.0, in other words the active phase occupies a disproportionately large proportion of the surface of such detergent tablets in comparison with their weight percentage.

An example of the above-mentioned basic bodies are the trough tablets which can be produced by tableting, in the trough of which the active phase can be incorporated by a number of different processes. For example, the trough can be filled by pouring a melt or a solution of the matrix material. Subsequent solidification then results in the detergent tablet with active phase according to the invention. The washing and / or cleaning substances can be in one Such processes, for example, optionally a) be contained in the melt or solution of the matrix material, b) are filled in particulate form before the melt or solution is poured into the depression and, optionally, are glued in the depression before the melt or solution is poured in, or c) after Pour the melt or solution of the matrix material into the well and meter it into the melt or solution in particulate form before it solidifies. The above-mentioned crystals, powders, granules, extrudates, compactates and castings are particularly suitable as active substance particles. A further possibility of incorporating the active phase into shaped articles according to the invention is to produce prefabricated active phases by pouring the matrix material melt or solution into casting molds and then allowing it to solidify. Prefabricated active phases produced in this way can then be removed from the casting molds and inserted into the depressions. The active phases can be fastened in the depressions, for example, by gluing. If a base body which has no depression is used in the aforementioned method, a prefabricated active phase can also be attached to a planar surface of this tablet by gluing.

Further preferred objects of the present application are therefore laundry detergent or cleaning product tablets, characterized in that the single-phase or multi-phase washing or cleaning product tablet has a trough which at least partially encloses the active phase, and laundry or cleaning product tablets, characterized in that the washing or detergent tablets has a planar outer surface on which the active phase, which partially covers the planar outer surface, adheres.

Also preferred are single-phase or multi-phase detergent tablets which contain the active phase in the form of a layer.

The single-phase or multi-phase detergent tablets according to the invention can be offered to the consumer in conventional containers made of all the usual water-insoluble packaging materials which are well known to the person skilled in the art in this field. In particular, hydrocarbon-based plastics are to be mentioned as preferred polymers. The particularly preferred polymers include polyethylene, polypropylene (more preferred oriented polypropylene) and polymer mixtures such as, for example, mixtures of the polymers mentioned with polyethylene terephthalate. There are also one or more polymers from the group consisting of polyvinyl chloride, polysulfones, polyacetals, water-insoluble cellulose derivatives, cellulose acetate, cellulose propionate,

Cellulose acetobutyrate and mixtures of the polymers mentioned or copolymers comprising the polymers mentioned in question.

A particularly preferred embodiment of the present invention, however, aims to provide the consumer with agents according to the invention which have a water-soluble packaging which the consumer can directly, i.e. without further handling steps. together with the packaging, for example in the washing machine or in the dishwasher. Such packages include water-soluble or decomposable packaging such as pouches made of water-soluble film (so-called pouches), pouches or other packaging made of water-soluble or decomposable nonwovens or else flexible or rigid bodies made of water-soluble polymers, preferably in the form of filled hollow bodies, for example by deep drawing or injection molding , Blow molding, calendering, etc. can be produced.

A preferred subject of the present invention are therefore single or multi-phase detergent tablets according to the invention which have a water-soluble packaging.

Shaped bodies according to the invention preferably have packaging that is completely or partially soluble in water. The shape of the packaging is not limited to certain shapes. Basically, all Archimedean and Platonic bodies, i.e. three-dimensional shaped bodies, can be used as forms of packaging. Examples of the shape of the packaging are capsules, cubes, spheres, egg-shaped moldings, cuboids, cones, rods or bags. Hollow bodies with one or more compartments are also suitable as packaging for the agents according to the invention. In preferred embodiments of the invention, the packaging is in the form of capsules, as are also used, for example, in pharmacy for the administration of medicaments, of spheres or of sachets. The latter are preferably welded or glued to at least one side, in particular as an adhesive preferred embodiments of the invention, an adhesive is used which is water-soluble.

The exact form of a preferred water-soluble packaging for agents according to the invention is not critical and can largely be adapted to the conditions of use. There are, for example, different shapes (such as hoses, pillows, cylinders, bottles, disks, etc.), processed plastic foils or sheets, capsules and other conceivable shapes. According to the invention, particular preference is given to films which, for example, can be glued and / or sealed to form packaging such as hoses, pillows or the like after they have been filled with one or more of the moldings according to the invention.

Plastic film packaging made of water-soluble polymer materials is further preferred according to the invention on account of the properties which can be adapted excellently to the desired physical conditions. Such films are basically known from the prior art.

In summary, both hollow bodies of any shape, which can be produced by injection molding, bottle blowing, deep drawing, etc., and hollow bodies made of foils, in particular bags (so-called pouches), are preferred as packaging for shaped bodies according to the invention. Preferred moldings according to the invention are thus characterized in that the water-soluble packaging comprises a bag made of water-soluble film and / or an injection molded part and / or a blow molded part and / or a deep-drawn part.

According to the invention, it is preferred that the water-soluble packaging is closed. This has the advantage that the agents are optimally protected against environmental influences, in particular against moisture.

In principle, all materials that can dissolve completely or partially in the aqueous phase under the given conditions of a washing process, rinsing process or cleaning process (temperature, pH value, concentration of detergent components) are suitable as materials for the completely or partially water-soluble packaging. The polymer materials can particularly preferably Groups (optionally partially acetalized) of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, coextrudates etc.) of the materials mentioned belong. Gelatin and polyvinyl alcohols and the two materials mentioned are particularly preferred in each case in combination with starch or modified starch. Inorganic salts and mixtures thereof can also be used as materials for the at least partially water-soluble packaging.

Preferred agents according to the invention are characterized in that the packaging comprises one or more materials from the group consisting of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.

Particularly preferred agents according to the invention are characterized in that the packaging contains one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and their mixtures, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).

"Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

contain. Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents. (Formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

In the context of the present invention, it is preferred that the packaging comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% ,

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the packaging, it being preferred according to the invention that the packaging comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmo ¹ , preferably from 11,000 to 90,000 gmor ¹ , particularly preferably from 12,000 to 80,000 gmoH and in particular from 13,000 to 70,000 gmol- ¹ .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols that are particularly suitable as packaging materials can be found in the table below:

Other polyvinyl alcohols suitable as packaging material are ELVANOL ^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK ).

The water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water. The reaction products made of PVAL and starch are extremely advantageous to use.

Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and so on Set the desired values. PVAL films are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Examples of suitable water-soluble PVAL films are the PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ^® ". Their solubility in water can be adjusted to the exact degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVP are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [O-CH ₂ -CH ₂ ] _n -OH

which are technically produced by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxyl end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is mainly produced by hydrolysis of the collagen contained in the skin and bones of animals acidic or alkaline conditions is obtained. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

Agents according to the invention are also preferred within the scope of the present invention, the packaging of which consists of at least partially water-soluble film made of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.

Starch is a homoglycan, the glucose units being linked _α- glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4-position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6-binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which can be obtained from starch by polymer-analogous reactions are also suitable for the production of water-soluble packaging of the detergent, detergent and cleaning agent portions in the context of the present invention. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn consists of two Molecules of glucose is built up. Suitable celluloses consist of approximately 500 to 5,000 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, carboxymethylceilulose (CMC), cellulose esters and ethers and aminocelluloses.

Preferred packages made of at least partially water-soluble film contain at least one polymer with a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol. Depending on the manufacturing process, the packaging has different material thicknesses, with automatic dishwashing agents according to the invention being preferred in which the wall thickness of the packaging is 10 to 5000 μm, preferably 20 to 3000 μm, particularly preferably 25 to 2000 μm and in particular 100 to 1500 μm.

If foil bags (so-called pouches) are chosen as packaging, the water-soluble foil that forms the packaging preferably has a thickness of 1 to 300 μm, preferably 2 to 200 μm, particularly preferably 5 to 150 μm and in particular 10 to 100 μm μm.

These water-soluble films can be produced by various manufacturing processes. In principle, blowing, calendering and casting processes should be mentioned here. In a preferred method, the foils are blown with air from a melt via a blow mandrel to form a tube. In the calendering process, which is also one of the preferred manufacturing processes, the raw materials plasticized by suitable additives are atomized to form the films. Here it may be necessary to connect drying to the atomization. The casting process, which is also one of the preferred manufacturing processes, is an aqueous polymer preparation is placed on a heatable drying roller; after the water has evaporated, cooling is optional and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal.

According to the invention, an embodiment is preferred according to which the packaging is water-soluble as a whole, ie. H. dissolves completely when used as intended for machine cleaning, if the conditions provided for loosening have been reached. Particularly preferred as completely water-soluble packaging are, for. B. capsules made of gelatin, advantageously made of soft gelatin, or bags made of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably balls made of soft gelatin. The main advantage of this embodiment is that the packaging can be released at least partially within a practically relevant short time - as a non-limiting example, from a few seconds to 5 minutes - under precisely defined conditions in the cleaning liquor and thus, according to the requirements, the wrapped content, i.e. H. introduces the single- or multi-phase detergent tablets according to the invention into the liquor.

In another embodiment of the invention, which is also preferred due to advantageous properties, the water-soluble packaging comprises areas which are less or not water-soluble at all or areas which are water-soluble only at a higher temperature and areas which are water-soluble or water-soluble at a low temperature. In other words: the packaging does not consist of a uniform material that has the same water solubility in all areas, but of materials with different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand. This can lead to certain areas of the packaging becoming detached when used as intended under adjustable conditions, while other areas remain intact. This forms a package with pores or holes into which water and / or liquor penetrate, washing-active, rinsing-active or cleaning-active Can loosen ingredients and remove them from the packaging. In the same way, packaging systems in the form of multi-chamber bags or in the form of hollow bodies arranged one inside the other (eg balls: “onion system”) can also be provided. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be manufactured.

The invention is not subject to any restrictions for the formation of such systems. Packaging can thus be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material. On the other hand, several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble one.

It corresponds to a particularly preferred embodiment of the invention that the less water-soluble areas or non-water-soluble areas or only at higher temperature water-soluble areas of the packaging are areas made of a material which chemically essentially that of the readily water-soluble areas or at lower temperature water-soluble areas corresponds, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or a content has water-insoluble salt components and / or contains a water-insoluble polymer. Even taking into account the fact that the packaging does not completely detach, detergent or cleaning agent portions according to the invention can be provided which have advantageous properties when releasing the dishwashing agents into the respective liquor. In addition to the targeted release of selected washing and / or cleaning-active substances through the active phase, the preferred agents according to the invention provided with such packaging thus offer a second regulation for the controlled release of active substances. The water-soluble covering material is preferably transparent. For the purposes of this invention, transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.

Agents according to the invention, which are packed in transparent packaging or containers, can contain a stabilizing agent as an essential component. Stabilizers in the sense of the invention are materials which protect the detergent components in their water-soluble, transparent packaging from decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesirable changes in the formulations caused by light radiation and thus radical decomposition, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3 ^'- thiodipropionic acid with C _{1 18} alkanols, in particular C _10th ₁₈ -alkanols, metal ion deactivators, which are able to complex the autooxidation-catalyzing metal ions, such as copper, such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the lightfastness of the formulation components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ^® H), are also phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position. , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid. Biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba, are of particular importance. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylide) camphor, are to be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, such as, for example, 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones, such as 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of Benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; , Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidenemethyl) benzene-sulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or shape which differs from the spherical shape in some other way. The pigments can also be surface treated, i.e. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.

UV absorbers can be present in the agents according to the invention in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight.

Another preferred class of stabilizers is the fluorescent dyes. They include the 4,4'-diamino-2,2'-stilbene disulfonic acids (Flavonic acids), 4,4'-distyrylbiphenylene, methyl umbelliferone, coumarins,

Dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles. Of particular importance are the sulfonic acid salts of the diaminostilbene derivatives and polymeric fluorescent substances, as are disclosed in US Pat. No. 5,082,578.

Fluorescent substances can be contained in the agents according to the invention in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.

In a preferred embodiment, the aforementioned stabilizing agents are used in any mixtures. The stabilizing agents are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.

Examples

Example 1 :

^Isomalt® ST-F (150 g, commercial product from Palatinit) was melted in a double-walled beaker at 150 ° C. with continuous stirring. After the formation of a homogeneous mass, dye (s) (optional) and zinc acetate dihydrate (17.4 g) were incorporated into the melt with stirring. The active substance-containing melt was poured into casting molds or tray tablets. After cooling, an opaque core was formed, and a colored-opaque core when adding a dye.

Example 2:

Isomalt ^® ST-F (150 g) was melted in a double-walled beaker at 150 ° C. with continuous stirring. After the formation of a homogeneous mass, dye (s) (optional) and manganese sulfate (3.6 g) were incorporated into the melt with stirring. The active substance-containing melt was poured into casting molds or tray tablets. After cooling, an opaque core was formed, and a colored-opaque core when adding a dye.

Example 3:

Casting molds (optionally tray tablets) were filled with particulate zinc acetate dihydrate (250 mg) and / or particulate manganese sulfate (100 mg). Isomalt ^® ST-F was melted in a double-walled beaker at 150 ° C. with continuous stirring, and 2.2 g of the homogeneous melt were poured into the casting molds. After solidification, the moldings had a transparent, high-gloss appearance. The salts used (zinc acetate dihydrate and / or manganese sulfate) were visible in the molded body.

Example 4:

Various machine dishwashing detergents containing manganese sulfate have been tested for their silver corrosion protection properties. For this, silver cutlery was washed in a continuously operated dishwasher with differently prepared machine dishwashing detergents at a water hardness of 0-1 ° dH. All agents contained 100 mg of manganese sulfate, this manganese sulfate as part of a compressed tablet phase (V 1), as part of a compressed core (V2) or as Part of an active phase (E 1) according to the invention was present. The rinsing process was repeated 100 times under the conditions described above. The overall appearance of the wash ware was assessed using the rating scale below. The results are shown in the table below (rating scale: 0 = no corrosion to 4 = severe corrosion):

The table shows that the automatic dishwasher detergent according to the invention with an active phase has significantly better silver corrosion properties under the conditions mentioned. The silver corrosion protection is improved by assembling the manganese sulfate in the active phase.

Claims

claims

1. Single- or multi-phase detergent tablets, which has at least one active phase, which consists of one or more washing and / or cleaning-active substance (s) and a solid matrix surrounding this substance (s), characterized in that the solid Matrix has a solubility above 100 g / L at 20 ° C and the weight fraction of the solid matrix in the total weight of the active phase is at least 10 wt .-%.

2. Detergent tablets according to claim 1, characterized in that the solid matrix (s) have a solubility above 200 g / L at 20 ° C, preferably above 300 g / L at 20 ° C.

3. Detergent tablets according to one of claims 1 or 2, characterized in that the proportion by weight of the solid matrix in the total weight of the active phase is at least 20% by weight, preferably at least 40% by weight, particularly preferably at least 80% by weight and in particular is at least 90% by weight.

4. Detergent tablets according to one of claims 1 to 3, characterized in that the active phase d) 10 to 98 wt .-% matrix material, e) 1.5 to 90 wt .-% of one or more washing and / or cleaning-active substance (s) and f) contains 0 to 1, 0% of a dye.

5. Detergent tablets according to one of claims 1 to 4, characterized in that the matrix material contains one or more meltable substance (s) which have a melting point between 30 and 250 ° C, preferably between 35 and 200 ° C and in particular between 40/180 ° C has / have.

6. Detergent tablets according to one of claims 1 to 5, characterized in that the matrix material is selected from the group of sugars and / or sugar acids and / or sugar alcohols, preferably from the group of sugars, particularly preferably from the group of oligosaccharides , Oligosaccharide derivatives, monosaccharides, disaccharides, monosaccharide derivatives and disaccharide derivatives and mixtures thereof, in particular from the group consisting of glucose and / or fructose and / or ribose and / or maltose and / or lactose and / or sucrose and / or maltodextrin and / or Isomalt ^® .

7. Detergent tablets according to one of claims 1 to 6, characterized in that the washing or cleaning-active substances enclosed by the solid matrix are selected from the group of the enzymes and / or the glass corrosion protection agents and / or the silver protection agents and / or the scale-inhibiting polymers and / or the pH adjusting agent.

8. shaped detergent or cleaning product according to one of claims 1 to 7, characterized in that the single-phase or multi-phase shaped detergent or cleaning product has a trough which at least partially encloses the active phase.

9. shaped detergent or cleaning product according to one of claims 1 to 8, characterized in that the single or multi-phase detergent or cleaning product contains the active phase in the form of a layer.

10. Detergent tablets according to one of claims 1 to 9, characterized in that the detergent tablets have a planar outer surface on which the active phase, which partially covers the planar outer surface, adheres.

11. shaped detergent or cleaning product according to one of claims 1 to 10, characterized in that the washing or cleaning active substances in the matrix surrounding them in pre-assembled form, preferably as Crystal (s) and / or powder and / or granules (e) and / or extrudate (s) and / or compact (s) and / or cast body are present.

12. Detergent tablets according to one of claims 1 to 11, that the detergent tablet is a textile detergent, the detergent and cleaning substances for textile cleaning being present in the matrix surrounding them in tableted form and this tablet (n) preferably have a breaking hardness below 30 N, particularly preferably below 25 N and in particular below 20 N.

13. Detergent tablets according to one of claims 1 to 11, characterized in that the detergent tablet is a machine dishwashing detergent, the washing and cleaning-active substances for machine dishwashing being tabletted in the matrix surrounding them Form are present and these tablet (s) preferably have a hardness below 100 N, particularly preferably below 85 N and in particular below 70 N.

14. Detergent tablets according to one of claims 1 to 13, characterized in that the proportion by weight of the active phase is at least 5% by weight, preferably at least 7.5% by weight and in particular at least 10% by weight of the total weight of the wash - Or detergent tablets.

15. Detergent tablets according to one of claims 1 to 14, characterized in that the phase, which consists of one or more, enclosed by a solid matrix, washing and / or cleaning substance, at least 5%, preferably at least 7.5 % and in particular at least 10% of the total surface of the detergent tablet.

16. Detergent tablets according to one of claims 1 to 15, characterized in that the quotient of the weight fraction of Active phase in the total weight of the detergent tablet, and the proportion of the active phase in the entire surface of the detergent tablet is at least 0.1, preferably at least 0.2, particularly preferably at least 0.4 and in particular at least 1.0.

17. Detergent or cleaning product tablet according to one of claims 1 to 16, characterized in that the tablet has a water-soluble packaging.