DE10221559A1 - Detergent tablets with active phase - Google Patents

Abstract

Single-phase or multi-phase detergent tablets, which have 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), this solid matrix having a solubility above 100 g / L and the proportion by weight of the solid matrix in the total weight of the active phase is at least 10% by weight, are distinguished by an improved performance profile, in particular with regard to the use of care additives.

Description

The present invention is in the field of detergent tablets as they are for example for portioning and dosing universal detergents for textiles or machine dishwashing detergents are used. In particular, the present invention relates single-phase or multi-phase detergent tablets which have an active phase, which in turn accelerates the provision of washing and cleaning-active substances, especially nourishing additive, and this improved performance profile with a improved product optics.

In the field of detergents and cleaning agents, detergents and Detergent tablets, in particular the detergent and cleaning tablets, due to their easy handling by consumers a high level of acceptance. Striving for one progressive improvement of these products have recently become so-called Combination products, which in addition to the classic cleaning effect, for example have additional fabric softener or rinse aid function. By integrating one or more additional function (s) in the conventional detergent or cleaning agent separate dosage of a corresponding second product (fabric softener, rinse aid, etc.) in an additional operation is unnecessary, and the entire operation is simplified. Prerequisite for the optimal effectiveness of the detergent or cleaning agent integrated additional function is the time-controlled release of this Additive. The means for assembly and controlled so far known in the prior art The release of detergent or cleaning agent additives is usually technically complex and often developed for the use of special additives and therefore not universally applicable.

For example, WO 00/51724 (Procter & Gamble Company) describes the use of molecular sieves a pore diameter above 8 angstroms for packaging and controlled Release of additives from laundry detergents such as fabric softeners or fragrances. The use of the disclosed molecular sieves is, however, comparatively complex technically. The insoluble Molecular sieves can also be used as insoluble residues after cleaning Objects remain.

WO 00/39259 and WO 01/64823 (Reckitt Benckiser) disclose water-soluble glasses and ceramic compositions for corrosion protection of glassware. The water-soluble glass or the ceramic contains at least one agent active for the corrosion protection of glassware (Example: Zn-oxide, Al-oxide, Ti-oxide) and are used in solid, paricular form in machine Dishwashing used. The glasses and ceramics described are only suitable for the Glaskorrsosionschutz. Additives for silver corrosion protection or to inhibit deposits can be used do not integrate into the stressed glasses.

The object of the present application was therefore to provide a washing or Detergent molded body, which is for the assembly of the above Combination products are suitable and at the same time a quick release of in them Combination products containing additives, especially additives with low Percentage by weight of the total formulation of the detergent tablets, made possible without to be limited to selected additives. At the same time, the corresponding washing or Detergent tablets have an improved appearance, in particular a direct Visualization of the additives contained in the combination product should be realized.

This task was solved by providing single or multi-phase washing or Detergent tablets which have at least one active phase. A first item the present application are therefore a single or multi-phase washing or Detergent tablets, which have 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 proportion by weight of the solid matrix in the total weight of the active phase is at least 10% by weight is.

The active phase (s) contained in the moldings according to the invention are therefore used for Packaging of washing and / or cleaning-active substances, 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 within the scope of the present application, the use of matrix materials a solubility above 100 g / L has been found to be suitable for achieving the object of the invention have, the advantageous effect of agents according to the invention by the use of Matrix materials with solubilities above 200 g / L are even further reinforced. Another one preferred subject of the present application are therefore washing or Detergent tablets according to claim 1, characterized in that the solid (n) Matrix / matrices 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, then Within the scope of the present invention, all matrix materials used 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 on.

A matrix structure in the context of the present application can be in different ways will be realized. In a first preferred embodiment, the matrix is a homogeneous, solid phase in which the washing and / or cleaning active substance (s) in homogeneous distribution. Such a homogeneous distribution can be achieved, for example, by Dissolving all washing and / or cleaning substances contained in the active phase in one Solution or melt of the matrix material and subsequent solidification of this solution or Melt can be achieved. The washing and cleaning active substances can in the However, the matrix according to the invention is also present in a heterogeneous distribution. Such heterogeneous Distributions can arise, for example, if solid particles of the wash and / or active cleaning substance (s) mixed with a solution or melt of the matrix material or be poured over without dissolving. Settling movements, for example on the ground different densities of the substances used can then result in a solidification cause uneven distribution of the solid particles within the matrix.

As can be seen from the preceding information, the assembly of washing and / or cleaning-active additives with the help of a melt of the matrix material in the context of present application preferred procedure. In another preferred Embodiment of the detergent tablets according to the invention are as Matrix material therefore one or more fusible substance (s) which have a melting point between 30 and 250 ° C, preferably between 35 and 200 ° C and in particular between 40 and 180 ° C contains / included. Particularly preferred in the context of the present application are active phases in which all matrix materials have a melting point between 30 and 250 ° C, preferably between 35 and 200 ° C and in particular between 40 and 180 ° C.

The following table summarizes some examples of matrix materials which are suitable for the purposes of the present invention and have a solubility above 100 g / L and which have the criterion of a melting point between 30 and 250 ° C.

In the context of the present invention, the matrix materials have proven to be particularly suitable Sugar, sugar acids and sugar alcohols have been proven. These substances are generally not only sufficiently soluble, but are also characterized by low costs and good processability out. This is how sugar and sugar derivatives, in particular the mono- and disaccharides and their Process derivatives, for example in the form of their melts, these melts being a good one Solvent power for dyes as well as for many washing and cleaning substances exhibit. The solid bodies resulting from the solidification of the sugar melts stand out also thanks to a smooth surface and an advantageous look, such as high surface brilliance or transparent appearance.

Preferred detergent tablets are in the context of the present invention therefore 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 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 the sugars preferred as matrix material in the context of the present application count 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. So are mixtures of Isomalt® and glucose, Isomalt® and lactose, Isomalt® and fructose, Isomalt® and ribose, Isomalt® and maltose, glucose and sucrose, Isomalt® and maltodextrin or Isomalt® and sucrose as matrix materials particularly preferred. The weight fraction of the 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 are also particularly preferred as matrix material, Maltodextrin and lactose, maltodextrin and fructose, maltodextrin and ribose, maltodextrin and Maltose or maltodextrin and sucrose. The weight fraction of maltodextrin in the total weight 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.

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

In the context of the present application, Isomalt® is a mixture of 6-O-α-D- called glucopyranosyl-D-sorbitol (1,6-GPS) and 1-O-α-D-glucopyranosyl-D-mannitol (1,1-GPM). In a preferred embodiment, the weight proportion of the 1,6-GPS is based on the total weight the mixture is less than 57% by weight. Such mixtures can be used industrially, for example by enzymatic rearrangement of sucrose to isomaltose and subsequent catalytic Hydrogenation of the isomaltose obtained to form an odorless, colorless and crystalline Produce solid.

Matrix materials used in the context of the present application are particularly preferred continue the sugar acids. Sugar acids can be used alone or in combination with others Substances such as the sugars mentioned above advantageously as part of the Use active phase, with sugar acids from the group gluconic acid, galactonic acid, Mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid are particularly preferred. Matrix materials which, in addition to the mentioned sugar acids continue to contain Isomalt®. The weight fraction of the Isomalt® on 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 Isomalt® with gluconic acid, Isomalt® with galactonic acid, Isomalt® with mannonic acid, Isomalt® with Fructonic acid, Isomalt® with arabinonic acid, Isomalt® with xylonic acid, Isomalt® with ribonic acid and Isomalt® with 2-deoxy-ribonic acid are particularly preferred.

A third group of matrix materials which can advantageously be used are the sugar alcohols of which in the Mannite, sorbitol, xylitol, dulcitol and arabitol are preferred in the context of the present application become. 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 can be used. Mixtures of sugar alcohols with Isomalt® are particularly preferably used, where Mixtures of Isomalt® with mannitol, Isomalt® with sorbitol, Isomalt® with xylitol, Isomalt® with dulcite and Isomalt® with arabite are particularly preferred. The weight fraction of the Isomalt® in the total weight these mixtures are 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 beginning, one of the tasks on which this application is based was Packaging additives with a low weight percentage of the total formulation of the washing or Detergent tablets with simultaneous direct visualization of the additive (s) conditional additional function (s). A preferred subject of the present application are for example, detergent tablets, the active phases of which are wash 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 Shaped body. Because the visual perception of these recipe components with little The proportion by weight made difficult by the consumer due to their small volume will be in one special embodiment of the present application such washing or Preferred detergent tablets, in which the weight fraction of the solid matrix on Total weight of the active phase at least 20% by weight, preferably at least 40% by weight, is particularly preferably at least 80% by weight and in particular at least 90% by weight. there However, it should be noted that with increasing proportion of the matrix material in the total weight of the Active phase also change the solution and release profile of the active phase. As a rule, the following applies: with increasing proportion of the matrix material in the total weight of the active phase the release of the enclosed washing and / or cleaning-active substances is delayed.

With a view to improved optics, preferred washing or cleaning agents according to the invention are Detergent tablets further characterized in that the proportion by weight of the active phase 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 detergent tablets.

In a particularly preferred embodiment, washing or The active phase is transparent to detergent tablets. Under transparency is in the sense of this Invention to understand that the transmittance within the visible spectrum of light (410 to 800 nm) greater than 20%, preferably greater than 30%, most preferably greater than 40% and is in particular greater than 50%. As soon as a wavelength of the visible spectrum of the Light has a permeability greater than 20%, it is transparent in the sense of the invention consider. Transparent active phases improve the overall look of molded articles according to the invention and offer another way of visualizing the washing contained in these active phases or cleaning-active substances, which, for example, in these transparent active phases Crystals or granules can be present, and due to the transparency of them at least partially surrounding active phases are visible to the consumer.

Another possibility to improve the optics of active phases according to the invention consists in their Staining. The active phases of those particularly preferred in the context of the present application Detergent tablets are therefore not only matrix material and detergent and / or cleaning-active substances also contain dyes. Preferred dyes whose Selection presents no difficulty to the person skilled in the art, has a high storage stability and Insensitivity to the other ingredients of the agent and to light and none pronounced substantivity towards tableware or textiles so as not to stain them.

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

In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in the active phase, however, is typically some 10 ^-3 to 10 ^-4 wt .-%.

• a) 10 bis 98 Gew.-% Matrixmaterial,
• b) 1,5 bis 90 Gew.-% einer oder mehrerer wasch- und/oder reinigungsaktiven Substanz(en) sowie
• c) 0 bis 1,0% eines Farbstoffes enthält.

In summary, preferred single-phase or multi-phase detergent tablets in the context of the present application can be described to the effect that the active phase

• a) 10 to 98% by weight of matrix material,
• b) 1.5 to 90 wt .-% of one or more washing and / or cleaning active substance (s) and
• c) contains 0 to 1.0% of a dye.

To the group of active washing and / or cleaning substances, which within or multiphase detergent or cleaning product, in particular within the Active phase according to the invention are present, generally count all those known to the person skilled in the art Substances, in particular individual substances or substance mixtures from the group of Bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, disintegration aids, Electrolytes, pH adjusting agents, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, Disintegration aids, anti-redeposition agents, optical brighteners, graying inhibitors, Anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, Germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, phobing and Impregnating agents, swelling and sliding resistant agents, non-aqueous solvents, fabric softener, Protein hydrolysates and UV absorbers.

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 O ₂ 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 peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid 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. B. dibenzoyl peroxide. Other 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 alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidthanoic acid paproacidaproacidoxyhexanoic acid , o-Carboxybenzamidoperoxycapronsäure, N- nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-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 Bleach activators contain one when cleaning at temperatures of 60 ° C and below to achieve improved bleaching effect. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, be used. Substances containing O- and / or N-acyl groups of the C- Bear atomic number and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (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, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso- NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called Bleaching catalysts are incorporated into the agents. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru, or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and are Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes usable as bleaching catalysts.

Preferred detergents or cleaning agents contain within the scope of the present application or more surfactant (s) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

Anion surfactants in acid form are preferably one or more substances from the group of Carboxylic acids, the sulfuric acid half-ester and the sulfonic acids, preferably from the group of Fatty acids, the fatty alkyl sulfuric acids and the alkylarylsulfonic acids used. To adequate The compounds mentioned should have surface-active properties have longer-chain hydrocarbon radicals, i.e. at least 6 carbon atoms in the alkyl or alkenyl radical exhibit. 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 that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits 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 in the present invention as an anionic surfactant in acid form 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 use in the context of the present compound is preferred 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), hexacosanoic acid (trisacetic acid), and triacidic acid Sizes 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- octadecenoic acid, linoleic acid 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreinic acid re (linolenic acid) For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids that are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _{18 "),} palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% C _12, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _{18 "),} tallow fatty acid (ca. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C ₁₆ ', 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% 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% by weight C ₁₇ , 63 wt .-% C _18: 1 wt .-% C _{18 '),} technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt. % C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 "} , 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 wt% 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 quantity, 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 Alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, differ in comparison to the alkyl sulfates due to higher water solubility and lower sensitivity to water hardness (solubility of Ca salts). Alkyl ether sulfuric acids are made like the alkyl sulfuric acids Fatty alcohols synthesized with ethylene oxide to 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 sulfation reactors Yields over 98% of the alkyl ether sulfuric acids in question.

Alkanesulfonic acids and olefin sulfonic acids are also within the scope of the present invention Anionic surfactants can be used in acid form. Alkanesulfonic acids can terminal the sulfonic acid group bound (primary alkanesulfonic acids) or along the C chain (secondary Alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance have. These are by sulfochlorination or sulfoxidation of linear hydrocarbons manufactured. Reed's sulfochlorination uses n-paraffins with sulfur dioxide and chlorine converted to the corresponding sulfochlorides under irradiation with UV light, which upon hydrolysis with alkali directly the alkanesulfonates, when reacting with water the alkanesulfonic acids. There in the sulfochlorination di- and polysulfochlorides as well as chlorinated hydrocarbons as by-products the radical reaction can occur, the reaction is usually only up to Implementation levels of 30% carried out and then canceled.

Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins can be reacted with sulfur dioxide and oxygen under irradiation with UV light. At this Radical reactions result in successive alkylsulfonyl radicals that add oxygen to the Alkylpersulfonylradiaklen continue to react. The reaction with unreacted paraffin gives one Alkyl radical and the alkyl persulfonic acid, which in an alkyl peroxysulfonyl radical and a Hydroxyl radical disintegrates. The reaction of the two radicals with unreacted paraffin provides the Alkyl sulfonic acids or water, which with alkyl persulfonic acid and sulfur dioxide Sulfuric acid reacts. To the yield of the two end products alkyl sulfonic acid and This reaction will keep sulfuric acid as high as possible and suppress side reactions Usually only carried out up to degrees of conversion of 1% and then terminated.

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 These sultones react to suitable conditions (alkaline or acid hydrolysis) Hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which are also anionic surfactant acids can be used.

Alkylbenzenesulfonates as powerful anionic surfactants have been ours since the 1930s Century known. At that time, by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation prepared alkylbenzenes that sulfonated with oleum and with Sodium hydroxide solution were neutralized. At the beginning of the fifties the production of Alkylbenzenesulfonates propylene tetramerized to branched α-dodecylene and the product over a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride Tetrapropylenbenzene implemented, which was then sulfonated and neutralized. This economic possibility of producing tetrapropylene benzene sulfonates (TPS) led to Breakthrough of this class of surfactants, which subsequently the soaps as the main surfactant in washing and Detergents displaced.

Due to the lack of biodegradability of TPS, there was a need for new ones To represent alkylbenzenesulfonates, which are characterized by improved ecological behavior distinguished. These requirements are met by linear alkylbenzenesulfonates, which today are almost exclusively manufactured alkylbenzenesulfonates and with the abbreviation ABS or LAS be occupied.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are made from linear olefins are accessible. For this purpose, petroleum fractions are used on an industrial scale Molecular sieves separated into the n-paraffins of the desired purity and into the n-olefins dehydrated, resulting in both α- and i-olefins. The resulting olefins are then in In the presence of acidic catalysts with benzene to the alkylbenzenes, the choice of Friedel-Crafts catalyst has an influence on the isomer distribution of the resulting linear Alkylbenzenes has: When using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight If hydrogen fluoride is used as a catalyst, the 2-phenyl isomer content can be increased to approximately 20% by weight. reduce. Finally, the sulfonation of linear alkylbenzenes is now possible on an industrial scale Oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the largest Has meaning. Special film or tube bundle reactors are used for the sulfonation Product to provide a 97 wt .-% alkylbenzenesulfonic acid (ABSS) within the scope of the present Invention can be used as anionic surfactant acid.

By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. 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. According to the invention, the preferred anionic surfactant in acid form is C _8-16 -, preferably C _9-13 -alkylbenzenesulfonic acids. In the context of the present invention, it is further preferred to use C _8-16 , preferably C _9-13 alkylbenzenesulfonic acids which are derived from alkylbenzenes 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 _9-13 -alkybenzenesulfonic acids used have a 2-phenyl isomer content of less than 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 can be used together. However, it is also possible and preferred that the anionic surfactant in Acid form before the addition to the carrier material (s) further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40% by weight, preferably 1 to 15% by weight and in particular from 2 to 10 wt .-%, each based on the weight of the the mixture to be reacted.

In the context of the present invention, suitable acidic reactants in addition to the "Surfactic 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 as well as in any mixtures. As ingredients of washing and Cleaning agents are particularly suitable for acidic detergent and cleaning agent ingredients for example phosphonic acids, which in neutralized form (phosphonates) as Incrustation inhibitors are part of many washing and cleaning agents. The use of (Partially neutralized) polymer acids such as polyacrylic acids is possible according to the invention. However, it is also possible to mix acid-stable ingredients with the anionic surfactant acid. Here So-called small components are available, for example, which are otherwise available in complex additional components Steps would have to be added, for example optical brighteners, dyes etc., where acid stability must be checked in individual cases.

Of course, it is also possible to use the anionic surfactants partially or fully neutralized. This Salts can then be present as a solution, suspension or emulsion in the granulating liquid, however also be part of the solid bed as a solid. There are cations for such anionic surfactants in addition to the alkali metals (in particular here according to claim and K salts) ammonium and mono-, Di- or triethanolalkonium ions. Instead of mono-, di- or triethanolamine, the analog representatives of mono-, di- or trimethanolamine or those of alkanolamines higher Alcohols 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 residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants, 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 that can be used satisfy the general formula RO (G) _z , 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, carbon atoms and G is the 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 preferred nonionic surfactants, 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.

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

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


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

[Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N Aryloxy-substituted compounds can then be reacted with fatty acid methyl esters in In the presence of an alkoxide as a catalyst converted into the desired polyhydroxy fatty acid amides become.

In the case of cleaning agents 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 alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as C ₁₁ -, 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 the use of 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 for the purposes of the invention. For the purposes of the present invention, very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. 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, automatic dishwashing agents according to the invention are preferred which contain surfactants of the general formula IV as nonionic surfactant (s)


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 , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ and the indices w, x, y, z independently 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 of alcohols of native origin having 12 to 18 carbon atoms, e.g. B. 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 is up 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 stand 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. Are the single or multi-phase detergent tablets for machine dishwashing used, they contain with particular preference nonionic surfactant that has a melting point above room temperature. As a result preferred agents, 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, included.

Suitable nonionic additives in addition to the nonionic surfactants contained in the agents according to the invention Surfactants that have melting or softening points in the temperature range mentioned For example, low-foaming nonionic surfactants that are solid at room temperature or can be highly viscous. If highly viscous nonionic surfactants are used at room temperature, this is the case preferred that this have a viscosity above 20 Pas, preferably above 35 Pas and have above 40 Pas in particular. Also nonionic surfactants, which are waxy at room temperature Have consistency are preferred.

Preferred nonionic surfactants to be used as solid at room temperature come from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures thereof Surfactants with structurally complicated 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 is included a melting point above room temperature an ethoxylated nonionic surfactant, which results from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 moles, in particular at least 20 moles, of ethylene oxide per mole Alcohol or alkylphenol has emerged.

A particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 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. Preferably make such PO units up to 25 wt .-%, particularly preferably up to 20 wt .-% and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Especially 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 such non-ionic surfactants. Preferred machine dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units in Molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the make up the total molecular weight of the nonionic surfactant.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a 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 Copolymers of polyoxyethylene and polyoxypropylene initiated with and containing trimethylolpropane 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Examples of nonionic surfactants that can be used with particular preference are available 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 ¹ O [CH ₂ CH (CH ₃ ) O] _x [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

R ¹ O [CH ₂ CH (R ³ ) O] _x [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. 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 represents 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 has} 9 to 14 C 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 ¹ O [CH ₂ CH (R ³ ) O] _x [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

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

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

In combination with the surfactants mentioned, anionic, cationic and / or amphoteric can also be used Surfactants are used, because of their foaming behavior in machine Dishwashing detergents are of minor importance and mostly only in amounts below 10% by weight, mostly even below 5% by weight, for example from 0.01 to 2.5% by weight, in each case based on the agent. The agents according to the invention can thus be used as Surfactant component also contain anionic, cationic and / or amphoteric surfactants.

In the context of the present invention, it is preferred that when using an inventive As a machine dishwashing detergent, preferably non-ionic (s) in this Surfactant (s), in amounts from 0.5 to 10% by weight, preferably from 0.75 to 7.5% by weight and in particular from 1.0 to 5% by weight, based in each case on the total composition, are present.

Cationic surfactants can also be used with advantage as washing or cleaning substances. The Cationic surfactant can be added directly to the mixer in its delivery form, or in the form a liquid to pasty form of cationic surfactant is sprayed onto the solid carrier. Such forms of cationic surfactants can be obtained, for example, by mixing them more commercially Cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols produce. Lower alcohols such as ethanol and isopropanol can also be used, the Amount of such lower alcohols in the liquid cationic surfactant formulation from the reasons mentioned above should be below 10 wt .-%.

All customary substances are suitable as cationic surfactants for the agents according to the invention, wherein Cationic surfactants with a fabric softening effect are 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:




wherein each R ^{1 group is} independently selected from C _1-6 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 ¹ 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) contain (s) additionally nonionic surfactant (s) as a washing or cleaning substance.

In addition to the ingredients mentioned, there are bleaches and bleach activators and surfactants Builders other important ingredients of detergents or cleaning agents. In the Agents according to the invention can all be used in cleaning agents Builders may be included, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates. The The builders mentioned can of course also be used in surfactant-free grain primates become.

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. 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 modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 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 / compaction 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 provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite which 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) ), developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

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

can be described. 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.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and especially the tripolyphosphates.

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 fabrics 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 ₄ P ₂ O ₇ and by condensation of NaH ₂ PO ₄ or des 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, those in the form of their alkali and in particular sodium salts of polycarboxylic acids, 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. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances, wherein in For the purposes of this invention, the alkali carbonates, in particular sodium carbonate, are preferred. Sodium bicarbonate or sodium sesquicarbonate can be used.

If the agents according to the invention are used for machine dishwashing, then there are Water-soluble builders preferred because they tend to be less on dishes and hard surfaces tend to form insoluble residues. Common builders are the low-molecular ones Polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their Salts, the carbonates, phosphates and silicates. Are preferred for the production of tablets for automatic dishwashing trisodium citrate and / or pentasodium tripolyphosphate and / or Sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders the class of disilicates and / or metasilicates. A builder system is particularly preferred containing a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system that is a mixture of tripolyphosphate and sodium carbonate Contains sodium disilicate.

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or fungi such as are particularly suitable Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are enzymatic agents obtained. Proteases of the subtilisin type and in particular proteases derived from Bacillus are preferred lentus are used. There are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but especially Mixtures of cellulase of particular interest. Also have peroxidases or oxidases proved to be suitable in some cases. The enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition.

In order to facilitate the disintegration of the agents according to the invention, these agents can Disintegration aids, so-called tablet disintegrants, contain. Under tablet disintegrants or decay accelerators are according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "textbook der pharmaceutical technology "(6th edition, 1987, pp. 182-184) understood auxiliary substances which are suitable for the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in provide resorbable form.

These substances, which are also referred to as "explosives" due to their effect, enlarge Water ingress their volume, whereby on the one hand the own volume increases (swelling), on the other hand A pressure can also be generated via the release of gases, which breaks the tablet down into smaller ones Particles disintegrate. Well-known disintegration aids are, for example Carbonate / citric acid systems, whereby 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 substances such as cellulose and Starch and its derivatives, alginates or casein derivatives. All disintegration aids mentioned can be used according to the invention.

In the context of the present invention, disintegration aids are preferred Disintegration aid based on cellulose, preferably in granular, cogranulated or compact form, used.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The cellulose derivatives mentioned are preferably not used alone as disintegrants Cellulose base used, but used in a mixture with cellulose. The salary of this Mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Particularly preferred Pure cellulose is used as a disintegrant based on cellulose, which is free of Is cellulose derivatives. As another disintegrant based on cellulose or as a component this component can use microcrystalline cellulose. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under such conditions that only the attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses completely dissolve, but leave the crystalline areas (approx. 70%) undamaged. A subsequent one The disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses which have primary particle sizes of approx. 5 µm and, for example, too Granules with an average particle size of 200 microns can be compacted.

In addition to or instead of the cellulose-based disintegration aid, the agents a gas-releasing system of organic acids and Contain carbonates / bicarbonates.

As organic acids from the carbonates / hydrogen carbonates in aqueous solution Releasing carbon dioxide are, for example, the solid mono-, oligo- and polycarboxylic acids used. 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. Commercially available and as Acidifying agent is also preferably used in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), Glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

The acids mentioned do not have to be stoichiometric to those contained in the compressed products Carbonates or bicarbonates are used.

A single-phase or multi-phase washing or preferred in the context of the present invention Detergent tablets also contain a shower system.

The gas-developing shower system consists of the agents according to the invention in addition to those mentioned organic acids from carbonates and / or hydrogen carbonates. With the representatives of this For reasons of cost, the alkali metal salts are clearly preferred. Both Alkali metal carbonates or bicarbonates, in turn, are the sodium and potassium salts Cost reasons clearly preferred over the other salts. Of course you don't have to the pure alkali metal carbonates or bicarbonates concerned are used; much more 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. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred.

To bring the pH of solutions of the agents according to the invention into the desired range bring, the use of pH adjusting agents may be appropriate. All of them can be used here known acids or alkalis, provided that their use does not result from application technology or for ecological reasons or for reasons of consumer protection. Usually The amount of these adjusting agents does not exceed 1% by weight of the total formulation. A special one preferred pH adjusting agent in the context of the present application is citric acid, the Citric acid both as a pure substance, for example as a monohydrate, or in the form of coated Particles can be used.

Individual perfume oils or fragrances can be used in the context of the present invention Fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone type, Alcohols and hydrocarbons can be used. Fragrance compounds are of the ester type z. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. Count among the ethers for example benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol Hydrocarbons mainly belong to the terpenes like limonene and pinene. To be favoured however, mixtures of different fragrances are used, which together make an appealing Generate fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as these are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang Ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandwood oil.

The general description of the perfumes that can be used (see above) is generally the different substance classes of fragrances. In order to be perceptible, a Fragrance be volatile, being in addition to the nature of the functional groups and the structure of the chemical compound also the molecular weight plays an important role. Most have that Fragrances Molar masses up to about 200 Daltons, while Molar masses of 300 Daltons and above tend to be to be an exception. Changed due to the different volatility of fragrances the smell of a perfume or fragrance composed of several fragrances during evaporation, whereby the olfactory impressions in "top note", "heart or Middle note "(middle note or body) and" base note "(end note or dry out). Since the Odor perception is largely based on the intensity of the odor Top note of a perfume or fragrance not only from volatile compounds, while the Base note for the most part from less volatile, i.e. H. non-stick fragrances. In the Composition of perfumes can make volatile fragrances, for example, to certain fixatives bound, which prevents them from evaporating too quickly. The following Classification of the odoriferous substances into "more volatile" or "adherent" odoriferous substances is therefore about Odor impression and whether the corresponding fragrance as a top or heart note is perceived, nothing is said.

Through a suitable selection of the fragrances or perfume oils mentioned, both the smell of the agents according to the invention (product fragrance), and, after the cleaning and Care process, in addition, for example, the scent of laundry can be influenced. While for the Influencing the product fragrance, particularly volatile fragrances, can be used To achieve a sufficient laundry fragrance, the use of more adhesive fragrances is advantageous. Adhesive fragrances 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 fir cone oil, elemi oil, eucalyptus oil, fennel oil, Spruce oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, Helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, Cardamom oil, cassia oil, pine needle oil, Kopaïvabalsam oil, coriander oil, spearmint oil, caraway oil, Cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm 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, thuja oil, thyme oil, verbena 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. But also the higher-boiling or solid fragrances natural or synthetic origin can be used in the context of the present invention as adhesive fragrances or fragrance mixtures, i.e. fragrances. These connections include the the following compounds and mixtures of these: ambrettolide, α- Amyl cinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, acetophenone, Benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, Benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, Geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, Hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, Isoeugenol methyl ether, isosafrol, jasmon, camphor, karvakrol, karvon, p-cresol methyl ether, Coumarin, p-methoxyacetophenone, methyl-n-amylketone, methylanthranilic acid methyl ester, p- Methyl acetophenone, methylchavicol, p-methylquinoline, methyl-β-naphthyl ketone, methyl-n- nonylacetaldehyde, methyl-n-nonyl ketone, muscon, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, Nitrobenzene, n-nonylaldehyde, nony alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β- Phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrol, Salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, Cyclohexyl salicylic acid, Santalol, Skatol, Terpineol, Thymen, Thymol, γ-undelactone, Vanilin, Veratrum aldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate. The more volatile fragrances include in particular the lower-boiling fragrances 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 Propionat, Menthol, Menthon, Methyl-n-heptenon, Phellandren, Phenylacetaldehyde, terpinylacetate, citral, citronellal.

In order to improve the aesthetic impression of agents according to the invention, these dyes contain. The use of dyes is not for the active phases according to the invention limited, but can also be used in a multi-phase detergent tablets or all other phases. To avoid repetitions, be on here the above remarks on the dyes that can be used.

Substances are characterized as hydrotropes or solubilizers by their presence other compounds practically insoluble in a particular solvent Make solvent soluble or emulsifiable (solubilization). There are solution mediators with the poorly soluble substance enter into a molecular compound and those that are caused by micell formation Act. One can also say that solubilizers are a so-called latent solvent lend its solvency. With water as (latent) solvent one speaks instead of Solubilizers mostly from hydrotropes, in certain cases better from emulsifiers.

Foam inhibitors which 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 antiredeposition 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 on methoxy groups from 15 to 30% by weight and on hydroxypropyl groups from 1 to 15% by weight, each based on the nonionic cellulose ether and those from the prior art known polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred from these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention to remove graying and yellowing of the treated textiles. These substances draw on the fiber and cause a lightening and feigned bleaching effect by Convert invisible ultraviolet radiation into visible longer-wave light, which is from the Sunlight absorbed ultraviolet light as a faint bluish fluorescence and is emitted with the yellow tone of the grayed or yellowed laundry results in pure white. Suitable connections originate, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (Flavonic acids), 4,4'-distyrylbiphenylene, methylumbelliferones, coumarins, dihydroquinolinones, 1,3- Diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well of pyrene derivatives substituted by heterocycles.

Graying inhibitors have the task of removing the dirt detached from the fiber in the liquor to keep suspended and thus prevent the dirt from re-opening. For this are Suitable water-soluble colloids mostly organic in nature, for example the water-soluble salts 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. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble ones Use starch preparations and starch products other than the above, e.g. B. dismantled Starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. As graying inhibitors Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and mixtures thereof.

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending, kinking. Presses and The agents according to the invention can be sensitive to squeezing across the grain contain synthetic anti-crease agents. These include, for example, synthetic products on the Basis of fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or Fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester. A special measure for textile equipment and care a suitable substance is cottonseed oil, which is obtained, for example, by pressing out the brown oil purified cotton seeds and refining with about 10% sodium hydroxide or by extraction can be produced with hexane at 60-70 ° C. Such cotton oils contain 40 to 55% by weight Linoleic acid, 16 to 26% by weight oleic acid and 20 to 26% by weight palmitic acid. More on Fiber smoothing and fiber care particularly preferred agents are the glycerides, especially those Monoglycerides of fatty acids such as glycerol monooleate or glycerol monostearate.

To control microorganisms, the agents according to the invention can be antimicrobial Contain active ingredients. A distinction is made depending on the antimicrobial spectrum and Mechanism of action between bacteriostatics and bactericides, fungistatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, Halogenphenols and Phenolmercuriacetat, with the agents according to the invention also entirely these connections can be dispensed with.

To unwanted, caused by oxygen and other oxidative processes Changes to the washing and cleaning agents and / or the treated textiles too prevent, the agents of the invention may contain antioxidants. To this Compound classes include, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines and organic sulfides, polysulfides, dithiocarbamates, phosphites and Phosphonates.

An increased wearing comfort of textiles can result from the additional use of antistatic agents result, which are additionally added to the agents according to the invention. Enlarge antistatic agents the surface conductivity and thus enable an improved flow of charges formed. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. Mostly Surface-active antistatic agents can be broken down into nitrogen-containing (amines, amides, quaternary Ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, Subdivide antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable also as antistatic agents for textiles or as an additive to detergents, with an additional Finishing effect is achieved.

Phobing and impregnation processes are used to finish textiles with substances that Prevent dirt from accumulating or make it easier to wash out. Preferred phobic and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical coupled, polymerizable compounds. Antistatic agents too can be included. The dirt-repellent finish with phobing and impregnating agents often classified as an easy care kit. The penetration of the impregnating agent in the form of Solutions or emulsions of the active substances in question can be facilitated by adding wetting agents that lower the surface tension. Another area of application of phobic and Impregnating agent is the water-repellent finishing of textile goods, tents, tarpaulins, leather etc., in which, in contrast to waterproofing, the tissue pores are not closed, the So the fabric remains breathable (hydrophobic). The ones used for hydrophobing Water repellents coat textiles, leather, paper, wood etc. with a very thin layer hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are z. B. paraffins, waxes, metal soaps, etc. with additives to aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl residues, urea derivatives, fatty acid modified melamine resins, chromium complex salts, silicones, tin organic compounds and Glutardialdehyde and perfluorinated compounds. The hydrophobized materials don't feel greasy on; nevertheless - similar to greased substances - water droplets roll off without them wet. 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 used in the agents according to the invention organic solvents, of which only the most important ones count may be listed: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), Glycols (ethylene glycol, diethylene glycol), ethers and. 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 u. a. Nitrogen Compounds (Dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (Carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene), Halogenated hydrocarbons (dichloromethane, chloroform, tetrachloromethane, tri-, tetrachloroethene, 1,2- Dichloroethane, chlorofluorocarbons), hydrocarbons (petrol, petroleum ether, cyclohexane, Methylcyclohexane, decalin, terpene solvent, benzene, toluene, xylenes). Alternatively, instead of pure solvents also their mixtures, which have, for example, the solution properties advantageously combine different solvents. Such and in the frame A particularly preferred solvent mixture in the present application is, for example White spirit, 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, in each case based on the Total weight of the mixture, preferably with a boiling range of 81 to 110 ° C.

To care for the textiles and to improve the textile properties such as a softer "handle" (Avivage) and reduced electrostatic charge (increased comfort) can agents according to the invention contain fabric softener. The active ingredients in fabric softener formulations are "Esterquats", quaternary ammonium compounds with two hydrophobic residues, such as that Disteraryldimethylammoniumchlorid, which however because of its insufficient biological Degradability is increasingly being replaced by quaternary ammonium compounds in their hydrophobic residues contain ester groups as predetermined breaking points for biodegradation. Such "esterquats" with improved biodegradability are, for example, thereby available that mixtures of methyldiethanolamine and / or triethanolamine with fatty acids esterified and then the reaction products in a conventional manner with alkylating agents quaternized. Dimethylolethylene urea is also suitable as a finish.

To improve the water absorption capacity, the rewettability of the Agents according to the invention with textiles treated with active phase and to facilitate ironing These textiles can, for example, use silicone derivatives in the agents according to the invention become. These additionally improve the rinsing behavior of the agents according to the invention through 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 in whole or in part are fluorinated. Preferred silicones are polydimethylsiloxanes, which may have been derivatized can and then are amino-functional or quaternized or Si-OH, Si-H and / or Si-Cl bonds exhibit. 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 within the scope of present invention preferred active substances from the field of washing and Cleaning supplies. Protein hydrolyzates are product mixtures that are acidic, basic or enzymatically catalyzed breakdown of proteins (proteins) can be obtained. 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 may also be in the form of salts. Preferred according to the invention is the use of protein hydrolyzates of plant origin, e.g. B. Soy, almond, rice, Pea, potato and wheat protein hydrolyzates. Although the use of protein hydrolyzates as such is preferred, can also be obtained otherwise in its place if necessary Amino acid mixtures or individual amino acids such as arginine, lysine, histidine or Pyrroglutamic acid can be used. The use of 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 act on the treated textiles and improve the lightfastness of the fibers. Connections that have the desired properties, for example those due to non-radiation Deactivation of active compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Substituted benzotriazoles are also substituted in the 3-position by phenyl Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid are suitable.

Detergents for automatic dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents and glass corrosion inhibitors 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, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, 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 of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) 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 ^IV (m-0) ₃ Mn ^IV (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ ,

[Me-MeTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ ,

[Me-TACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ and

[Me-MeTACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ ,

where Me-TACN stands for 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 of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole.

In addition to the aforementioned silver protection agents, agents according to the invention can furthermore have one or contain several substances to reduce glass corrosion. As part of the present Registration includes in particular additions of zinc and / or inorganic and / or organic Zinc salts and / or silicates, for example the layered crystalline sodium disilicate SKS 6 Clariant GmbH, and / or water-soluble glasses, for example glasses that lose weight of at least 0.5 mg under the conditions specified in DIN ISO 719, for Reduction of glass corrosion preferred. Particularly preferred agents contain at least one Zinc salt of an organic acid, preferably selected from the group zinc oleate, zinc stearate, Zinc gluconate, zinc acetate, zinc lactate and zinc citrate.

As explained at the beginning of this description, an object of the present application was in the provision of a shaped detergent or cleaning product which is suitable for assembly and optimized release of additives, in particular additives with a low proportion by weight on the overall formulation of the detergent tablets. While everyone aforementioned washing and / or cleaning-active substances generally also as active substances in the active phase detergent tablets according to the invention are used can, in the context of the present application, the packaging in particular Assembly of washing or cleaning active substances from the group of enzymes, Glass corrosion protection agent, silver protection agent, deposit-inhibiting polymers and the pH adjusting agent and their mixtures have proven to be particularly advantageous.

Another preferred subject of the present application are therefore washing or Detergent tablets, characterized in that those enclosed by the solid matrix washing or cleaning-active substances are selected from the group of enzymes and / or Glass corrosion protection agent and / or the silver protection agent and / or the deposit inhibitor Polymers and / or the pH adjuster.

Mixtures of active substances are particularly preferred Glass corrosion protection and silver protection agents, of glass corrosion protection agents and scale-inhibiting polymer (s), of silver protection agents and scale-inhibiting polymer (s) or of glass corrosion protection agents, silver protection agents and deposit-inhibiting polymer (s).

Are glass corrosion protection agents or silver protection agents or deposit-inhibiting polymers or the aforementioned particularly preferred mixtures according to the invention in the active phases Detergent tablets are used, the weight percentage of these is washing or active cleaning substances on the total weight of the active phase, 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 exhibit. Single-phase detergent tablets in the context of the present Registration are, for example, moldings which have only one active phase, in which the active substance (s) contained are present in a homogeneous distribution. Such molded articles can be, as described in the beginning, for example by solidifying an active substance Make melt.

However, active phases according to the invention are also suitable for the shaping processed washing and / or cleaning active substances. So can be in the invention Active phases, for example also crystals, powders, granules, extrudates, compactates or castings, incorporate substances that are active in washing and / or cleaning. Washing or Detergent tablets which contain the washing or cleaning substances in them enclosing matrix in pre-assembled form, preferably as crystal (s) and / or powder and / or contain granulate (s) and / or extrudate (s) and / or compact (s) and / or cast body, are therefore preferred in the context of the present application. Because of their advantageous appearance, especially in combination with transparent active phases, crystals and / or tablets are considered Form of confection for the active washing and / or cleaning substances contained in the active phase particularly preferred. The tablets that can be used range from the "mini-tabs" weighing in Range from 50 to 500 mg, preferably 100 to 250 mg, up to weight tablets above 1 g, preferably above 5 g. With such packaged tablets, it improves them surrounding active phase not only their appearance and release profile, but also increases their Fracture stability. Tablets made up in this way can therefore generally be compared to Manufacture of commercially available detergent tablets with reduced stamp printing be tabletted and have not only improved disintegration properties but also accordingly reduced fracture hardness, with regard to these tablets with reduced fracture hardness between Detergent tablets for machine dishwashing and textile detergent tablets must be distinguished. A preferred subject of the present application are therefore Shaped body for textile cleaning, characterized in that the washing or cleaning active Substances for textile cleaning are present in the surrounding matrix in tablet form and this tablet (s) preferably has a breaking hardness below 30 N, particularly preferably below 25 N and in particular below 20 N. Another preferred subject of the present Registration are shaped detergent tablets for automatic dishwashing characterized in that the washing or cleaning substances for the machine Dishwashing in the matrix surrounding them in tablet form and this tablet (s) preferably a breaking hardness below 100 N, particularly preferably below 85 N and in particular below 70 N. (The hardness of the tablet is determined by exercising a force on the side surfaces of the tablet until the tablet breaks and determine the maximum force that the tablet can withstand.)

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

The production of such shaped articles can be carried out by all methods known to the person skilled in the art respectively. Active phases according to the invention, however, are preferred after production of a detergent or cleaning agent base body subsequently integrated into this base body. The The base body is preferably produced by tableting and / or molding and / or extrusion, but preferably by tableting and / or molding.

Basically, such basic bodies are particularly suitable for taking up the active phase, which ones after the integration of the active phase, the presentation of the active phase on the surface of the resulting detergent or cleaning tablets allow, because in this way both advantageous solution profile and an advantageous appearance can be guaranteed. preferred Detergent tablets are distinguished in the context of the present application characterized in that the phase, which consists of one or more, of a solid matrix enclosed, washing and / or cleaning active substance, at least 5%, preferably at least 7.5% and in particular at least 10% of the total surface of the washing or Consists of detergent tablets, in a further preferred embodiment, the The ratio of the weight of the active phase to the total weight of the washing and Detergent tablet, and the proportion of the active phase in the entire surface of the washing or detergent tablets at least 0.1, preferably at least 0.2, particularly is preferably at least 0.4 and in particular at least 1.0, the active phase with others Words have a disproportionately large proportion of the surface compared to their proportion by weight takes such detergent or cleaning product tablets.

An example of the aforementioned basic bodies are those that can be produced by tableting Trough tablets, in the cavity of which the active phase is carried out by a number of different processes can be incorporated. For example, the trough can be cast by pouring a melt or a Solution of the matrix material are filled. Subsequent solidification then results in the Detergent tablets according to the invention with active phase. The wash and / or In such a process, cleaning-active substances can, for example, optionally a) in the Melt or solution of the matrix material may be contained, b) in particulate form before filling the Melt or solution can be filled in the trough and optionally before filling the melt or Solution are glued in the well or c) after filling the melt or solution of the Matrix material into the well and before it solidifies in particulate form in the melt or Solution be dosed. The aforementioned are particularly suitable as active substance particles Crystals, powders, granules, extrudates, compactates and castings. Another way of Incorporation of the active phase into molded articles according to the invention consists in the production prefabricated active phases by pouring the matrix material melt or solution into casting molds and then freeze. Prefabricated active phases produced in this way can Connection removed from the molds and inserted into the troughs. The attachment of the Active phases in the troughs can take place, for example, by gluing. Will in the aforementioned If a basic body is used that has no trough, a prefabricated body can be used Active phase can also be attached by gluing to a planar surface of this tablet.

Further preferred subjects of the present application are therefore washing or Detergent tablets, characterized in that the single or multi-phase washing or Detergent molded body has a trough, which at least partially the active phase encloses, as well as detergent or cleaning tablets, characterized in that the Detergent tablets have a planar outer surface on which the active phase, which partially hides the planar outer surface.

Also preferred are single-phase or multi-phase detergent tablets which comprise the Active phase in the form of a layer included.

The single- or multi-phase detergent tablets according to the invention can the consumer in conventional containers made of all common water-insoluble Packaging materials exist that are well known to those skilled in the art, Tobe offered. In particular, plastics are preferred polymers To name hydrocarbon base. The particularly preferred polymers include polyethylene, Polypropylene (more preferably oriented polypropylene) and polymer blends such as for example mixtures of the polymers mentioned with polyethylene terephthalate. Come on also one or more polymers from the group of polyvinyl chloride, polysulfones, polyacetals, water-insoluble cellulose derivatives, cellulose acetate, cellulose propionate, cellulose acetobutyrate and Mixtures of said polymers or copolymers comprising said polymers into question.

However, a particularly preferred embodiment of the present invention aims to To give consumers inventive agents on hand, which is a water-soluble packaging have that the consumer directly without further handling steps, d. H. together with the Packaging, for example in the washing machine or in the dishwasher. Such packages include water-soluble or decomposable packages such as bags water-soluble film (so-called pouches), bags or other packaging made of water-soluble or decomposable nonwovens or also flexible or rigid bodies made of water-soluble polymers, preferably in the form of filled hollow bodies, for example by deep drawing, injection molding, Blow molding, calendering, etc. can be produced.

A preferred subject of the present invention are therefore one or more multiphase detergent tablets, which are water-soluble packaging exhibit.

Shaped bodies according to the invention preferably have a completely or partially soluble in water Packaging on. The shape of the packaging is not limited to certain shapes. in principle all Archimedean and Platonic bodies, i.e. three-dimensional shaped bodies, come as shapes the packaging in question. Examples of the shape of the packaging are capsules, cubes, balls, egg-shaped moldings, cuboids, cones, rods or bags. Hollow bodies with one or more Compartments are suitable as packaging for the agents according to the invention. In preferred Embodiments of the invention have the packaging in the form of capsules as they do for example also used in pharmacy for the administration of medicaments by Bullets or bags. The latter are preferably welded on at least one side or glued, wherein as an adhesive in particularly 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 be largely adapted to the conditions of use. Coming for example in various forms (such as hoses, pillows, cylinders, bottles, disks processed plastic foils or plates, capsules and other conceivable shapes in question. According to the invention, particular preference is given to films which, for example, form packaging such as Hoses, pillows or the like can be glued and / or sealed after they have been individually or more of the moldings according to the invention were filled.

Are further preferred according to the invention because of the excellent physical desired Properties adaptable properties Plastic film packaging made of water-soluble Polymer materials. Such films are basically known from the prior art.

In summary, both hollow bodies of any shape that are produced by injection molding, Bottle blowing, deep drawing etc. can be produced, as well as hollow bodies made of foils, in particular bags (so-called pouches) as packaging for moldings according to the invention prefers. Preferred moldings according to the invention are thus characterized in that the water-soluble packaging a bag made of water-soluble film and / or an injection molded part and / or comprises 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 brings the advantage with it that the agents optimally against environmental influences, in particular against Are protected from moisture.

In principle, all come as materials for the fully or partially water-soluble packaging Materials in question under the given conditions of a wash, rinse or cleaning process (temperature, pH, concentration of detergent components) in completely or partially dissolve aqueous phase. The polymer materials can be special preferably the groups (optionally partially acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, Polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, coextrudates etc.) of the above Belong to materials. Gelatin and polyvinyl alcohols as well as the mentioned two materials in combination with starch or modified starch. Coming also inorganic salts and mixtures thereof as materials for the at least partially water soluble packaging.

Preferred agents according to the invention are characterized in that the packaging contains one or several materials from the group of polymers containing acrylic acid, 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 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, further preferred (optionally acetalized) Polyvinyl alcohol (PVAL).

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


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


contain.

Commercially available polyvinyl alcohols with white-yellowish powder or granules Degree of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered have degrees of hydrolysis of 98-99 or 87-89 mol%, so they still contain one Residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturers by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the Saponification number or 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); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. Polyvinyl alcohols classified as toxicologically safe and are at least partially biodegradable. The Water solubility can be achieved by post-treatment with aldehydes (acetalization) Complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax reduce. The coatings made of polyvinyl alcohol are largely impenetrable for gases such as Oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.

In the context of the present invention, it is preferred that the packaging is a polyvinyl alcohol comprises, the degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly is 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 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 up to 80,000 gmol ^-1 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, particularly preferred between about 240 to about 1680 and especially between about 260 to about 1500th

The polyvinyl alcohols described above are widely available commercially, for example under the trademark Mowiol® (Clariant). Particularly within the scope of the present invention 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 K.K.).

The water solubility of PVAL can be increased by post-treatment with aldehydes (acetalization) or Ketones (ketalization) can be changed. As particularly preferred and because of their Extremely good solubility in cold water has been found to be particularly advantageous in polyvinyl alcohols underlined that with the aldehyde or keto groups of saccharides or polysaccharides or Mixtures thereof can be acetalized or ketalized. To be used as extremely advantageous Reaction products made from PVAL and starch.

Furthermore, water solubility can be achieved by complexing with Ni or Cu salts or by Change treatment with dichromates, boric acid, borax and thus target the desired values to adjust. PVAL films are largely impenetrable for gases such as oxygen, nitrogen, Helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.

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

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

PVPs are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVP have molar masses in the range of approx. 2,500 to 750,000 g / mol and are called white, hygroscopic Powder or offered 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 produced industrially 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 hydroxy end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is predominantly due to Hydrolysis of the collagen contained in animal skin and bones under acidic or alkaline Conditions is won. The amino acid composition of the gelatin corresponds largely that of the collagen from which it was obtained and varies depending on it Provenance. The use of gelatin as a water-soluble coating material is particularly in the Pharmaceuticals in the form of hard or soft gelatin capsules are extremely widespread. In the form of foils only finds gelatin because of its high price compared to the aforementioned polymers minor use.

Agents according to the invention are also preferred within the scope of the present invention Packaging from at least partially water-soluble film from at least one polymer from the Starch and starch derivatives group, cellulose and cellulose derivatives, in particular methyl cellulose and Mixtures of this consists.

Starch is a homoglycan, with the glucose units linked α-glycosidically. Strength is out built up two components of different molecular weight: from approx. 20 to 30% more straight-chain Amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MG. Approx. 300,000 to 2,000,000). There are also small amounts of lipids, phosphoric acid and cations contain. While the amylose is long, helical forms intertwined chains with about 300 to 1,200 glucose molecules, the chain branches at Amylopectin after an average of 25 glucose building blocks through 1,6 binding to a branch-like one Formations with about 1,500 to 12,000 molecules of glucose. In addition to pure starch are used to manufacture water-soluble packaging of the detergent, detergent and cleaning agent portions in the Within the scope of the present invention, starch derivatives are also suitable, which are produced by polymer analogs Reactions from starch are available. Such chemically modified starches include for example products from esterifications or etherifications in which hydroxy Hydrogen atoms have been substituted. But also strengths in which the hydroxy groups are against functional groups that are not linked via an oxygen atom can be replaced use as starch derivatives. The group of starch derivatives includes, for example, alkali starches, Carboxymethyl starch (CMS), starch esters and ethers and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 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, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

Preferred packaging made of at least partially water-soluble film contains 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. The packaging depends on Manufacturing process on different material thicknesses, machine according to the invention Dishwashing detergents are 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 is.

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

These water-soluble films can be produced by various manufacturing processes. Here blowing, calendering and casting processes are to be mentioned in principle. In a preferred method the films are made from a melt with air through a blow mandrel Blown hose. In the calendering process, which is also preferred Manufacturing process belongs, the raw materials plasticized by suitable additives Forming the foils atomized. In this case, it may be necessary in particular to apply an atomizer Drying, connect. In the casting process, which is also the preferred One of the manufacturing processes is an aqueous polymer preparation on a heatable drying roller given, after the water has evaporated, cooling is optional and the film is removed as a film. If necessary, this film is additionally powdered off before or during the removal.

An embodiment is preferred according to the invention, according to which the packaging as a whole is water soluble, d. H. when used as intended for mechanical cleaning, completely dissolves when the conditions for solving are met. Especially preferred as completely water-soluble packaging are, for. B. capsules made of gelatin, with advantage Soft gelatin, or bags made of (optionally partially acetalized) PVAL or balls made of Gelatin or (optionally partially acetalized) PVAL or one or more organic and / or inorganic salts, preferably balls of soft gelatin. essential The advantage of this embodiment is that the packaging is within a practically relevant short Time - as a non-limiting example, can be a few seconds to 5 minutes - under exactly at least partially resolves the defined conditions in the cleaning liquor and thus corresponds to the Requirements the wrapped content, d. H. the single-phase or multi-phase washing or detergent tablets into the liquor.

In another embodiment, which is also preferred due to advantageous properties Invention comprises the water-soluble packaging less or not at all water-soluble or only areas that are water-soluble at higher temperatures and readily water-soluble or at lower ones Temperature water soluble areas. In other words, the packaging does not consist of one uniform material that has the same water solubility in all areas, but from Materials of different water solubility. Areas of good water solubility are on the one hand to be distinguished from areas with less good water solubility, with poor or even lack of water solubility or in areas where water solubility is only at higher levels Temperature or only at a different pH value or only at a changed one Electrolyte concentration reaches the desired value, on the other hand. This can lead to Intended use under adjustable conditions certain areas of the Detach packaging while leaving other areas intact. So one forms with pores or Holed packaging into which water and / or liquor penetrate, wash-active, rinse-active or detach active ingredients and discharge them from the packaging. In the same Ways of packaging systems in the form of multi-chamber bags or in the form of hollow bodies arranged one inside the other (e.g. balls: "onion system") are provided. Let it be systems with controlled release of washing-active, rinsing-active or cleaning-active Manufacture ingredients.

The invention is not subject to any restrictions on the formation of such systems. So can Packaging is provided in which a single polymer material has small areas incorporated compounds (for example salts) which are more water soluble than the polymer material. On the other hand, several polymer materials with different ones can also be used Water solubility can be mixed (polymer blend) so that the more rapidly soluble polymer material is disintegrated faster than that under defined conditions by water or the fleet slower soluble.

It corresponds to a particularly preferred embodiment of the invention that the less well water-soluble areas or non-water-soluble areas or only at a higher temperature water-soluble areas of the packaging areas are made of a material that is chemically in the essentially that of the readily water-soluble areas or at a lower temperature corresponds to water-soluble areas, but has a greater layer thickness and / or changed degree of polymerization of the same polymer and / or a higher Has 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 one Has content of water-insoluble salt components and / or a content of has water-insoluble polymers. Even taking into account the fact that the Packaging does not completely dissolve, so detergent or cleaning agent portions can be made according to the Invention are provided which have advantageous properties in releasing the Have dish detergent in the respective fleet. In addition to the targeted release selected active washing and / or cleaning substances through the active phase offer the one preferred means according to the invention provided in such packaging thus form a second regulatory for the controlled release of active substances.

The water-soluble covering material is preferably transparent. Under transparency is in the sense of this Invention to understand that the transmittance within the visible spectrum of light (410 to 800 nm) greater than 20%, preferably greater than 30%, most preferably greater than 40% and is in particular greater than 50%. As soon as a wavelength of the visible spectrum of the Light has a permeability greater than 20%, it is transparent in the sense of the invention consider.

Agents according to the invention, which are packed in transparent packaging or containers, may contain a stabilizing agent as an essential component. Stabilizing agent in the sense The invention relates to materials which contain the detergent components in their water-soluble, Protect transparent packaging against decomposition or deactivation by light. Antioxidants, UV absorbers and fluorescent dyes have proven particularly suitable here proved.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesired changes to 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 _10-18 alkanols, metal ion deactivators which are capable of metal ions which catalyze the autooxidation, e.g. As copper, to complex, 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 recipe components. Among them are organic Understand substances (light protection filters) that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, e.g. B. to release heat again. Compounds which have these desired properties are, for example, those by radiation-free deactivation effective compounds and derivatives of benzophenone with 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), 3-position phenyl-substituted acrylates (Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni Complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid are suitable. Special Biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb® FD or Tinosorb® FR ex Ciba are available. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. B. 3- (4-Methylbenzylidene) camphor; 4 Aminobenzoic acid derivatives, preferably 4- (dimethylamino) 2-ethylhexyl benzoate, 4- 2-octyl (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of Cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, 4- Isamyl methoxy cinnamate, 2-ethylhexyl 2-cyano-3,3-phenyl cinnamate (octocrylene); ester salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4- methoxybenzophenone; Esters of benzalmalonic acid, preferably 4-methoxybenzmalonic acid di-2- ethylhexyl ester; Triazine derivatives, such as. B. 2,4,6-Trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazon or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as e.g. B. 1- (4- tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Farther 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, Alkyl ammonium, alkanol ammonium 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. B. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane are particularly suitable as typical UV-A filters, such as for example 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-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 be used. In addition to the soluble substances mentioned, there are also insoluble ones for this purpose Light protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts in question. 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 as well as their mixtures. As salts Silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already in the form of pigments for skin-care and skin-protecting emulsions and decorative Cosmetics used. 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. she can have a spherical shape, but such particles can also be used come that have an ellipsoidal or otherwise different shape from the spherical shape have. The pigments can also be surface treated, i.e. H. hydrophilized or hydrophobized available. Typical examples are coated titanium dioxide, such as. B. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones and, in particular, come as hydrophobic coating agents especially trialkoxyoctylsilane or simethicone in question. Micronized zinc oxide is preferred 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, contain particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight his.

Another class of stabilizers to be used preferably are Fluorescent dyes. These include the 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'- Distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, Naphthalimide, benzoxazole, benzisoxazole and benzimidazole systems and by Heterocycle-substituted pyrene derivatives. The sulfonic acid salts are of particular importance Diaminostilbene derivatives, as well as polymeric fluorescent agents, as disclosed in US 5,082,578 become.

Fluorescent substances can be present 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 be included.

In a preferred embodiment, the aforementioned stabilizing agents are used in any Mixtures used. 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 used.

Examples example 1

In a double-walled beaker, Isomalt® ST-F (150 g, commercial product of the company Palatinit) melted at 150 ° C with continuous stirring. After a homogeneous mass were stirred with dye (s) (optional) and zinc acetate dihydrate (17.4 g) incorporated the melt. The active substance-containing melt was in casting molds or Shed trough tablets. After cooling, an opaque, with the addition of a dye a colored opaque core.

Example 2

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

Example 3

Casting molds (optional tray tablets) were made with particulate zinc acetate dihydrate (250 mg) and / or filled with particulate manganese sulfate (100 mg). In a double-walled beaker Isomalt® ST-F melted at 150 ° C with continuous stirring and 2.2 g each homogeneous melt poured into the molds. After solidification, the moldings had one transparent high-gloss appearance. The salts used (zinc acetate dihydrate and / or Manganese sulfate) was 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 purpose, 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 being present as part of a compressed tablet phase (V1), as part of a pressed core (V2) or as part of an active phase according to the invention (E1). 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 machine dishwashing detergent according to the invention with active phase among the conditions mentioned has significantly better silver corrosion properties. Through the Assembling the manganese sulfate in the active phase improves the silver corrosion protection.

Claims (17)

1. Single-phase or multi-phase detergent tablet, which has at least one active phase, which consists of one or more active washing and / or cleaning 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. laundry detergent or cleaning product according to claim 1, characterized in that the solid matrix (s) a solubility above 200 g / L at 20 ° C, preferably above 300 g / L at 20 ° C. 3. shaped detergent or cleaning product according to one of claims 1 or 2, characterized characterized in that the weight fraction of the solid matrix in the total weight of the active phase at least 20% by weight, preferably at least 40% by weight, particularly preferably is at least 80% by weight and in particular at least 90% by weight. 4. shaped detergent or cleaning product according to one of claims 1 to 3, characterized in that the active phase a) 10 to 98% by weight of matrix material, b) 1.5 to 90 wt .-% of one or more washing and / or cleaning active substance (s) and c) contains 0 to 1.0% of a dye. 5. shaped detergent or cleaning product according to one of claims 1 to 4, characterized characterized in that the matrix material contains one or more meltable substance (s) contains which has a melting point between 30 and 250 ° C, preferably between 35 and 200 ° C and in particular between 40 and 180 ° C has / have. 6. Detergent tablets according to one of claims 1 to 5, characterized 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 their Mixtures, in particular from the group 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 characterized in that the wash or enclosed by the solid matrix cleaning-active substances are selected from the group of enzymes and / or Glass corrosion protection agent and / or the silver protection agent and / or the deposit inhibitor Polymers and / or the pH adjuster. 8. shaped detergent or cleaning product according to one of claims 1 to 7, characterized characterized in that the single- or multi-phase 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 characterized in that the single or multi-phase detergent or cleaning tablets Contains active phase in the form of a layer. 10. Detergent tablets according to one of claims 1 to 9, characterized characterized in that the detergent or cleaning product shaped body has a planar outer surface on which the active phase, which partially covers the planar outer surface, adheres. 11. Detergent tablets according to one of claims 1 to 10, characterized characterized in that the washing or cleaning active substances in the enclosing matrix in pre-assembled form, preferably as a crystal (s) and / or Powder and / or granulate (s) and / or extrudate (s) and / or compact (s) and / or Castings are present. 12. Detergent tablets according to one of claims 1 to 11 that it is the detergent tablet is a textile detergent, the active washing and cleaning substances for textile cleaning in the enclosing Matrix present in tablet form and this tablet (s) preferably have a hardness below 30 N, particularly preferably below 25 N and in particular below 20 N exhibit. 13. Detergent or cleaning product tablet according to one of claims 1 to 11, characterized characterized in that it is a in the detergent tablets machine dishwashing detergent, the washing and cleaning active substances for machine dishwashing in the surrounding matrix in a tablet form are present and this tablet (s) preferably has a breaking hardness below 100 N, especially preferably have below 85 N and in particular below 70 N. 14. Detergent tablets according to one of claims 1 to 13, characterized 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 Detergent tablets is. 15. shaped detergent or cleaning product according to one of claims 1 to 14 characterized in that the phase, which consists of one or more, of a solid matrix enclosed, washing and / or cleaning active substance, at least 5%, preferably at least 7.5% and in particular at least 10% of the total Makes up the surface of the detergent or cleaning product tablet. 16. Detergent tablets according to one of claims 1 to 15, characterized characterized in that the quotient of the weight fraction of the active phase on Total weight of the detergent tablets, and the proportion of Active phase on the entire surface of the detergent tablet at least 0.1, preferably at least 0.2, particularly preferably at least 0.4 and in particular is at least 1.0. 17. Detergent tablets according to one of claims 1 to 16, characterized characterized in that the molded body has a water-soluble packaging.