EP1524313B1 - Machine dishwadhing composition with improved rinsing properties - Google Patents

Abstract

Dishwasher detergent composition comprises a carry over surfactant.

Description

The invention is directed to a detergent composition for dishwashers whose ingredients lead to an improved dishwashing result. In particular, a lower "filming" with simultaneously reduced "spotting" is achieved.

Machine dishwashing generally consists of a pre-rinse cycle, one or more intermediate rinses, a rinse cycle and a drying cycle. This applies in principle to mechanical washing both in households, as well as in the commercial sector.

The aim of machine rinsing is to obtain an optimum result, without mechanical rubbing or wiping being possible, as is the case with manual rinsing. In particular, the rinse result is intended to prevent the formation of a film ("filming") or the retention of "spotting" on the dishes.

A common procedure for obtaining the desired washing result was to fill the dishwasher with a detergent composition, a rinse aid and a salt, the cleaner composition achieved the actual washing result, the salt is filled in the ion exchanger in the machine dishwashing detergent and thus to reduce the water hardness during the Cleaning and rinsing leads; the rinse aid causes the rinse water to run more efficiently on the dishes to minimize "spotting".

More recently, these individual functions have been increasingly offered in a compact form, for example in so-called "3 in 1" dishwashing tablets. Here a 3in1 tablet takes on the task of cleaning, clear rinsing and prevents the precipitation of Ca and Mg ions in the form of salts. Preferably, the various functions are released at different times during the flushing process.

The detergents used for machine washing of dishes can be liquid, powdery, pasty or tablet-shaped. The use of tablets is particularly popular because of the ease of handling and metering.

The object of the invention is to provide a detergent composition for use in machine dishwashing detergents which gives particularly good results in terms of "filming", ie forming a film on the washed dishes, and at the same time forming "spotting" on the dishes to avoid washed dishes.

This object is achieved by a detergent composition for machine dishwashing detergents which comprises (a) at least one carry over surfactant having the general formula R ¹ O (CH ₂ CH ₂ O) _x (CH ₂ CH ₂ CH ₂ O) _y H, wherein R ^{1 is} a linear or branched, saturated or unsaturated hydrocarbon radical having 6 to 30 carbon atoms, preferably 8 to 26, particularly preferably 10 to 24 carbon atoms, x is an integer between 15 and 200, y is an integer smaller is 100 and x + y is less than 200, (b) a salt-functional polymer is formed from monomers of acrylic acid and / or maleic acid in combination with at least one monomer selected from the group 2-acrylamido-2 methylpropanesulfonic acid, methallylsulfonic acid, styrene or sulfonated styrene, which salt functional polymer may be in acidic or neutral form.

A "carry over" surfactant according to the present invention is to be understood as meaning a surfactant which, because of its structure and properties, is "carried away" during the entire cleaning process up to the last rinse in the dishwasher. The details of this type of surfactants will be discussed in more detail below.

The detergent composition contains a salt-functional polymer which prevents the precipitation of Ca and Mg ions in the form of salts or prevents the crystal growth of already formed precipitates.

In a preferred embodiment, the detergent composition also includes a dispersant for non-water soluble compounds / salts.

The cleanser composition may be formulated in any commercial form, e.g. liquid, pasty, in powder, granular or particulate form (e.g., beads, or so-called "pearls"), but is preferably used in the form of a pressed molding. The shaped body can be single-phase or multi-phase. A particularly preferred embodiment is a multi-phase pressed molded body, wherein the individual phases can be solved in the rinsing liquor at different times. Such a pressed molding may contain a suitable disintegrant in individual (or all) phases.

The ingredients Carry over surfactant, salt functional polymer and dispersants may be present in multi-phase tablets in different phases or in different concentrations in the individual phases, so that they are released at different times (in different concentrations) in the rinsing liquor, but also in all Phases of multiphase tablets evenly distributed.

The formation of the film on the dishes is due, inter alia, to the fact that the fatty acids are saponified by the triglycerides of the food residues present in the machine dishwasher by the ingredients of the detergent composition. Lime soaps as typical organic salts melt above certain temperatures. The melting temperature is determined by the chain length of the fatty acid. Below this melting temperature, however, they precipitate out as insoluble soaps and settle on the dishes. To prevent the precipitation in the form of soaps, either the temperature profile of dishwashers can be varied so that the rinse water temperature does not fall below the failure limit of lime soaps, or it can be as high as possible complexing of calcium and magnesium ions in the wash liquor with a Salt or an agent can be controlled with a salt function.

"Spotting" refers to the formation of droplet residues, which can be seen even after drying the dishes, especially on glasses. These residual drops of dissolved salts leave stains on the dishes and glasses. In order to prevent this drop formation surfactants are used in conventional dishwashing detergents, which reduce the surface tension and thus allow a better drainage of the drops from the dishes.

The inventive use of carry over surfactant (s), salt functional polymer (s) and dispersant (s) in the dishwashing detergent composition also reduces spotting. Without wishing to be bound by the following explanation, the reduced residue on the dishes presumably causes the water droplets to drain better from the smoother surfaces. This effect is achieved through the use of carry-over surfactants and additionally reinforced by the salt-functional polymer and a dispersant.

Conventional surfactant compositions typically use surfactants having an alcohol content of up to C20 and an EO content of up to a maximum of 25 moles of E0. The use of surfactants with longer E0 chains in detergent compositions has not previously been described.

Suitable dispersants for the saponified fatty acids are all agents which are capable of producing water-insoluble organic compounds, e.g. To disperse lime soaps in an aqueous composition, especially at temperatures at which these compounds are present in the aqueous medium as insoluble compounds.

Such dispersants are known to those skilled in, among other things, the fields of toilet cleaning articles, cutting oils, textile processing and industrial cleaning. Under the heading "lime soap dispersant" common dispersants are easily on the Internet to find. Examples of such dispersants are alkyl monopropionates, alkyl dipropionates, cocoamphocarboxyglycinates, alcohol ethoxycarboxylates, amine oxides, alkyl dimethyl betaines, terephthalic acid, cocoamido propyl dimethyl betaines, alkylamino diacetates and citronell esters, in addition polymers based on acrylic acid, maleic acid and alpha olefins. The dispersants are used in the detergent compositions according to the invention in amounts of from 0 to 8% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight and especially preferably from 0.8 to 2% by weight.

Carry-over surfactants are surfactants which, due to their hydrophilic-hydrophobic balance, are "carried away" by the individual cleaning and rinsing cycles in the course of the cleaning and rinsing process in a dishwashing machine. An explanation, which is not binding for the invention, is that these surfactants are not subject to the usual Nernst distribution due to their hydrophilic-hydrophobic properties (ie are not removed with the wash liquor and the rinse water), but also during the cleaning process. and rinsing increasingly adsorb to surfaces. This means that these surfactants are present not only in the first wash or rinse cycle in the wash liquor, but also in the last rinses, although there in lower concentrations. This causes even in the last rinses the surface tension of the water is kept lowered, allowing a better drainage of the drops of water from the dishes.

Surfactants which fulfill this object are surfactants of the general formula R ¹ O (CH ₂ CH ₂ O) _x (CH ₂ CH ₂ CH ₂ O) _y H, where R ^{1 is} a linear or branched, saturated or unsaturated hydrocarbon radical having 6 to 30 C atoms, preferably 8 to 26, particularly preferably 10 to 24 carbon atoms, x is an integer between 15 and 200, y is an integer less than 100 and x + y is less than 200. In a preferred embodiment, in at least one of the used carry over Surfactants x at least 26, more preferably greater than 30, and particularly preferably greater than 40, but less than 200. R ¹ is preferably a linear, saturated hydrocarbon radical.

Further suitable surfactants are nonionic surfactants of the formula R ² O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ³ ], in which R ^{2 is} a linear or branched one R ³ denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y for a value of at least 15, is preferred of at least 25 stands.

Further preferred nonionic surfactants which may be used are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ⁴ O [CH ₂ CH (R ⁵ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ⁶ in which R ⁴ and R ^{5 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{6 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 X is butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value is x 2, each R ⁶ in the above formula may be different. R ⁴ and R ⁵ are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ⁶ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ⁶ in the above formula may be different if x is 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ⁶ can be selected to be ethylene oxide (R ⁶ = H) or propylene oxide. (R ⁶ = CH ₃ ) form units which may be joined together in any order, for example (E0) (P0) (E0), (E0) (E0) (P0), (E0) (E0) (E0), (P0) (E0) (P0), (P0) (P0) (E0) and (P0) (P0) (P0). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (E0) groups combined with a small number (P0) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ⁴ O [CH ₂ CH (R ⁶ ) O] _x CH ₂ CH (OH ) CH ₂ OR ⁵ simplified. In the latter formula, R ⁴ , R ⁵ and R ^{6 are} as defined above and x is 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 ⁴ and R ^{5 have} 9 to 14 C atoms, R ^{6 is} H and x assumes values of 6 to 15.

Particularly preferred carry over surfactants of the present invention consist of more than 45% of their molecular weight as hydrophilic groups, preferably more than 60%, particularly preferably more than 70%. The melting point or solidification point of preferred carry-over surfactants is above 25 ° C., preferably above 30 ° C. and particularly preferably above 35 ° C. Preferred carry over surfactants have a cloud point in distilled water above 85 ° C, preferably above 90 ° C and more preferably above 95 ° C.

In one embodiment of the present invention, a carry over surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 25 mol, more preferably at least 30 mol, especially at least 40, 50 or 80 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A preferred room temperature solid nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C ₁₆ -C ₂₀ alcohol), preferably a C ₁₈ alcohol and at least 25 mol, preferably at least 30 mol and especially at least 40, 50 or Obtained 80 moles of ethylene oxide. Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Other suitable surfactants are so-called gemini surfactants. These are generally understood to mean those compounds which are present as dimers and have excellent adsorption behavior in comparison with monomeric surfactants. The Gemini Sides will be discussed in more detail below.

All said carry-over surfactants are used in the detergent compositions according to the invention in amounts of from 0.2 to 20% by weight, preferably from 0.5 to 10% by weight, particularly preferably from 1 to 6% by weight. In addition to the carry over surfactants, further surfactants may be present in the cleaner compositions, as described in more detail below.

In a preferred embodiment of the invention, the detergent composition contains at least two different carry over surfactants, for example two surfactants having the same basic formula but different (EO) / (PO) units, for example two carry over surfactants both having the basic formula R ¹ O (CH ₂ CH ₂ O) _x (CH ₂ CH ₂ CH ₂ O) _y H, wherein R ¹ in both surfactants is a linear or branched, saturated or unsaturated hydrocarbon radical having 6 to 30 carbon atoms and x in one Surfactant is an integer between 15 and 30 and in the other surfactant is an integer between 50 and 100, y each an integer less than 100 and x + y is less than 200. But it can also at least two carry over Surfactants are used with various basic formulas described above.

In order to ensure the salt function as well as a threshold effect (minimizing the precipitation of salts of Ca and Mg ions) in the rinse at high water hardnesses, a polymer is preferably used in the cleaning composition according to the invention. Such salt-functional polymers are known from the prior art, in particular from the field of water treatment. Examples of such polymers are products of the type Acusol 587 (Rohm & Haas), which are equally praised as calcium phosphate inhibitors, anti-filming and dispersing agents.

A copolymer to be used according to the invention consists of monomers of acrylic acid and / or maleic acid in combination with at least one monomer selected from 2-acrylamido-2-methylpropanesulfonic acid, methallylsulfonic acid, styrene or sulfonated styrene, whereby the salt-functional polymer may be in acidic or neutral form. The sulfonation of the individual monomers can be present before the polymerization, or can be introduced only after polymerization has taken place. The term "copolymer" in this context includes a polymer having two or more different types of monomers including, for example, terpolymers.

Such a salt-functional polymer has a molecular weight in the range of 3,000 to 100,000, preferably 4,000 to 80,000.

Preferably, in the copolymer of sulfonated / non-sulfonated monomers, the proportion of non-sulfonated monomers in the salt functional polymer is from 10% to 90%, preferably from 50% to 80%, the proportion of sulfonated monomers from 10% to 90%, preferably from 20% to 50%.

Such a salt-functional polymer is used in the composition according to the invention in amounts of from 0.2 to 20% by weight, preferably from 0.5 to 10% by weight, particularly preferably from 0.8 to 5% by weight.

The detergent tablets may be pressed from only one detergent composition (single-phase tablets), or they may consist of several phases, layers or regions, e.g. two- or three-phase molded bodies (e.g., "3 in 1"). In this case, individual components of the cleaning agent can be separated from each other, so that they are provided at different times during the cleaning process.

The spatial form of the moldings can be adapted in their dimensions of the dispensing compartment of the dishwasher, but all reasonable manageable shapes can be designed. These include e.g. also cylindrical embodiments with an oval or circular cross-section and shaped body with a plate or panel-like structure. A preferred shaped body consists of alternately thick long and thin short segments, so that individual segments of such a bar at predetermined breaking points, which are represented by the short thin segments, can be broken off and entered into the metering chamber or the cutlery basket of the machine. This principle of the bar-shaped shaped body can also be realized in other geometric polygonal shapes.

A tablet produced in this way preferably has a weight of from 5 to 120 g, more preferably from 10 to 30 g.

Detergent tablets for different purposes, especially for dishwashers are basically known.

Formulated detergent formulations of this type generally contain builders, bleaching agents and bleach activators, Surfactants, tableting aids, disintegrants and other common additives and auxiliaries.

Incidentally, in the invention described herein, the detergent composition may contain the usual ingredients for dishwashing detergents. The ingredients of the cleaner composition described below are merely preferred embodiments.

Examples of known and customary cleaning formulations in the field of machine dishwashing detergents are described inter alia in the laid-open patent applications DE 101 40 535 A1, DE 199 59 589 A1, EP 0 282 482 or DE 101 36 002 A1.

A preferred embodiment of the invention is a phosphate-containing dishwashing detergent tablet containing: 10 to 75 parts by weight Polyphosphate (s), 60 to 0 parts by weight other inorganic builders, 20 to 0 parts by weight organic builders, 3 to 20 parts by weight peroxide bleaching agent, 6 to 0.5 parts by weight Bleach activator (s), 0.2 to 16 parts by weight Carry over surfactant (s), 0 to 8 parts by weight dispersants 0.2 to 8 parts by weight Salt function polymer (s) 2 to 6 parts by weight other, customary auxiliaries and additives.

For all embodiments, both mono-, as well as double or triple tablets are preferred.

In all layers / phases of the cleaning tablet, a disintegrant may be included, but is preferably contained in only one or in two (in the presence of multiple layers / phases) layers / phases. This is preferable to a first layer / phase that comes into effect quickly contains constituents that dissolve in the rinse water in a short time and thus provide the constituents, while another layer / phase, which contains constituents which are to be used at a later time of the cleaning process, dissolves more slowly since it has no or no " slower "disintegrant contains.

Suitable builders in the detergent composition are all customary and known builders, in particular polyphosphates, pyrophosphates, metaphosphates or phosphonates, sheet silicates, amorphous silicates, amorphous disilicates and zeolites, and fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium bicarbonate, citrate and citric acid, Succinic, tartaric and malic acid. Frequently co-builders and dispersants are used as auxiliary builder. Such co-builders or dispersants may be, inter alia, polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.

Typical bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, and H ₂ O ₂ -forming peracidic salts, peracids, such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids. However, other known bleaching agents or bleach systems may also be present in the composition.

As for the use in agents according to the invention suitable peroxygen compounds are in particular hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts to which alkali metal perborates such. Sodium perborate tetrahydrate and sodium perborate monohydrate, further include alkali metal carbonate perhydrates such as sodium carbonate perhydrate ("sodium percarbonate") and persilicates and / or persulfates such as caroate. Most often in addition to these inorganic peroxy compounds, the bleach system of the detergent formulation inorganic or organic peracids, in particular percarboxylic acids, contain, for. B. C ₁ -C ₁₂ -Percarbonsäuren, C ₈ -C ₁₆ -Dipercarbonsäuren, Imidopercapronsäuren or Aryldipercapronsäuren. Preferred examples of acids which can be used are peracetic acid, perbenzoic acid, linear or branched octane, nonane, decane or dodecane monoperacids, decane and dodecane diperacid, mono- and diperphthalic acids, isophthalic acids and terephthalic acids. Phthalimidopercaproic acid, terephthaloyldiamidopercaproic acid and e-phthalimido peroxohexanoic acid (PAP). These percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. A particularly preferably used peracid is the peracid available under the trade name Eureco® (Ausimont, Italy). Peroxygen compounds are present in amounts of preferably up to 50% by weight, more preferably from 5% to 30% and most preferably from 8% to 25% by weight. The addition of minor amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.

The content of bleaching agents in tablets is preferably 0.5-50% by weight, and more preferably 1-30% by weight.

The bleach catalysts used are usually quaternized imines or sulfonimines, as described, for example, in US Pat. No. 5,360,568, US Pat. No. 5,360,569 and EP-A-453,003, as well as manganese complexes, as described, for example, in WO-A 94/21777 are. Other useful metal-containing bleach catalysts are described in EP-A-458,397, EP-A-458,398 and EP-A-549,272. Bleach catalysts are generally used in amounts of up to 10 wt .-%, in particular 0.1 to 6 wt .-%, based on the detergent formulation. Suitable bleach activators are the H ₂ O ₂ organic peracids forming N-acyl and O-acyl compounds, preferably N, N'-tetraacylated diamines, carboxylic anhydrides and esters of polyols such as glucose pentaacetate. Further, acetylated mixtures of sorbitol and mannitol may be used. Particularly suitable as bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol-mannitol. Mixtures (SORMAN).

In addition, compounds of the substance classes of polyacylated sugar or sugar derivatives with C ₁ -C ₁₀ -acyl radicals can be used, preferably with acetyl, propionyl, octanoyl, nonanoyl or benzoyl radicals, in particular acetyl radicals. Suitable sugars or sugar derivatives are mono- or disaccharides and their reduced or oxidized derivatives, preferably glucose, mannose, fructose, sucrose, xylose or lactose. Particularly suitable bleach activators of this class of substances are, for example, pentaacetylglucose, xylose tetraacetate, 1-benzoyl-2,3,4,6-tetraacetylglucose and 1-octanoyl-2,3,4,6-tetraacetylglucose.

Further suitable as bleach activators are O-Acyloximester such. O-acetylactone oxime, O-benzoylacetone oxime, bis (propylimino) carbonate or bis (cyclohexylimino) carbonate. Such acylated oximes and oxime esters are described, for example, in EP-A-028 432 and EP-A-267 046.

Also useful as bleach activators are N-acyl caprolactams, such as N-acetyl caprolactam, N-benzoyl caprolactam, N-octanoyl caprolactam, N-octanoyl caprolactam, or carbonyl biscaprolactam.

• N-diacylierte und N,N'-tetracylierte Amine, z. B. N,N,N',N'-Tetraacetylmethyldiamin und -ethylendiamin (TAED), N,N-Diacetylanilin. N,N-Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5-dimethylhydantoin;
• N-Alkyl-N-sulfonyl-carbonamide, z. B. N-Methyl-N-mesyl-acetamid oder N-Methyl-N-mexyl-benzamid;
• N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, z. B. Monoacetyl-maleinsäurehydrazid;
• O,N,N-trisubstituierte Hydroxylamine, z. B. O-N,N-trisubstituierte Hydroxylamine, z. B. O-Benzoyl-N,N-succinylhydroxylamin, 0-Acetyl-N,N-succinyl-hydroxylamin oder O,N,N-Triacetalhydroxylamin;
• N,N'-Diacyl-sulfurylamide, z. B. N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N'-Diethyl-N,N'-dipropionyl-sulfurylamid;
• Triacylcyanurate, z. B. Triacetylcyanurat oder Tribenzoylcyanurat;
• Carbonsäureanhydride, z. B. Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid oder Phthalsäureanhydrid;
• 1,3-Diacyl-4,5-diacyloxy-imidazolin, z. B. 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• Tetraacetylglycoluril und Tetrapropionylglycoluril;
• Diacylierte 2,5-Diketopiperazine, z. B. 1,4-Diacetyl-2,5-diketopiperazin;
• Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff, z. B. Tetraacetylpropylendiharnstoff.
• α-Acyloxy-polyacyl-malonamide, z. B. α-Acetoxy-N,N'-diacetylmalonamid;
• Diacyl-dioxohexahydro-1,3,5-triazine, z. B. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin.

Further usable as bleach activators

• N-diacylated and N, N'-tetracyclized amines, e.g. N, N, N ', N'-tetraacetylmethyldiamine and ethylenediamine (TAED), N, N-diacetylaniline. N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;
• N-alkyl-N-sulfonyl-carboxamides, eg. N-methyl-N-mesyl-acetamide or N-methyl-N-mexyl-benzamide;
• N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. Monoacetyl-maleic hydrazide;
• O, N, N-trisubstituted hydroxylamines, e.g. B. ON, N-trisubstituted hydroxylamines, eg. O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetalhydroxylamine;
• N, N'-diacyl-sulfurylamides, e.g. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionyl-sulfurylamide;
• Triacylcyanurates, e.g. Triacetyl cyanurate or tribenzoyl cyanurate;
• Carboxylic anhydrides, eg. Benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• 1,3-Diacyl-4,5-diacyloxy-imidazoline, e.g. B. 1,3-diacetyl-4,5-diacetoxyimidazoline;
• Tetraacetylglycoluril and tetrapropionylglycoluril;
• Diacylated 2,5-diketopiperazines, e.g. For example, 1,4-diacetyl-2,5-diketopiperazine;
• Acylation products of propylene diurea and 2,2-dimethylpropylenediurea, e.g. B. tetraacetylpropylenediurea.
• α-acyloxy-polyacyl malonamides, e.g. For example, α-acetoxy-N, N'-diacetylmalonamide;
• Diacyl-dioxohexahydro-1,3,5-triazines, e.g. For example, 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine.

Also usable as bleach activators are 2-alkyl- or 2-aryl- (4H) -3,1-benzoxain-4-ones, as described, for example, in EP-B-332 294 and EP-B-502 013. In particular, 2-phenyl- (4H) -3,1-benzoxain-4-one and 2-methyl- (4H) -3,1-benzoxain-4-one are useful.

In addition, bleach activators from the classes of N- or 0-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetyl-glucose are used.

However, a preferred bleach activator is a quaternized glycine nitrile from the group consisting of N-methylmorpholinium acetonitrile methylsulfate, sulfate and hydrogen sulfate.

As a bleach system (bleaching agents and bleach activators), it is also possible for all of the bleaching agents and activators mentioned in DE 199 59 589 A1 to be present. In addition, the bleach systems mentioned in European patent application EP 02 028 958.3 can also be used.

It is preferred that the different constituents of the detergent composition are contained in different phases / layers / regions of the moldings. In particular, it is preferable that a component to be provided at an earlier time of the cleaning operation is in a phase / layer / region in which a disintegrant is contained.

In addition to the carry-over surfactants described above, the cleaning agents may also comprise one or more other surfactants from the group of nonionic, anionic, cationic and / or amphoteric surfactants.

Other important ingredients of detergents come from the groups of enzymes, corrosion inhibitors and dyes and perfumes. These substances are described below.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the automatic dishwashing detergent tablets according to the invention comprise nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 E0 per mole of alcohol. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 E0 or 4 E0, C ₉ -C ₁₁ -alcohol with 7 E0, C ₁₃ -C ₁₅ -alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C ₁₂ -C ₁₈ -alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 E0 and C ₁₂ -C ₁₈ -alcohol with 5 E0. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 E0 can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0.

Particular preference is given to detergent tablets according to the invention which contain a nonionic surfactant which has a melting point above Room temperature. Accordingly, preferred detergent tablets are characterized in that they contain as ingredient c) nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and in particular between 26, 6 and 43.3 ° C included.

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

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (P0 / E0 / PO) surfactants. Such (P0 / E0 / P0) nonionic surfactants are also characterized by good foam control. Preferably, the P0.Einheiten make up to 25 wt .-%, more preferably 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.

Further particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene block polymer blend, of 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

Further preferred detergent tablets according to the invention contain 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 having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15 ,

Further preferred nonionic surfactants which may be used 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 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 X is butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value is x 2, each R ³ in the above formula may 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, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly prefers. 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 may be different if x is 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when 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 may be joined in any order, for example (E0) ( P0) (E0), (E0) (E0) (P0), (E0) (E0) (E0), (P0) (E0) (P0), (P0) (P0) (E0) and (P0) ( P0) (P0). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (E0) groups combined with a small number (P0) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1 such that the above formula is R ¹ O (CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH ) CH ₂ OR ^2. In the latter 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 surfactants are in which the radicals R ¹ and R ^{2 have} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

In addition, alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol can be used as nonionic surfactants in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. B. off Coconut, palm, tallow fat or oleyl alcohol, and on average from 2 to 8 E0 per mole of alcohol. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 E0 or 4 E0, C ₉ -C ₁₁ -alcohols with 7 E0, C ₁₃ -C ₁₅ -alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C ₁₂ -C ₁₈ -alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 E0 and C ₁₂ -C ₁₈ -alcohol with 5 E0. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 E0 can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0. In addition, as further nonionic surfactants and alkyl glycosides of the general formula R0 (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of this nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half thereof.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

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

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

In the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyaryl radical having 1 to 8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

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

Conversely, however, can also by the content of individual phases or the entire molding, d. H. all phases, on certain surfactants a positive effect can be achieved. The incorporation of the alkylpropyl glycosides described above has proved to be advantageous, so that detergent tablets are preferred in which at least one phase of the moldings contains alkylpolyglycosides.

Other suitable surfactants are so-called gemini surfactants. These are generally understood to mean those compounds which are present as dimers and have two hydrophobic groups per molecule in comparison with monomeric surfactants. These groups are usually separated by a so-called hydrophilic spacer. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis- and trimercarbon tris-sulfates and ether sulfates according to the German patent application DE-A-195 03 061. Endgroup-capped dimer or trimeric mixed ethers according to the German patent application DE-A-195 13 391 are characterized in particular by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in automatic washing or cleaning processes.

However, it is also possible to use gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO-A-95/19955.

Suitable enzymes in the detergent tablets according to the invention are, in particular, those from the classes of hydrolases, such as proteases, esterases, lipases or lipolytic enzymes, glucosidases, such as amylases, mannanase or cellulase, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens as well as from their genetically modified variants obtained enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or Mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%. In the context of the present invention preferred detergent tablets are characterized in that they contain protease and / or amylase.

Due to the fact that the detergent tablets according to the invention can contain the enzyme (s) in different phases, it is possible to provide tablets with very precisely defined enzyme release and action. The table below gives an overview of possible enzyme distributions in novel two-phase detergent tablets: Phase 1 Phase 2 amylase protease lipase Amylase + protease Amylase + lipase Protease + lipase Amylase + protease + lipase amylase protease lipase Amylase + protease Amylase + lipase Protease + lipase Amylase + protease + lipase amylase amylase protease amylase Amylase + protease amylase amylase protease protease protease Amylase + protease protease amylase Amylase + protease protease Amylase + protease Amylase + protease Amylase + protease lipase amylase Amylase + lipase amylase Protease + lipase amylase Amylase + protease + lipase amylase lipase protease Amylase + lipase protease Protease + lipase protease Amylase + protease + lipase protease lipase Amylase + protease Amylase + lipase Amylase + protease Protease + lipase Amylase + protease Amylase + protease + lipase Amylase + protease

If the enzymes are used only in one phase of the moldings according to the invention, detergent moldings are preferred in which the enzyme (s) is / are not contained in one phase together with the bleach-enhancing active ingredient combination.

The separation of the bleaching agent from the enzymes is hereby preferred. Detergent tablets characterized in that at least one phase contains bleach while at least one other phase contains enzymes are also preferred embodiments of the present invention.

The detergents according to the invention may contain corrosion inhibitors for protecting the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, above all, silver protectants can be selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

If the detergent tablets contain corrosion inhibitors, they are preferably separated from the bleaching agents. Accordingly, detergent tablets in which at least one phase contains bleach while at least one other phase contains corrosion inhibitors are preferred.

Preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8 to C18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty acids which in themselves constitute nonionic surfactants (see description below). In turn, sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Preferred anionic surfactant mixtures contain combinations of alk (en) ylsulfates, in particular mixtures of saturated and unsaturated fatty alk (en) ylsulfates, and alkylbenzenesulfonates, sulfonated fatty acid glycerol esters and / or α-sulfofatty acid esters. In particular, mixtures are preferred here which contain as anionic surfactants alk (en) ylsulfates and alkylbenzenesulfonates, alk (en) ylsulfates and α-sulfofatty acid methyl esters and / or sulfonated fatty acid glycerol esters.

As further anionic surfactants are in particular soaps, preferably in amounts of 0.1 to 5 wt.% Into consideration. Suitable examples are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Particularly preferred are those soap mixtures which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₂₄ fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The anionic surfactants and soaps can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of their sodium salts.

Further preferred ingredients are inorganic salts which react alkaline in water. To these inorganic alkaline salts In particular, bicarbonates, carbonates or mixtures thereof. Preferably, alkali metal carbonate and especially sodium carbonate are used. As additional alkaline salts are the alkali metal silicates in amorphous or crystalline form with a Na20 to SiO 2 ratio of 1: 1 to 1: 2,8 to call. Also used are the cogranulates of carbonates and silicates, which are available on the market as so-called NABION (Rhodia).

Examples of other customary additives and auxiliaries are magnesium silicates, aluminum aluminates, benzotriazole, glycerol, magnesium stearate, polyalkylene glycols, hexametaphosphate and phosphonates.

Another component of the detergent composition are substances which have an anti-corrosion effect on glass. As glass corrosion protection, all known corrosion protection agents can be used. Examples of these are metal oxides, e.g. Oxides of zinc, aluminum, tin, magnesium, calcium, strontium, silicon, titanium, zirconium, manganese and lanthanum, or insoluble inorganic zinc compounds, as described in EP 0383482, or zinc or magnesium salts of organic compounds, such as they are described in DE 101 40 535.

In addition, colorants and fragrances may be added to the automatic dishwashing compositions according to the invention in tablet form in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to the performance. As perfume oils or perfumes, individual fragrance compounds, eg. As the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, Styrallyl propionate and Benzylsalicylate. The ethers include, for example, benzyl ethyl ether to the aldehydes z. B. the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. The alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and termpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, Olibanumöl, galbanum oil and labdanum oil and orange blossom oil, neroliol. Orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the moldings of the invention, but it may also be advantageous to apply the fragrances on carriers. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients. An incorporation of the fragrances as ingredient d) in the detergent components of the invention is possible and leads to a fragrance impression when opening the machine.

In order to improve the aesthetic impression of the agents according to the invention, it (or parts thereof) can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to those treated with the agents Substrates such as glass, ceramics or plastic dishes, so as not to stain them. In particular, the coloring of individual phases for optical differentiation is preferred.

The invention will be explained in more detail with reference to embodiments, without being limited to these. All data are by weight unless otherwise indicated in individual cases.

The tablets mentioned in the examples can be used as mono-, double- and triple-phase tablets. The individual constituents can be distributed in different regions / phases of the shaped bodies.

example 1

Table 1: Examples of compositions of dishwashing tablets according to the invention (all amounts in parts by weight). formulation 1 2 3 4 Component: Na tripolyphosphate 35,00 45,00 18,00 60,00 Na carbonate 25,00 20.00 10.00 - Na-bicarbonate - - 10.00 - silicate 4.00 10.00 5.00 - citrate - 5.00 10.00 - Na-percarbonate or Na-perborate 15.00 8.00 20.00 20.00 TAED 4.00 5.00 2.00 2.00 Lime soap dispersant (1) 5 0.2 - 2 Carry over surfactant (2) 2.00 1.00 5.00 2.00 Nonionic surfactant - - - 2 phosphonate 1.00 0.50 2.00 - Sulphonated polycarboxylate (3) 1 8th 2 4 Acrylate-maleate copolymer 1.00 - 5.00 3.00 enzymes 2.00 1.00 3.00 2.00 Polyethylene glycol 1,500 - 10,000 2.00 3.00 1.00 2.00 Perfume 0.50 0.05 2.00 1.00 explosives 3.50 - 7.00 - (1) AMA 100 (Lakeland) (a dipropionate)
(2) Lutensol AT 25 (BASF) (nonionic surfactant C16 / 18 25 E0)
(3) Acusol 587D (Rohm & Haas)

Example 2: Comparative Example: Investigation of the "filming" and "spotting" of commercial products on the market

Various dishes and cutlery are subjected to a complete, pre-programmed wash and rinse cycle in a commercial dishwasher. As pollution in each case a standard pollution is used. Upon completion of the program, the cleaned dishes and cutlery are visually patterned and rated according to the following scale:

• 4 = keine Filmbildung, vollständig klar
• 3 = geringe Filmbildung
• 2 = starke Filmbildung
• 1 = sehr starke Filmbildung, Glas erscheint trübe

Classification "Filming":

• 4 = no filming, completely clear
• 3 = low film formation
• 2 = strong film formation
• 1 = very strong film formation, glass appears cloudy

• 8 = keinerlei Flecke oder Streifen
• 7 = sehr wenig schwache Streifen und/oder sehr wenige kleine Flecke
• 6 = einige schwache Streifen und/oder kleine Flecke
• 5 = schwache bis mittelstarke Streifen und/ oder wenige mittelgroße Flecke
• 4 = einige mittelstarke Streifen und /oder mittelgroße Flecke
• 3 = mittelstarke Streifen und/oder einige größere Flecke
• 2 = einige längere Streifen und/oder größere Flecke
• 1 = lange Streifen und/oder viele große Flecke
• 0 = sehr große Streifen und/oder eine Vielzahl großer Flecke

Classification "spotting":

• 8 = no stains or stripes
• 7 = very few faint streaks and / or very few small stains
• 6 = some faint streaks and / or small spots
• 5 = weak to medium streaks and / or a few medium stains
• 4 = some medium streaks and / or medium stains
• 3 = medium streaks and / or some larger stains
• 2 = some longer stripes and / or larger spots
• 1 = long stripes and / or many large spots
• 0 = very large stripes and / or a variety of large spots

Conclusion: The filming of common commercial products is between 2 and 3, the spotting varies depending on the surface relatively strong, but reached a maximum value of 4.1 for the examined commercial products.

Example 3: Filming and spotting of various formulations, with and without dispersant, carry over surfactant and salt functional polymer

Used base formulation for a detergent composition to study the effect on filming and spotting ingredient % w / w sodium tripolyphosphate 64.1 Sodium disilicate 3 soda 7 sodium 17 TAED 3 phosphonate 0.3 enzymes 2.5 perfume oil 0.1 PEG 4000 E 3 100

The additives which are tested for their effect are added to this base formulation. The classification of the rinsing results is carried out as in Example 2. Table 2: Formulations and results: Basic formulation 1 2 3 4 5 6 7 3% carry over surfactant (1) - - - Yes Yes Yes Yes 2% salt functional polymer (2) - Yes Yes - - Yes Yes 1.5% dispersing agent (3) - - Yes - Yes - Yes Results: spotting Longdrink glasses 0.2 1.3 1.8 3.0 3.2 4.4 4.6 Plate of black glass 0.0 2.9 4.4 4.2 4.0 5.8 5.8 Plate black porcelain 0.0 2.5 2.7 3.0 3.7 5.7 6.0 Mean: spotting 0.1 2.2 2.9 3.4 3.6 5.3 5.4 Results: Filming Longdrink glasses 3.0 3.0 3.0 2.9 2.9 3.0 2.9 Plate of black glass 3.0 3.0 3.0 2.9 3.0 3.0 3.0 Plate black porcelain 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Average: Filming 3.0 3.0 3.0 2.9 3.0 3.0 3.0 (1) Lutensol AT 25 (BASF) (nonionic surfactant C16 / 18 25 E0)
(2) Acusol 567D (Rohm & Haas)
(3) AMA 100 (Lakeland) (a dipropionate)

The table shows that the addition of a carry over surfactant causes a significant reduction in flocculation, which is further enhanced by the addition of a salt functional polymer. The addition of a dispersant additionally causes an improvement in the washing results. In particular, improved "spotting" is achieved with good "filming" compared to commercially available products.

Example 4:

The filming and spotting of the composition according to the invention is compared with the filming and spotting of compositions in which the constituents correspond to surfactant, salt functional polymer or dispersants of conventionally employed substances. The base composition of the cleaner composition used was the same base formulation as in Example 3. The classification of the results is made as in Example 2. Basic formulation 8th 9 10 11 12 2.5% carry over surfactant (1) Yes StDt Yes Yes StDt 3% salt functional polymer (2) Yes StDt Yes StDt Yes 1% dispersing agent (3) Yes StDt StDt Yes Yes Results: spotting Longdrink glasses 4.7 0.5 4.2 4.1 1.1 Plate of black glass 4.5 0.3 4.0 3.5 1.2 Plate black porcelain 5.5 0.7 5.0 4.7 1.5 Knife (one piece) 5.0 0.8 5.5 4.0 2.3 Mean: spotting 4.9 0.6 4.7 4.1 1.5 Results: Filming Longdrink glasses 2.8 3.0 2.8 2.7 2.9 Plate of black glass 3.0 3.0 2.8 2.8 3.0 Plate black porcelain 3.0 3.0 2.8 2.9 3.0 Knife (one piece) 3.0 3.0 2.8 2.8 2.9 Average: Filming 3.0 3.0 2.8 2.8 3.0 (1) Yes = Lutensol AT80 (2%) and AT25 (0.5%) (BASF) (80 and 25 EO nonionic surfactants) StdT = according to the state of the art: Lutensol AT11 (C16-18, 11 E0)
(2) Yes = Acusol 587D (Rohm & Haas) StdT = Sokolan CP45 (maleic acid-acrylic acid copolymer)
(3) Yes = AMA 100 (Lakeland) (a dipropionate) StdT = Lutensol A030 (C13-15, 30 E0)

The results of these comparative experiments show that even the use of carry over surfactants leads to a significantly improved performance with respect to the spotting on the washed dishes compared to conventionally used surfactants, whereby still a very good filming value is achieved , The additional use of a salt-functional polymer according to the invention makes it possible to reduce staining even further, whereas the use of the dispersant according to the invention improves the "filming" values of the composition.

Claims (7)

1. A detergent composition for dishwashing machines, which comprises

   (a) at least one "carry over" surfactant which has the general formula R¹O(CH₂CH₂O)_x(CH₂CH₂CH₂O)_yH, in which R¹ represents a linear or branched, saturated or unsaturated hydrocarbon residue with 6 to 30 C atoms, preferably 8 to 26, particularly preferably 10 to 24 C atoms, x is an integer between 15 and 200, y is an integer of less than 100 and x+y is less than 200,

   (b) a salt function polymer which is formed from monomers of acrylic acid and/or maleic acid in combination with at least one monomer which is/are selected from the group 2-acrylamido-2-methylpropanesulfonic acid, methallylsulfonic acid, styrene or sulfonated styrene, wherein the salt function polymer may be present in acidic or neutral form.
2. A detergent composition according to claim 1, characterised in that at least one carry over surfactant has the general formula R¹O(CH₂CH₂O)_x(CH₂CH₂CH₂O)_yH, in which R¹ represents a linear or branched, saturated or unsaturated hydrocarbon residue with 6 to 30 C atoms, preferably 8 to 26, particularly preferably 10 to 24 C atoms, x is an integer between 26 and 200, y is an integer of less than 100 and x+y is less than 200.
3. A detergent composition according to any one of claims 1 or 2, characterised in that at least two different carry over surfactants are used.
4. A detergent composition according to any one of claims 1 to 3, characterised in that a dispersant is moreover present.
5. A detergent composition according to any one of claims 1 to 4, characterised in that it contains: 10 to 75 pbw of polyphosphate(s), 60 to 0 pbw of other inorganic builders, 20 to 0 pbw of organic builders, 3 to 20 pbw of peroxide bleaching agent, 6 to 0.5 pbw of bleaching activator(s), 0.2 to 16 pbw of carry over surfactant(s), 0 to 8 pbw of dispersant 0.2 to 8 pbw of salt function polymer(s) 2 to 6 pbw other conventional auxiliary substances and additives.
6. A detergent composition according to any one of claims 1 to 5, characterised in that it assumes the form of a single-phase or multi-phase pressed moulding or a powder.
7. Use of at least one carry over surfactant as defined in claim 1 in combination with a salt function polymer as defined in claim 1 in a detergent composition for machine dishwashing agents.