EP1524313A1 - 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, their ingredients to an improved dishwashing result to lead. In particular, a lower "filming" at the same time reduced "spotting" achieved.

Machine dishwashing generally consists of a pre-wash cycle, one or more intermediate rinses, a rinse cycle and a Drying cycle. This applies in principle to the machine rinsing both in Households, as well as in the commercial sector.

The aim of machine rinsing is to obtain an optimal result without mechanical rubbing or wiping as in the case of rinsing is possible by hand. In particular, the rinsing result is to form a Films ("filming") or the remaining of spills ("spotting") prevent on the dishes.

A common procedure for obtaining the desired rinsing result was So far, the dishwasher with a cleaner composition, a Rinse a rinse aid and a salt, wherein the cleaner composition the actual washing result scored the salt in the ion exchanger is filled in the machine dishwashing detergent and thus for reduction the water hardness during the cleaning and rinsing process leads; the rinse aid causes the improved rinsing of the rinse water on the Crockery to minimize "spotting".

More recently, these individual functions have become more common in a compact form, e.g. in so-called "3 in 1" dishwashing tablets offered. Here, a 3in1 tablet takes over the task of Cleaning, rinsing and prevents the precipitation of Ca and Mg ions in the form of salts. Preferably, the various functions become different Time points during the flushing released.

The means used for the automatic cleaning of dishes can be liquid, powdery, pasty or tablet-shaped. The application of tablets is because of the ease of handling and dosing Popular.

The object of the invention is a cleaning composition for an application in machine dishwashing detergents which provide particularly good Results regarding the "filming", ie the making of a film effecting the rinsed dishes while at the same time forming drip residues ("Spotting") on the rinsed dishes to avoid.

This object is achieved by a detergent composition for Machine dishwashing detergent comprising at least one carry over surfactant.

Under a "carry over" surfactant according to the present invention is a To understand surfactant, because of its structure and its properties over the entire cleaning process up to the last rinse in the Dishwasher is "kidnapped". On the details of this type of Surfactants will be discussed in more detail below.

In a preferred embodiment, the detergent composition contains in addition, a salt-functional polymer which promotes the precipitation of Ca and Mg ions in the form of salts prevent or crystal growth prevents already formed precipitates.

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

The cleanser composition may be formulated in any commercial form be, so for example liquid, pasty, in powder, granule or particle form (e.g., beads, or so-called "pearls"), but is preferred used in the form of a pressed molding. The shaped body can be one or be multi-phase. A particularly preferred embodiment provides a multi-phase pressed molded body, wherein the individual phases in the rinsing liquor can be solved at different times. Such a Pressed molding can enter into individual (or all) phases include suitable disintegrant.

The ingredients mentioned carry over-surfactant, salt-functional polymer and Dispersants can be used in multi-phase tablets in different phases or in different concentrations in the individual phases, so they at different times (in different concentrations) can be released into the rinsing liquor, but can also be used in all phases of multiphase tablets evenly distributed.

Forming the film on the dishes comes u.a. by the fact that from the triglycerides of the food residues present in the machine dishwasher by the ingredients of the cleaner composition the fatty acids be saponified. Lime soaps as typical organic salts melt above certain temperatures. The melting temperature is determined by the chain length the fatty acid. Fall below this melting temperature They do, however, as insoluble soaps and sit on the dishes from. To prevent precipitation in the form of soaps, either the Temperature profile of dishwashers can be varied so that the rinse water temperature the failure limit of lime soaps does not fall below or it can be as high as possible complexation of calcium and magnesium ions in the rinsing liquor with the aid of a salt or an agent a salt function are controlled.

By "spotting" is meant the formation of droplet residues, too after drying the dishes, especially on glasses can be seen. These residual drops of dissolved salts leave stains on the dishes and glasses. To prevent this dripping Surfactants used in conventional dishwashing detergents are the surface tension decrease and thus a better drainage of the drops of Allow dishes.

Through the use according to the invention of carry over surfactant (s), salt functional polymer (s) and dispersant (s) in the dishwashing detergent composition Spotting is also reduced. Without the following The explanation is probably due to the fact that it is bound to be bound Residue on the dishes that the water drops from the thus smoother Surfaces can run better. This effect is due to the use achieved by carry over surfactants and by the salt functional polymer and a dispersant additionally reinforced.

Conventional surfactant compositions are commonly used in detergent compositions with an alcohol content of up to C20 and an EO content of up to a maximum of 25 mol E0 used. The use of surfactants with longer E0 Chains in detergent compositions have not previously been described.

As dispersants for the saponified fatty acids all agents come in Consider that are capable of not water-soluble organic compounds such as. To disperse lime soaps in an aqueous composition, especially at temperatures at which these compounds in the aqueous medium are present as insoluble compounds.

Such dispersants are those skilled in the art, inter alia from the fields the toilet cleaning articles, the cutting oils, from textile processing and the field of industrial cleaning. Under the keyword "Lime soap dispersant" are common dispersants readily available 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, as well Polymers based on acrylic acid, maleic acid and alpha olefins. The Dispersants come in the detergent compositions of 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 more preferably from 0.8 to 2% by weight used.

"Carry-over" surfactants are surfactants that are based on their hydrophilic-hydrophobic balance in the course of the cleaning and rinsing process in a dishwasher by the individual cleaning and Rinses are "delayed". A statement that is not binding on the Invention is to be interpreted that these surfactants due to your Hydrophilic-hydrophobic properties not the usual Nernst distribution subject (so not with the wash and the rinse water removed), but also during the cleaning and rinsing process increasingly adsorb to surfaces. This means that these surfactants not only in the first wash or rinse cycle in the rinsing liquor, but also in the last rinse cycles, although there in lesser Concentration. This causes, even in the last rinses the Surface tension of the water is kept low, which is a better Drain the water drops allowed by the dishes.

Surfactants which fulfill this object are, for example, 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 C 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 carry-over surfactants used, x is 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 form ethylene oxide (R ⁶ = H) or propylene oxide (R ⁶ = 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 ⁴ O [CH ₂ CH (R ⁶ ) O] _x CH ₂ CH (OH ) CH ₂ 0R 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 an ethoxylated room temperature Nonionic surfactant resulting from the reaction of a monohydroxyalkanol or A1-kylphenol with 6 to 20 carbon atoms, preferably at least 25 mol, especially preferably at least 30 mol, in particular 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. this includes In general, such compounds are understood to be dimers present and compared to monmeren surfactants excellent adsorption behavior exhibit. The Gemini Sides will be more detailed below received.

All said carry over surfactants are in the detergent compositions of the invention used in amounts of from 0.2 to 20% by weight, preferably from 0.5 to 10% by weight, more preferably from 1 to 6% by weight. Next The carry over surfactants can still be found in cleaner compositions be included further surfactants, as detailed below again.

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, where 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. However, at least two carry over surfactants with different basic formulas described above can also be used.

To the salt function as well as a threshold effect (minimization of precipitation salts of Ca and Mg ions) in the rinse at high water hardnesses to ensure is in the cleaning composition of the invention preferably a polymer is used. Such salt-function polymers are from the prior art, especially in the field of water treatment known. Examples of such polymers are products of the type Acusol 587 (Rohm & Haas), which are equally known as calcium phosphate inhibitors, Anti-filming and dispersants are solicited. Particularly suitable and preferred polymers are acrylates, acrylate-maleate copolymers as well as copolymers with sulfonated groups, in particular sulfonated polycarboxylates. Particularly preferred salt-function polymers are copolymers from sulfonated and non-sulfonated monomers. The term "copolymer" in this context includes a polymer having two or more different ones Types of monomers including, for example, terpolymers. A preferred copolymer may include, among others, the following monomers each preferably in either acidic or neutral form: acrylic acid, Maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, methallylsulfonic acid, Styrene or sulfonated styrene. The sulfonation of the individual Monomers may be present prior to polymerization, or only after be initiated polymerization initiated.

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

Preferred is in the copolymer of sulfonated / non-sulfonated monomers the proportion of non-sulfonated monomers in the salt-functional polymer 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 incorporated into the composition of the invention in amounts of from 0.2 to 20% by weight, preferably from 0.5 to 10% by weight, particularly preferably used from 0.8 to 5% by weight.

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

The spatial form of the moldings can in their dimensions of Einspülkammer be adapted to the dishwasher, but all reasonable shape manageable shapes. 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 one 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, canceled and entered into the metering chamber or cutlery basket of the machine can be. This principle of the bar-shaped molding can also be realized in other geometric polygonal shapes.

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

Detergent tablets for different purposes, in particular for Dishwashers are basically known.

Contain such molded as a molded body detergent formulations usually builders, bleaches and bleach activators, Surfactants, tableting aids, disintegrants and other common additives and adjuvants.

In the invention described herein, the composition of the cleaning agent Incidentally, the usual ingredients for dishwashing detergents contain. The ingredients of the cleaner composition described below represent only preferred embodiments.

Examples of known and customary cleaning formulations in the field The machine dishwashing detergents are among others in the published 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 prefers.

In all layers / phases of the cleaning tablet can be a disintegrating agent be included, but is preferred in only one or two (in the presence multiple layers / phases) layers / phases. This is preferred to a first layer / phase, which quickly come into effect contains constituents to dissolve in a short time in the rinse water and to provide the ingredients with while a another layer / phase that contains ingredients that become a later Time of the cleaning process to be used, slower solves because it contains no or a "slower" explosive.

As builders in the detergent composition, all conventional and as such, known builders are used, in particular Polyphosphates, pyrophosphates, metaphosphates or phosphonates, phyllosilicates, amorphous silicates, amorphous disilicates and zeolites, and fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium bicarbonate, Citrate as well as citric acid, succinic acid, tartaric acid and malic acid. Frequently used as Hilfgerüststoff Cobuilder and dispersants concomitantly. Such co-builders or dispersants may, inter alia Polyacrylic acids or copolymers with polyacrylic acid and its sodium salts be.

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. In most cases, in addition to these inorganic peroxy compounds, the bleach system of the detergent formulation may contain inorganic or organic peracids, especially percarboxylic acids, e.g. 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 diperacids, mono- and diperphthalic acids, isophthalic 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 in particular 1-30% by weight.

As bleach catalysts are usually quaternized imines or Sulfone imines used, for example, in US-A-5,360,568, US-A-5,360,569 and EP-A-453 003, as well as manganese complexes, as described, for example, in WO-A 94/21777. Other usable metal-containing bleach catalysts are described in EP-A-458 397, EP-A-458,398 and EP-A-549,272. Bleach catalysts are incorporated in the rule in amounts of up to 10 wt .-%, in particular 0.1 to 6 wt .-%, based on the detergent formulation used.

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 usable as bleach activators are 0-acyloxime esters such. B. 0-acetylactone oxime, 0-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 for example, N-acetylcaprolactam, N-benzoylcaprolactam, N-octanoylcaprolactam, N-octanoylcaprolactam or carbonylbiscaprolactam.

• 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 useful 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 the EP-B-502 013 are described. In particular, 2-phenyl- (4H) -3,1-benzoxain-4-one and 2-methyl (4H) -3,1-benzoxain-4-one.

In addition, bleach activators from the classes of N- or O-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 esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose be used.

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

As a bleach system (bleach and bleach activators) can also all the bleaching agents and activators mentioned in DE 199 59 589 A1 be included. In addition, the bleach systems, the mentioned in the European patent application EP 02 028 958.3 are used become.

It is preferred that the different components of the detergent composition in different phases / layers / areas of the Shaped bodies are included. In particular, it is preferred that a Component provided at an earlier stage of the cleaning process should be in a phase / layer / area, in which contains a disintegrant.

The cleaning agents can be used in addition to the "carry over" described above. Surfactants also include one or more other surfactant (s) 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 fragrances. 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 as ingredient c) nonionic (s) 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, the melting or softening points in have mentioned temperature range, for example, low-foaming nonionic surfactants that are solid or highly viscous at room temperature could be. If high-viscosity nonionic surfactants are used at room temperature, so it is preferred that these have a viscosity above 20 Pas, preferably 35 Pas and in particular above 40 Pas. Also nonionic surfactants, which are waxy at room temperature, are preferred.

Preferably as nonionic surfactants which are solid at room temperature from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (P0 / E0 / P0) surfactants. Such (P0 / E0 / P0) -nonosides draw Beyond that by good foam control. Preferably do the P0.Einheiten up to 25 wt .-%, particularly preferably 20 wt .-% and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant out. Particularly preferred nonionic surfactants are ethoxylated Monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene Have block copolymer units. The alcohol or A1-kylphenolteil such nonionic surfactant molecules preferably makes more than 30 wt .-%, more preferably more than 50 wt .-% and in particular more as 70 wt .-% of the total molecular weight of such nonionic surfactants.

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

Nonionic surfactants which can be used with particular preference are, for example, under the name Poly Tergent® SLF-18 of the Company Olin Chemicals available.

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 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 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 simplified. In the latter formula, R ¹ , R ² and R ^{3 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 ¹ and R ^{2 has} 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. 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 -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, the either as sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

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 alkanolamide may be suitable. The amount of this nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of them.

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.

In der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Arylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.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 prepared by reductive amination of a reduced sugar obtained, for example, glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy-substituted Compounds can then be prepared by reaction with fatty acid methyl esters in Presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.

Conversely, however, can also by the content of individual phases or the entire Shaped body, d. H. all phases, 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 a phase of the shaped bodies containing alkylpolyglycosides.

Other suitable surfactants are so-called gemini surfactants. this includes In general, such compounds are understood to be dimers present and compared to monomeric surfactants two hydrophobic groups own per molecule. These groups are usually by a so-called hydrophilic "spacer" separated from each other. Such surfactants are generally characterized by an unusually low critical Micelle concentration and the ability to increase the surface tension of the water to greatly reduce, out. In exceptional cases, however, under the Expression Gemini surfactants not only dimeric but also trimeric surfactants Understood.

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

But can also be used 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.

As enzymes come in the detergent tablets according to the invention especially 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 said Enzymes in question. All of these hydrolases contribute to the removal of Stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Especially good are suitable from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens and their genetically modified variants enzymatic agents. Preferably, subtilisin type proteases and in particular proteases derived from Bacillus lentus be used. These are 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, in particular however, protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. examples for Such lipolytic enzymes are the known cutinases. Also Peroxidases or oxidases have proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, Pullulanases and pectinases.

The enzymes can be adsorbed to carriers or embedded in enveloping substances be to protect them against premature decomposition. The amount The enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% amount. As part of are preferred detergent tablets according to the present invention 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 inventive two-phase detergent moldings: 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 only in one phase of the inventive molding used, so detergent tablets are preferred in which the enzyme (s) not in a phase together with the bleach-enhancing Active ingredient combination is / are included.

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

The cleaning agents according to the invention can be used to protect the items to be washed or the machine contain corrosion inhibitors, with particular silver protectants in the field of automatic dishwashing a special Have meaning. Can be used, the known substances of the state of the technique. In general, especially silver protectants can be selected are selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferable to use are benzotriazole and / or alkylaminotriazole. One finds in cleaner formulations In addition, frequently active chlorine-containing agents that corrode the silver surface can significantly reduce. In chlorine-free Cleaners are especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, Pyrogallol or derivatives of these classes of compounds. Likewise Zinc compounds used to prevent corrosion of items to be washed become.

If the detergent tablets contain corrosion inhibitors, they are these are preferably separated from the bleaching agents. Accordingly, detergent tablets, where at least one phase is bleach contains at least one other phase corrosion inhibitor, prefers.

Preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which also be referred to as sulfosuccinates or as sulfosuccinic and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols represent. Preferred sulfosuccinates contain C8 to C18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue that is different from ethoxylated fatty acids which represent non-ionic surfactants per se (See description below). Again, sulfosuccinates, whose Fatty alcohol residues of ethoxylated fatty alcohols with concentrated Derive homolog distribution particularly preferred. It is also possible Alk (en) ylsuccinic acid having preferably 8 to 18 C atoms in the Alk (en) ylkette or their salts to use.

Preferred anionic surfactant mixtures contain combinations of Alk (en) ylsulfates, in particular mixtures of saturated and unsaturated Fatty alkylsulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerine esters and / or α-sulfofatty acid esters. In particular are In this case, preference is given to mixtures which, as anionic surfactants, contain alk (en) ylsulfates and alkylbenzenesulfonates, alk (en) ylsulfates and α-sulfofatty acid methyl ester and / or sulfated 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 may be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine present. Preferably, the anionic Surfactants in the form of their sodium or potassium salts, in particular in the form their sodium salts.

Other preferred ingredients are alkaline in water inorganic salts. 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, the alkali metal silicates are in amorphous or crystalline form with a Na 2 O to SiO 2 ratio of 1: 1 to 1: 2,8. Also used are the cogranulates of carbonates and silicates, which are available on the market as so-called NABION (Rhodia).

Examples of other common 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 is an anticorrosive effect for glass to have. As glass corrosion protection, all known means for corrosion protection be used. Examples of these are metal oxides, such as 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 also zinc or magnesium salts of organic compounds, as described in the DE 101 40 535 are described.

In addition, the dishwasher detergents according to the invention can in tablet form dyes and fragrances are added to the aesthetic To improve the impression of the resulting products and to the consumer in addition to the performance a visually and sensory "typical and unmistakable" To provide product. As perfume oils or perfumes can individual fragrance compounds, eg. B. the synthetic Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Perfume compounds of the ester type are z. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, Linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and Benzylsalicylate. To the Ethern For example, include benzyl ethyl ether to the aldehydes z. B. the linear Alkanals of 8 to 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. The ionones, α-isomethyl ions and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and termpineol, to the hydrocarbons belong mainly the terpenes like limonene and pinene. However, mixtures are preferred different fragrances used, which together create an appealing Create a fragrance. Such perfume oils can also be natural fragrance mixtures contain as accessible from plant sources are, for. 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, lime blossom oil, juniper berry oil, vetiver oil, Olibanumöl, Galbanumöl and Labdanumöl as well as Orange Blossom Oil, Neroliol, Orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the moldings according to the invention be, but it can also be beneficial to the fragrances Apply carrier. As such carrier materials, for example Cyclodextrins proven, the cyclodextrin-perfume complexes in addition can still be coated with other excipients. Also an incorporation of the fragrances as ingredient d) in the inventive Detergent components 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 may be colored (or parts thereof) with suitable dyes. Preferred dyes whose selection the expert no difficulty prepares, possess a high storage stability and insensitivity to the other ingredients of the agent and against light and none pronounced substantivity to those treated with the means 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 further elucidated on the basis of exemplary embodiments explained without being limited to these. All information refer to weight, unless it is in the individual case something specified otherwise.

The tablets mentioned in the examples are mono-, double- and Triple-phase tablets can be used. The individual components can be distributed in different areas / phases of the moldings.

example 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 5 0.2 - 2 Carry over surfactant 2.00 1.00 5.00 2.00 Nonionic surfactant - - - 2 phosphonate 1.00 0.50 2.00 - Sulphonated polycarboxylate 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 -

Example 2:

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

Einstufung "Filming":

4 = keine Filmbildung, vollständig klar

3 = geringe Filmbildung

2 = starke Filmbildung

1 = sehr starke Filmbildung, Glas erscheint trübe

Einstufung "Spotting":

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

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:

Classification "Filming":

4 = no filming, completely clear

3 = low film formation

2 = strong film formation

1 = very strong film formation, glass appears cloudy

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 quite a bit depending on the surface, but it did the investigated commercial products have a maximum value of 4.1.

Example 3:

Filming and spotting of various formulations, with and without dispersants, 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. Formulations and results: Basic formulation 1 2 3 4 5 6 7 3% carry over surfactant - - - Yes Yes Yes Yes 2% salt functional polymer - Yes Yes - - Yes Yes 1.5% dispersing agent - - 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

The table shows that the addition of a carry over surfactant a significant Reduction of flocculation caused by the addition a salt functional polymer is still supported. The addition of a Dispersant additionally causes an improvement in the washing results. In particular, an improved "spotting" at - compared to commercially available products - good "Filming" achieved.

Example 4:

The filming and spotting of the composition of the present invention is compared with the filming and spotting of compositions in which the ingredients are surfactant, salt functional polymer, and dispersants, respectively, 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 Yes StDt Yes Yes StDt 3% salt functional polymer Yes StDt Yes StDt Yes 1% dispersing agent 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 08.02 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

The results of these comparative experiments show that already the use of carry over surfactants compared to conventionally used surfactants to a significantly improved stain performance ("Spotting") on the washed dishes, with one still very good filming value is achieved. Due to the additional use of a The salt functional polymer of the present invention can further promote staining be reduced, whereas the inventive use of the dispersant improve the "filming" values of the composition.

Claims (10)

Detergent composition for dishwashers containing at least includes a "carry over" surfactant. Detergent composition according to claim 1, characterized in that it also contains a salt-functional polymer. A detergent composition according to claim 2, characterized in that the 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 detergent composition according to any one of claims 1 to 3, characterized in that at least one carry over surfactant has 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 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 smaller than 100 and x + y is less than 200. A detergent composition according to any one of claims 1 to 4, characterized in that at least one carry over surfactant has 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 26 and 200, y is an integer less than 100 and x + y is less than 200 Detergent composition according to one of claims 1 to 5, characterized in that at least two different carry over surfactants are used. Detergent composition according to one of claims 1 to 6, characterized in that it also contains a dispersing agent. A detergent composition according to any one of claims 1 to 7, characterized in that it contains: 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. Detergent composition according to any one of claims 1 to 8, characterized in that it is in the form of a single or multi-phase pressed molded body or a powder. Use of at least one carry over surfactant in a detergent composition for machine dishwashing detergents.