DE19925275A1 - Non-aqueous liquid dish detergent - Google Patents

Abstract

The invention relates to non-aqueous liquid dishwashing compositions for dishwashers that are characterized by a high physical (deposition behavior) and chemical (decomposition of bleaching agent) stability and good cleaning properties without requiring high quantities of surfactants. The inventive dishwashing agents contain 20 to 50 wt.-% of one or more water-soluble builders, 1 to 25 wt.-% glycerol, 5 to 40 wt.-% of a polyethylene glycol that is liquid at room temperature and optionally up to 20 wt.-% 1,2-propanediol and </= 2 wt.-% free water in addition to other optional detergent ingredients.

Description

The present invention is not related to non-aqueous dishwashing detergents surfactant, water-soluble liquids, which, in addition to builders, optionally contain bleach, Bleach activators, enzymes and other ingredients of automatic dishwashing detergents contain.

Means for the automatic cleaning of dishes in household dishwashers Nen are available in various designs on the market. In addition to the earlier Common powder detergents have moldings, d. H. Reini drug tablets established. However, when formulating liquid funds you come across difficulties because certain ingredients such as builders and bleach are solid and either do not dissolve or are difficult to sediment into the liquids have it incorporated. When using water as a liquid base, stabilizers exist problems for a number of ingredients. A solution to this problem consists in increasing the viscosity of the agent so that the finely divided solids on the Sedimentation can be prevented. Another problem with liquid funds is the one The stability of the bleaching agents in such cleaning agents. Also incompatibilities between mutually incompatible substances, for example bleaching agents and enzymes, come to the fore with liquid formulations. There is a solution here approach in the formulation of non-aqueous, d. H. essentially water-free cleaning medium.  

Despite numerous proposed solutions in the prior art, it has not been possible to date a liquid non-aqueous cleaning agent for use in household To provide dishwashers that trade the range and strength of trade Certain forms of offer reached or even exceeded.

The European patent application EP 518 721 (Colgate-Palmolive Company) describes for example non-aqueous liquid dishwashing detergents, the protease and amylase and optionally a thickening system made of clay minerals, hydroxypropyl cellulose and Contain polyacrylate polymers. The liquid matrix, the 40 to 65 wt .-% of the total according to the teaching of this document consists of higher glycols, in particular special polyethylene glycols. The settling behavior is controlled by a stabilization system, which contains silicate, controls. The funds also contain large amounts of nonionic surfactants. The use of glycerin is not mentioned in this document still suggested. Although the use of bleaching agents and bleach activators after the Disclosure of this document should be possible are the Zu disclosed in the examples compositions free of these substances.

In the European patent application EP 611 206 (Colgate-Palmolive Company) also non-aqueous liquid dishwasher detergent containing protease and amylase, which contain 5 to 25% by weight of a polymeric swelling or gelling agent (e.g. polypropylene glycols), 0.1 to 10% by weight hydroxypropyl cellulose Polymer and optionally contain polyacrylate polymer. Also open in this document Beard agents contain high amounts of nonionic surfactants. A use of glycerin is also not mentioned or suggested in this document. Although the use of Bleaching agents and bleach activators are in turn possible after the disclosure of this document Here, too, are the compositions disclosed in the examples tongues free of these substances.

Viscoelastic, thixotropic dish detergent with 0.001 to 5 wt .-% surfactant as well Enzymes and an enzyme stabilization system made of boric acid and polyhydroxyverbin are in the international patent application WO 93/21299 (Procter & Gamble)  described. The agents disclosed here also contain 0.1 to 10% by weight of one or several thickeners.

The cited documents disclose liquid dishwashing detergents for dishwashing seem to be advantageous in some areas of the requirement profile for such means have shafts. However, no means has so far been disclosed in the prior art that is superior to conventional agents in terms of as many properties as possible, since advantages with certain properties (flowability, residual emptiness, appealing product appearance etc.) with disadvantages in other properties (settling behavior, storage stability activity, performance, etc.). The task therefore still was to To provide means that have advantageous rheological properties (flowability, rest emptiness etc.), advantageous product characteristics (appearance, cleaning power, la stability, etc.) and a technically easy to implement and inexpensive Combine the production to be carried out.

In particular with regard to the performance of the products to be provided and their physical (settling behavior) and chemical (bleach decomposition) stability should improved products are provided within the scope of the present invention, which combine high performance with high storage and transport stability. So should the Incorpora tion of bleaching agents and bleach activators wherever possible and without problems good cleaning performance can also be achieved without the use of high amounts of surfactants can. A high level of performance should preferably also be used with amounts of surfactant below 1 % By weight or without the use of surfactants.

It has now been found that liquid dish detergents based on a liquid matrix are made up of glycerol and polyethylene glycols liquid at room temperature fulfill the specified requirement profile. The liquid matrix can optionally be supplemented by diols be, with 1,2-propanediol is particularly suitable.

The invention relates to liquid non-aqueous cleaning agent compositions for automatic dishwashing, which, in addition to other optional detergent ingredients

• a) 20 to 50% by weight of one or more water-soluble builders,
• b) 1 to 25% by weight glycerol,
• c) 5 to 40 wt .-% of a liquid at room temperature polyethylene glycol and
• c) 0 to 20 wt .-% 1,2-propanediol and
• e) ≦ 2% by weight of free water

contain.

The term "free water" denotes the water content of the agent, which is not in the form is bound by water of hydration and / or constitutional water, d. H. in the means as Be Part of the liquid matrix is present. According to the invention, this is 2% by weight or below, preferably below 1.5% by weight, particularly preferably below 1% by weight, and in particular in particular even less than 0.5% by weight, based in each case on the composition. Through a Corresponding content of free water labeled detergent composition tongues are therefore preferred. Accordingly, water can essentially only in chemically and / or physically bound form or as a component of as a solid existing raw materials or compounds, but not as a liquid, solution or disper sion contained in the compositions of the invention. Advantageously the compositions according to the invention have a total water content of not more than 15% by weight, so this water is not in liquid free form, but is chemically and / or physically bound, and it is particularly preferred is that the content of water not bound to carbonates and / or silicates in the compositions according to the invention not more than 10% by weight and in particular is not more than 7% by weight. In the manufacture of the assembly according to the invention settlements, water-containing liquids can be used, provided that they are added an "internal desiccant", for example a hydratable substance in not hydrated form, the free water content kept below the stated limit becomes.

Water-soluble builders are used in the compositions according to the invention mainly used to bind calcium and magnesium. Usual builders working in the Rah men of the invention preferably in amounts of 22.5 to 45 wt .-%, preferably of 25 up to 40 wt .-% and in particular from 27.5 to 35 wt .-%, each based on the Reini  agent composition, are present, the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the Carbonates, phosphates and sodium and potassium silicates. Low molecular weight polycarboxylic acid Ren in the sense of the present invention are substances that two or more carboxyl Wear functions and have molecular weights below 2000. In particular fall into this group the following acids and their salts: tartaric acid, succinic acid, malon acid, adipic acid, maleic acid, fumaric acid, oxalic acid and in particular citric acid re. Commercially available and also within the scope of the present invention Sokalan® DCS (trademark of BASF), a mixture of amber, can also be used acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight). Trisodium citrate is preferred for the cleaning agents according to the invention and / or pentasodium tripolyphosphate and silicate builders from the class of the alkali disilicates used. In general, the potassium salts are the natri in the case of the alkali metal salts prefer salting, since they often have a higher water solubility. Preferred Water-soluble builders are, for example, tripotassium citrate, potassium carbonate and Potash water glasses.

Particularly preferred detergent compositions contain water-soluble ones Builders phosphates, preferably alkali metal phosphates, with particular preference pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphos phat).

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages:
They act as alkali carriers, prevent limescale deposits and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ° C, in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with caustic soda and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when he heats of Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O is formed when he heats disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] that crystallizes with 6 H ₂ O. _n -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 20 ° approx. 20 g, at 100 ° around 32 g of the salt free of water; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).

Sodium tripolyphosphate can be contained in the agents according to the invention, but it is also possible to dispense with its use and other water-soluble builders,  especially potassium phosphates. The content of the agents according to the invention Sodium tripolyphosphate is in preferred means between 0 and 20 wt .-%, esp more preferably between 0 and 15 wt .-%.

Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium poly phosphates are widely used in the detergent and cleaning agent industry. Potassium tripolyphosphate is a particularly preferred builder in the context of the present invention, which is used in preferred compositions in amounts of 15 to 40% by weight. Particularly preferred agents contain 20 to 35% by weight potassium tripolyphosphate, in particular contents of 22.5 to 30% by weight are preferred.

In addition to the water-soluble builders, the composition according to the invention contains tongues a liquid matrix made up of glycerin, one or more at room temperature liquid polyethylene glycols and optionally 1,2-propanediol.

Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1.261 that solidifies at 18.2 ° C. Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediate stages of allyl chloride and epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the glycide stage.

In the context of the present invention, glycerol is particularly preferred the component of the liquid matrix. The content of preferred detergent compositions tongues of glycerin is 1.25 to 24 wt .-%, preferably 2 to 17.5 wt .-% and ins particularly 4 to 16% by weight, based in each case on the composition.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are polymers of ethylene glycol which have the general formula I

H- (O-CH ₂ -CH ₂ ) _n -OH (I)

are sufficient, where n can have values between 1 (ethylene glycol) and approx. 16. Relevant Lich when evaluating whether a polyethylene glycol can be used according to the invention is included the physical state of the PEG at room temperature, d. H. the freezing point of the PEG must be below 25 ° C. There are different nomenclatures for polyethylene glycols, that can lead to confusion. The specification of the middle is technically common relative molecular weight following the indication "PEG", so that "PEG 200" is a poly characterized ethylene glycol with a relative molecular weight of about 190 to about 210. To this nomenclature are technically in the context of the present invention Chen polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and a number follows the hyphen directly, which corresponds to the number n in the above formula I. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-4, PEG-6, PEG-8, PEG 9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used according to the invention.

Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone- Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher Numbers.

In the context of the present invention, PEG 400 is used with particular preference, possibly with other of the above and below optional stock parts of the liquid matrix can be mixed. Preferred agents have a content PEG 400, which is 6 to 37.5% by weight, preferably 8 to 27.5% by weight and in particular 12 to 24 wt .-% is.  

There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3-propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet schmec kenden liquid of density 1.0597, which solidifies at -32 ° C and boils at 214 ° C. The Her Provision of 1,3-propanediol is possible from acrolein and water with subsequent catalyzing table hydrogenation. Technically far more important is 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which - 60 ° C solidifies and boils at 188 ° C. 1,2-propanediol is made from propylene oxide Water accumulation produced. 1,2-propanediol is within the scope of the present invention a preferred component of the liquid matrix. 1,2-propanediol optionally used according to the invention and can be present in amounts of up to 20% by weight in the compositions according to the invention may be included. Preferred compositions contain 0.5 to 18% by weight, preferably 1.5 to 12.5% by weight and in particular 4 to 11 % By weight of 1,2-propanediol.

In addition to the ingredients of the liquid matrix mentioned, of which glycerin and Polyethylene glycols liquid at room temperature are mandatory according to the invention and 1,2- Propane diol can be used optionally, other non-surfactant, non-aqueous rivers be contained in the agents according to the invention. In addition to lower alcohols such as Methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3- Methyl 1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol and 1- Hexanol in particular have diols such as ethanediol (glycol), 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol and 1,5-pentanediol, at room temperature temperature liquid carbonic acid esters (carbonates) such as propylene carbonate and glycerine carbonate as well as propylene glycols.

The other constituents of the liquid matrix mentioned can be used, for example, in quantities from 0 to 5% by weight, preferably in amounts of 0.5 to 2.5% by weight become. However, particularly preferred liquid matrixes consist only of glycerol and PEG or from mixtures of 1,2-propanediol and PEG and glycerin. Especially before Drawn detergent compositions are characterized in that they are 1.5 to 22.5% by weight, preferably 2.5 to 20% by weight and in particular 5 to 15% by weight of glyce  rin, 5 to 35% by weight, preferably 7.5 to 30% by weight and in particular 10 to 20% by weight a polyethylene glycol mixture which is liquid at room temperature and 0 to 17.5% by weight, preferably 1 to 15% by weight and in particular 2.5 to 10% by weight of 1,2-propanediol contain.

The cleaning agents according to the invention can be used as further ingredient (s) compositions optionally contain 0.05 to 5 wt .-% of one or more surfactants. The detergent compositions preferably additionally contain nonionic (s) and / or anionic surfactant (s), preferably nonionic surfactant (s) in amounts of 0.1 to 4% by weight, preferably 0.15 to 3% by weight and in particular 0.2 to 2 % By weight, based in each case on the detergent composition.

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 residue is linear or preferably in the 2-position May be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxoalko radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO; 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Usable alkyl polyglycosides satisfy the general formula RO (G) ₂ , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycosyl unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used. The compositions according to the invention can preferably contain alkyl polyglycosides, APG contents of more than 0.2% by weight, based on the total composition, being preferred.

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

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

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

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

in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or 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, for example, according to the teaching of international application WO-A-95/07331 by reaction with fatty acid remethyl esters in the presence of an alkoxide as a catalyst in the desired polyhy droxy fatty acid amides are transferred.

Preferred anionic surfactants are those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products; into consideration. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated Methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DANK, are also suitable anionic surfactants.

Preferred for the compositions according to the invention with regard to the intended use of automatic dishwashing are the nonionic surfactants described above and here above all the low-foaming nonionic surfactants. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also lead to the substance class of the “closed” alcohol ethoxylates, which can also be used in the sense of the invention. Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

The liquid detergent compositions according to the invention can be used position of a possibly desired higher viscosity viscosity regulator or Verdic agent included. All known thickeners can be used here those based on natural or synthetic polymers.

Natural polymers that are used as thickeners for example agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, buttocks lyose, guar flour, locust bean gum, starch, dextrins, gelatin and casein. Modified natural products mainly come from the group of modified starches and celluloses, for example carboxymethyl cellulose and other cellulose ethers, Hydroxyethyl and propyl cellulose and core meal ether called.

A large group of thickeners that differ widely in use the most diverse fields of application are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimi ne, polyamides and polyurethanes.

Thickeners from the classes of substances mentioned are widely available commercially and are, for example, under the trade names Acusol®-820 (Methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral®-GT-282-S (alkyl polyglycol ether, Akzo), Deuterol®-Polymer-11 (Dicarboxylic acid copolymer, Schönes GmbH), Deuteron®-XG (anionic Heteropolysaccharide based on β-D-glucose, D-manose, D-glucuronic acid, more beautiful GmbH), Deuteron®-XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan®-Thickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse  Chemistry), EMA®-81 and EMA®-91 (ethylene-maleic anhydride copolymer, Monsanto), Thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox®-AM (anionic acrylic acid-acrylic acid ester copolymer dispersion, 25%) in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo®-S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo®-XA (xanthan biopolymer, stabilized with formaldehyde, Shell) available.

A preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide, that of Xanthomonas campestris and some others Species is produced under aerobic conditions and has a molecular weight of 2 to 15 mils ion dalton. Xanthan is made from a chain with β-1,4-bound glucose (Cel lulose) with side chains. The structure of the subgroups consists of glucose, Mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units being the Viscosity of xanthan determined.

Xanthan can be described by the following formula:

In the context of the present invention, thickening likewise to be used preferably middle are polyurethanes or modified polyacrylates, which, based on the whole Agents, for example in amounts of 0.1 to 5 wt .-% can be used.

Polyurethanes (PUR) are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula III

in which R ^{1 is} a low molecular weight or polymeric diol radical, R ^{2 is} an aliphatic or aromatic group and n is a natural number. R ¹ is preferably a linear or branched C _2-12 alk (en) yl group, but can also be a residue of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from the above formula I in that the radical R ¹ further -O- CO-NH groups are bound.

Technically important PUR are made of polyester and / or polyether diols and example. B. from 2,4- or 2,6-toluenediisocyanate (TDI, PF = C ₆ H ₃ -CH ₃ ), 4,4'-methylenedi (phenyl isocyanate) (MDI, PF = C ₆ H ₄ -CH ₂ - C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ² = (CH ₂ ) ₆ ].

Commercial polyurethane-based thickeners are, for example, among the Name Acrysol®PM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel® L75-N (non-ionic PUR dispersion, 50% in Water, Borchers), Coatex® BR-100-P (PUR dispersion, 50% in water butylglycol, Dimed), Nopco® DSX-1514 (PUR dispersion, 40% in water / butyltrigylcol, Henkel- Nopco), thickener QR 1001 (20% PUR emulsion in water / digylcol ether, Rohm & Haas) and Rilanit® VPW-3116 (PUR dispersion, 43% in water, Henkel) er true.  

Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula IV

in which R ^{3 is} H or a branched or unbranched C _1-4 alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 alk (en ) yl radical, R ^{5 is} H or R ⁴ and n is a natural number. Such modified polyacrylates are generally esters or amides of acrylic acid or an α-substituted acrylic acid. Preferred among these polymers are those in which R ^{3 is} H or a methyl group. In the case of the polyacrylamides (X = NR ⁵ ), both (R ⁵ = H) and doubly (R ⁵ = R ⁴ ) N-substituted amide structures are possible, the two hydrocarbon radicals attached to the N atom being can be selected independently of one another from optionally alkoxylated branched or unbranched C _8-22 alk (en) yl radicals. Among the polyacrylic esters (X = O), preference is given to those in which the alcohol has been obtained from natural or synthetic fats or oils and is additionally alkoxylated, preferably ethoxylated. Preferred degrees of alkoxylation are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.

Since the polymers that can be used are technical compounds, the designation of the radicals bound to X represents a statistical mean value, which can vary in individual cases with regard to chain length or degree of alkoxylation. Formula 11 only gives formulas for idealized homopolymers. However, copolymers in which the proportion of monomer units which satisfy formula 11 is at least 30% by weight can also be used in the context of the present invention. For example, copolymers of modified polyacrylates and acrylic acid or their salts can also be used which still have acidic H atoms or basic --COO ^- groups.

Modified polyacrylates to be preferably used in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula IVa

in which R ^{4 is} a preferably unbranched, saturated or unsaturated C _8-22 alk (en) yl radical, R ⁶ and R ⁷ independently of one another are H or CH ₃ , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number Number between 2 and 30, preferably between 10 and 20. R ⁴ is preferably a fatty alcohol residue obtained from natural or synthetic sources, the fatty alcohol in turn preferably being ethoxylated (R ⁶ = H).

Products of the formula IVa are commercially available, for example, under the name Acuso® 820 (Rohm & Haas) in the form of 30% by weight dispersions in water. In the commercial product called ge R ⁴ is a stearyl, R ⁶ is a hydrogen atom, R ⁷ is H or CH ₃ and the degree of ethoxylation is a 20th

Preferred detergent compositions in the context of the present invention are characterized in that they additionally contain 0.1 to 5% by weight, preferably 0.2 to 4% by weight, particularly preferably 0.3 to 3% by weight and in particular 0, 5 to 1.5% by weight of a polymeric thickener, preferably from the group of the polyurethanes or the modified polyacrylates, with particular preference for thickeners of the formula IV

in which R ^{3 is} H or a branched or unbranched C _1-4 alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 alk (en ) yl radical, R ^{5 is} H or R ⁴ and n is a natural number.

The viscosity of the agents according to the invention can be determined using customary standard methods (at for example, Brookfield viscometer LVT-II measured at 20 rpm and 20 ° C, spindle 3) and is preferably in the range from 500 to 5000 mPa.s. Preferred Reini Detergent compositions have viscosities of 1000 to 4000 mPa.s, with values between 1300 and 3000 mPa.s are particularly preferred.

The pH of the undiluted products according to the invention is preferably in one Range from 6 to 11, particularly preferably between 7 and 10 and in particular between 7.5 and 9.

In addition to the liquid matrix and the components mentioned builder and viscosity Regulator can the agents according to the invention contain other ingredients that the technical and / or aesthetic properties of the cleaning agents together further improve settings. Included within the scope of the present invention detergent compositions continue one or more substances from the  Group of bleaches, bleach activators, electrolytes, non-aqueous solvents, pH Agents, fragrances, dyes, enzymes and enzyme stabilizers.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as per benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Bleaches from the group of organic bleaches can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. Dibenzoyl peroxide. Other typical organic bleaching agents are the peroxyacids, examples of which are alkyl peroxyacids and arylperoxyacids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoper phthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalonic acid [ε-phthalimide [ Phthaloiminoperoxy hexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxyacid, diperoxyacid Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Preferred detergent compositions in the context of the present invention also contain bleach; preferably bleaching agents based on oxygen  particular preference for sodium perborate monohydrate and sodium percarbonate, in Amounts from 2.5 to 25% by weight, preferably from 5 to 20% by weight and in particular from 7.5 to 15 wt .-%, each based on the composition.

To improve bleaching when cleaning at temperatures of 60 ° C and below To achieve this, bleach activators can be incorporated into the detergent compositions be incorporated. As bleach activators, compounds that are under Perhydroly aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid give, be used. Substances containing the O- and / or N-acyl groups are suitable mentioned number of carbon atoms and / or optionally substituted benzoyl groups. Be Preference is given to multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5- triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially special n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid reanhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular special triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the moldings. With this stuff fen are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or -carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N containing tripod ligands and Co, Fe, Cu and Ru amine complexes are bleached catalysts can be used.

Preferred detergent compositions in the context of the present invention additionally contain one or more bleach activators, preferably from the group the O- and / or N-acylated alcohols or amines with particular preference from Tetraacetylethylenediamine (TAED), n- or iso-nonanoyloxybenzenesulfonate (n- or iso- NOBS), 1,2,3-triacetoxypropane, n-methyl-morpholinium-acetonitrile-methyl sulfate  (MMA) and their mixtures, in amounts of 1 to 15 wt .-%, preferably from 2 to 12% by weight and in particular from 4 to 8% by weight.

The cleaning agents according to the invention can be combined as further ingredients Setting to improve cleaning performance on certain types of soiling contain enzymes or enzyme preparations. According to the cleaning agent Enzymes and / or enzyme preparations, preferably protease (s) and / or amylase (s), for example in amounts of 1 to 5% by weight, preferably of 1.5 to 4.5 and in particular from 2 to 4 wt .-%, each based on the cleaning agent composition can be added to increase the performance of the detergent like or under milder conditions, the cleaning performance of the same quality guarantee.

Enzymes in particular come from the class of proteases, lipases and amyl ases, cellulases or their mixtures in question. Bak are particularly well suited strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus-derived enzymatic agents. Proteases from the subti lisin type and in particular proteases obtained from Bacillus lentus puts. There are enzyme mixtures, for example from protease and amylase or Pro tease and lipase or protease and cellulase or from cellulase and lipase or from Pro tease, amylase and lipase or protease, lipase and cellulase, but especially Cel Mixtures of lulase of particular interest. Also peroxidases or oxidases have proven to be suitable in some cases. The enzymes can on carriers adsorbed and / or embedded in enveloping substances to prevent them from premature decomposition to protect.

The most commonly used enzymes include lipases, amylases, cellulases and Proteases. Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase -M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or aspen rase® from Gist Brocades or Savinase® from Novo. Particularly suitable Cel Lulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk. Be special use as amylases are Termamyl® 60 T and Termamyl® 90 T from  Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Broca des and Purafect OxAm4000G® from Genencor but also other enzymes can be turned.

In addition to the solid enzyme preparations mentioned, Erfin In particular, the use of liquid enzyme preparations is preferred. Such liquid Enzyme concentrates are either homogeneously based on propylene glycol / water or heterogeneous as a slurry, or they are in a microencapsulated structure. Preferred Liquid proteases are e.g. B. Savinase® L, Durazym® L, Esperase® L, and Everlase® from Fa. Novo Nordisk, Optimase® L, Purafect® L, Purafect® OX L, Properase® L from Genencor International, and BLAP® L from Biozym Ges.m.b.H. Preferred amylases are ter mamyl® L, Duramyl® L, and BAN® from Novo Nordisk, Maxamyl® WL and Purafect® HPAm L from Genencor International. Preferred lipases are Lipolase® L, Lipolase® ultra L and Lipoprime® L from Novo Nordisk and Lipomax® L from Genencor Inter national.

As slurries or microencapsulated liquid products such. B. Products like those with SL or LCC designated products from Novo Nordisk are used. The above commercially available liquid enzyme preparations contain, for example, 20 to 90% by weight Propylene glycol or mixtures of propylene glycol and water. As part of the present Preferred detergent compositions according to the invention are thereby characterized records that it one or more liquid amylase preparations and / or one or several liquid protease preparations in amounts of 0.1 to 10 wt .-% each preferably from 0.2 to 7.5% by weight and in particular from 0.5 to 4% by weight.

Overall, the use of enzymes in the agents according to the invention is advantageous which is why detergent compositions which additionally contain enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or Amy lase preparations, in amounts of 1 to 5 wt .-%, preferably from 1.5 to 4.5 and in particular from 2 to 4% by weight, in each case based on the detergent composition tongue, contain, are preferred.  

The detergent compositions according to the invention can also - if they contain enzymes - substances are also added that stabilize the enzymes and so on prevent loss of activity. These substances, the selection of which no expert Difficulties arise, for example, from the short-chain car group bonic acids, the hydroxycarboxylic acids, the dicarboxylic acids, the boron compounds, in particular special boric acid, the Ca salts or the polyfunctional amines such as mono-, di- or Triethanolamine. Preferred detergent compositions according to the invention white a content of boron compounds, especially boric acid. Particularly preferred Agents contain 0.5 to 3 wt .-% boric acid, in particular 1 to 2 wt .-%, each based on all means.

Carbonates, hydrogen carbonates and silicates can be used in particular as water-soluble builders which bring the pH of the compositions into the desired range. Among these, hydrated and anhydrous sodium carbonate, hydrated and anhydrous potassium carbonate, sodium sesquicarbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, amorphous sodium and potassium silicates and crystalline sodium and potassium silicates have particular advantages. Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values are for × 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred. Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6 can also be used. which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdry X-ray amorphous silicates.

Preferred detergent compositions within the scope of the present invention additionally contain alkali carriers from the groups of carbonates, hydrogen carbonates, Amorphous and crystalline silicates, especially disilicates, in amounts from 1 to 15 % By weight, preferably from 2 to 12% by weight and in particular from 3 to 9% by weight, each Weil based on the detergent composition.

As organic cobuilders in the dishwasher according to the invention agents in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, As Paraginic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phosphonates are used.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, with such carboxylic acids under polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen. The acids themselves can also be used. The acids have besides theirs Builders typically also have the property of an acidifying component and thus also for setting a lower and milder pH value of Reini agents. In particular, citric acid, succinic acid, glutaric acid, adi pinic acid, gluconic acid and any mixtures of these.  

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. For the purposes of this document, the molecular weights given for polymeric polycarbonate boxylates are weight-average molecular weights M _{W of} the particular acid form, which were basically determined by gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 to 70,000 g / mol preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The content of (co) polymeric polycarboxylates in the agent is before preferably 0 to 5% by weight, in particular 0.5 to 2.5% by weight.

Another class of substances with cobuilder properties are the phosphonates it is in particular hydroxyalkane or aminoalkanephosphonates. Under  the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Ho mologist in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferred as a builder from the phosphonate class turns. The aminoalkanephosphonates also have a pronounced heavy metal bin de assets. Accordingly, it can, especially if the agent also ent bleach hold, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned. The salary of preferred rice Detergent compositions on phosphonates is 0 to 3% by weight, preferably 0.1 to 2.5% by weight and in particular 0.2 to 2% by weight.

A wide number of different salts can be used as the electrolyte. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the compositions according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

The cleaning agent compositions according to the invention can protect the Washware or machine corrosion inhibitors, especially silver protective agents in the field of automatic dishwashing ha ben. The known substances of the prior art can be used. In general, Above all, silver protection agents selected from the group of triazoles, the benzotria zoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and over gear metal salts or complexes are used. To be used particularly preferably are benzotriazole and / or alkylaminotriazole. One finds in cleaner formulations In addition, agents often containing active chlorine, which indicate the corroding of the silver surface Lich diminish. In chlorine-free cleaners, oxygen and stick are particularly important organic redox-active compounds containing substances, such as di- and trihydric phenols,  e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyro gallol or derivatives of these classes of compounds. Also salt and complex inorganic Chemical compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often found Use. The transition metal salts selected from are preferred the group of manganese and / or cobalt salts and / or complexes, particularly preferred the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, chlorides of cobalt or manganese and manganese sulfate. You can also Zinc compounds are used to prevent corrosion on the wash ware.

Preferred detergent compositions in the context of the present invention additionally contain one or more silver protection agents from the group of the triazoles, the Benzotriazoles, the Bisbenzotriazole, the Aminotriazole, the Alkylaminotriazole and the Transition metal salts or complexes in amounts of 0.05 to 2.5% by weight, preferably from 0.1 to 2% by weight and in particular from 0.1 to 1% by weight, with benzotriazoles and / or alkylaminotriazoles are particularly preferred.

The agents according to the invention can be prepared by simply mixing them into conti Nuclear or discontinuous processes take place. Advantageously Production of the water-soluble builders dissolved or suspended in the liquid matrix and stirred intensively in a mixer. Optional can also be used at this stage Components are added, in particular the addition of surfactants Viosko sitätsreglern is recommended at this time, if the agents of this invention Should contain substances. Alternatively, the solution or dispersion can also be at 30 to 50 ° C be heated to accelerate the homogeneous distribution.

Below are other optional ingredients such as dyes, electrolytes u. Ä. admixed, wherein temperature-labile substances such as perfume and / or Enzymes are advantageously stirred in only after cooling. If desired, the resulting product can be further diluted.  

Examples

By mixing the liquid components and adding the finely ground solids the formulations E1 and E2 according to the invention were prepared, their composition Table 1 shows:

Table 1

Non-aqueous dishwashing detergent (% by weight)

The physical data of the liquid detergent compositions E1 and E2 are summarized in Table 2.  

Table 2

Physical data of detergent compositions

The agents E1 and E2 according to the invention were in a household dish dishwasher (Miele G 590 with universal program) under the following washing conditions tested against a commercially available dish detergent in powder form: 55 ° C / 16 ° d Water hardness measured in the main wash cycle (i.e. "harsh conditions").

The dosage for both the commercially available powder and for the aqueous invention the respective products were 25 g each. Table 2 shows the results of the evaluation by an expert panel, using the following assessment scheme: Visu Elle evaluation for tea, milk, baked meat and E1 / milk by comparison with an image catalog. The starch removal is determined by gravimetric determination of the type dirt removal determined. Evaluation scheme: grade 0 for original soiled Dishes, grade 10 for absolutely clean dishes.

Table 3

Cleaning performance

The liquid detergent compositions according to the invention achieve Lei performance level of conventional powder detergents (E1 / milk, starch) or exceed this even (tea, milk).

Claims (14)

1. Liquid non-aqueous detergent compositions for machine dishwashing, containing, in addition to other optional detergent ingredients

• a) 20 to 50% by weight of one or more water-soluble builders,
• b) 1 to 25% by weight glycerol,
• c) 5 to 40 wt .-% of a liquid at room temperature polyethylene glycol and
• d) 0 to 20% by weight of 1,2-propanediol
• e) ≦ 2% by weight of free water.

2. Detergent compositions according to claim 1, characterized in that it is less than 1.5% by weight, preferably less than 1% by weight and in particular contain less than 0.5% by weight of free water. 3. Detergent compositions according to one of claims 1 or 2, characterized characterized in that they contain citrates and / or phosphates as water-soluble builders, preferably alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate). 4. detergent compositions according to any one of claims 1 to 3, characterized ge indicates that it contains the water-soluble builder (s) in amounts of 22.5 up to 45% by weight, preferably from 25 to 40% by weight and in particular from 27.5 to 35 % By weight, based in each case on the detergent composition. 5. detergent compositions according to any one of claims 1 to 4, characterized ge indicates that they 1.5 to 22.5 wt .-%, preferably 2.5 to 20 wt .-% and ins particular 5 to 15% by weight glycerol, 5 to 35% by weight, preferably 7.5 to 30% by weight and in particular 10 to 20% by weight of a polyethylene which is liquid at room temperature lengglycol mixture and 0 to 17.5 wt .-%, preferably 1 to 15 wt .-% and ins contain in particular 2.5 to 10% by weight of 1,2-propanediol.   6. detergent compositions according to any one of claims 1 to 5, characterized ge indicates that it additionally contains non-ionic and / or anionic surfactant (s), preferably nonionic surfactant (s) in amounts of 0.1 to 4% by weight, preferably as from 0.15 to 3 wt .-% and in particular from 0.2 to 2 wt .-%, each based on the detergent composition. 7. detergent compositions according to any one of claims 1 to 6, characterized in that they additionally 0.01 to 5 wt .-%, preferably 0.02 to 4 wt .-%, particularly preferably 0.05 to 3 wt .-% and in particular 0.1 to 1.5% by weight, of a polymeric thickener, preferably from the group of the polyurethanes or the modified polyacrylates, with particular preference for thickeners of the formula IV
in which R ^{3 is} H or a branched or unbranched C _1-4 alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 alk ( en) yl radical, R ^{5 stands} for H or R ⁴ and n stands for a natural number. 8. detergent compositions according to any one of claims 1 to 7, characterized ge indicates that they also contain bleach; preferably acid bleach fabric base with particular preference for sodium perborate monohydrate and natri percarbonate, in amounts of 2.5 to 25% by weight, preferably 5 to 20% by weight and in particular from 7.5 to 15% by weight, in each case based on the composition, contain.   9. detergent compositions according to any one of claims 1 to 8, characterized ge indicates that it additionally contains one or more bleach activators, preferably from the group of the O- and / or N-acylated alcohols or amines, in particular Preference for tetraacetylethylenediamine (TAED), n- or iso- Nonanoyloxybenzenesulfonate (n- or iso-NOBS), 1,2,3-triacetoxypropane, n-methyl- Morpholinium acetonitrile methyl sulfate (MMA) and mixtures thereof, in quantities from 1 to 15% by weight, preferably from 2 to 12% by weight and in particular from 4 to 8 % By weight. 10. detergent compositions according to any one of claims 1 to 9, characterized ge indicates that they additionally enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in Amounts from 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4 wt .-%, each based on the detergent composition. 11. Detergent compositions according to one of claims 1 to 10, characterized characterized in that they additionally contain alkali carriers from the groups of the carbonates, Hy drug carbonates, amorphous and crystalline silicates, especially disilicates, in amounts of 1 to 15% by weight, preferably 2 to 12% by weight and in particular from 3 to 9% by weight, based in each case on the detergent composition hold. 12. Detergent compositions according to one of claims 1 to 11, characterized characterized in that they additionally contain one or more silver protection agents from the group the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkyla minotriazoles and the transition metal salts or complexes in amounts from 0.05 to 2.5% by weight, preferably from 0.1 to 2% by weight and in particular from 0.1 to 1 % By weight, with benzotriazoles and / or alkylaminotriazoles being particularly preferred are preferred.   13. Detergent compositions according to one of claims 1 to 12, characterized characterized in that they have a viscosity of 500 to 5000 mPa.s, preferably of 1000 to 4000 mPa.s and in particular from 1300 to 3000 mPa.s. 14. Detergent compositions according to one of claims 1 to 13, characterized characterized in that the pH of a 1 wt .-% solution of the composition in distilled water between 7 and 11, preferably between 8 and 10 and especially is in particular between 8.5 and 9.5.