EP3047003B1 - Use of modified polyaspartic acids in detergents - Google Patents

Description

The present invention relates to the use of modified polyaspartic acids in dishwashing agents, in particular as dispersants, deposit inhibitors and spot inhibitors.

Polymers obtained by free radical polymerization and made from carboxyl group-containing monomers have been an important component of phosphate-containing and phosphate-free automatic dishwashing agents for many years. With their dirt-dispersing and deposit-inhibiting effect, they make a significant contribution to the cleaning and rinsing performance of automatic dishwashing detergents. In this way, they ensure that no salt deposits from the hardness-forming calcium and magnesium ions remain on the dishes. Homo- and copolymers of acrylic acid are frequently used for this purpose.

A disadvantage of these polymers obtainable by free radical polymerization from carboxyl group-containing monomers is that they under aerobic conditions, such as are e.g. prevail in a municipal sewage treatment plant, are not biodegradable.

Due to increasing environmental awareness, the demand for biodegradable polymer alternatives to the polycarboxylates based on acrylic acid is growing. Biodegradable polymers that have hitherto been available on the market, such as polyaspartic acid or carboxymethylated inulin, have, however, proven to be difficult to implement commercially. The reasons are manifold: insufficient effect in the specific application, too high costs due to complex manufacturing processes and / or expensive starting materials, no or only little flexibility of the polymer synthesis. Thus, in contrast to the processes for the production of polyacrylic acids, the methods practiced for the production of polyaspartic acid do not allow any great variations in terms of structure, molecular weight and degree of neutralization. The polyaspartic acid is obtained in neutralized form as the sodium salt. The molecular weights range between 2000-3000 g / mol or between 5000-6000 g / mol, depending on the manufacturing process. An adaptation of the polymer structure or the molecular weight to specific application requirements through targeted process changes is not possible or only possible to a very limited extent.

In WO 2011/001170 detergent compositions for automatic dishwashing are described, containing polyaspartic acid, a liquid nonionic surfactant and at least one solid nonionic surfactant, the production of polyaspartic acid not being described. In WO 2009/095645 Detergent and cleaning agent compositions are described which contain subsequently modified polyaspartic acids with polyaspartic acid as the backbone to prevent deposits. The modified polyaspartic acids are obtained by reacting polyaspartic acid or polysuccinimide with PO / EO block copolymers, polyethyleneimine or adenosine triphosphate. Such a polyaspartic acid backbone is difficult or impossible to adjust with regard to its molecular weight. WO94 / 01486 discloses the use of modified polyaspartic acid as an additive in detergent.

The object of the invention was therefore to provide polymers as detergent additives, in particular as an additive to phosphate-free detergent formulations for machine dishwashing, which can be used to inhibit deposits in water-bearing systems, are variably adjustable in their polymer structure and molecular weight and are biodegradable. The molecular weight of the polymers can ideally be set between 1,000 and 10,000 g / mol.

This object was achieved by the present invention in accordance with the claims and the following description and examples.

1. (i) 50 bis 99 mol% Asparaginsäure; und
2. (ii) 1 bis 50 mol% mindestens einer carboxylhaltigen Verbindung

und anschließender Hydrolyse der Cokondensate unter Zugabe einer Base, wobei (ii) keine Asparaginsäure ist. Die erfindungsgemäße Spülmittelzusammensetzung enthält neben den hier beschriebenen und erfindungsgemäß einzusetzenden modifizierten Polyasparaginsäuren auch Komplexbildner, Builder und/oder Co-Builder, nichtionische Tenside, Bleichmittel und/oder Bleichaktivatoren, Enzyme und ggf. weitere Zusatzstoffe.The present invention relates to the use of modified polyaspartic acids as an additive in detergents, as well as detergent compositions comprising modified polyaspartic acids. The modified polyaspartic acids used in connection with the present invention can be prepared by polycondensation of

1. (i) 50 to 99 mole percent aspartic acid; and
2. (ii) 1 to 50 mol% of at least one carboxyl-containing compound

and subsequent hydrolysis of the cocondensates with the addition of a base, (ii) not being aspartic acid. In addition to the modified polyaspartic acids described here and to be used according to the invention, the detergent composition according to the invention also contains complexing agents, builders and / or co-builders, nonionic surfactants, bleaching agents and / or bleach activators, enzymes and possibly other additives.

As a result of the production process for polyaspartic acid described here, the polyaspartic acid is initially obtained in salt form after the hydrolysis step with addition of a base, as the person skilled in the art can easily recognize. The acid form of polyaspartic acid can easily be obtained by a further step of acidifying the salt, which can be carried out in a manner known to the person skilled in the art. Suitable acids for this include mineral acids, for example sulfuric acid or hydrochloric acid. If only the salt of polyaspartic acid is desired, for example as an intermediate stage, the step of subsequent acidification can be dispensed with. If polyaspartic acid is mentioned in connection with the present invention, its corresponding salts are accordingly also encompassed, as they are obtainable or are obtained by the mentioned subsequent acidification step and as recognized by the person skilled in the art.
The optional acidification of the salt of the modified polyaspartic acid can take place, for example, by adding a defined amount of a concentrated or dilute mineral acid such as sulfuric acid or hydrochloric acid to an aqueous sodium salt solution of the modified polyaspartic acid. The acidification can also be done by treatment with an acidic ion exchanger such as Amberlite IR 120 (hydrogen form), by allowing the aqueous Na salt solution of the modified polyaspartic acid to flow over a column packed with the ion exchanger.

1. (i) 50 bis 99 mol%, bevorzugt 60 bis 95 mol%, besonders bevorzugt 80 bis 95 mol% Asparaginsäure; und Methansulfonsäure in einem Verhältnis von 200:1 bis 5:1 und
2. (ii) 1 bis 50 mol%, bevorzugt 5 bis 40 mol%, besonders bevorzugt 5 bis 20 mol% mindestens einer carboxylhaltigen Verbindung,

und anschließender Hydrolyse der Cokondensate unter Zugabe einer Base, beispielsweise Natronlauge, wobei (ii) keine Asparaginsäure ist.
Die vorliegende Erfindung betrifft auch Spülmittelzusammensetzungen, insbesondere Spülmittelzusammensetzungen für maschinelles Geschirrspülen, umfassend modifizierte Polyasparaginsäuren herstellbar wie hier dargestellt und beschrieben. Die Beschreibung der Herstellung von modifizierten Polyasparaginsäuren im Zusammenhang mit der vorliegenden Erfindung betrifft also generell sowohl die erfindungsgemäße Verwendung solcher modifizierter Polyasparaginsäuren als Zusatzstoff in Spülmitteln, als auch ihren Einsatz als Bestandteil von erfindungsgemäßen Spülmittelzusammensetzungen.
Als Asparaginsäure (i) im Zusammenhang mit der Herstellung der erfindungsgemäß einzusetzenden Polyasparaginsäure kann sowohl L- als auch D- und DL-Asparaginsäure eingesetzt werden. Bevorzugt wird L-Asparaginsäure eingesetzt.
Als carboxylhaltige Verbindung (ii) im Zusammenhang mit der Herstellung der erfindungsgemäß einzusetzenden Polyasparaginsäure kann unter anderem eine Carbonsäure (Monocarbonsäure oder Polycarbonsäure), eine Hydroxycarbonsäure und/oder eine Aminosäure (außer Asparaginsäure) eingesetzt werden. Solche Carbonsäuren oder Hydroxycarbonsäuren sind bevorzugt mehrbasisch. In diesem Zusammenhang können also bei der Herstellung der erfindungsgemäß einzusetzenden Polyasparaginsäure mehrbasische Carbonsäuren eingesetzt werden, z.B. Oxalsäure, Adipinsäure, Fumarsäure, Maleinsäure, Itaconsäure, Aconitsäure, Bernsteinsäure, Malonsäure, Korksäure, Azelainsäure, Diglykolsäure, Glutarsäure, C₁-C₂₆ Alkylbernsteinsäuren (z.B. Octylbernsteinsäure), C₂-C₂₆ Alkenylbernsteinsäuren (z.B. Octenylbernsteinsäure), 1,2,3-Propantricarbonsäure, 1,1,3,3-Propantetracarbonsäure, 1,1,2,2-Ethantetracarbonsäure, 1,2,3,4-Butantetracarbonsäure, 1,2,2,3-Propantetracarbonsäure, oder 1,3,3,5-Pentantetracarbonsäure. Ferner können in diesem Zusammenhang mehrbasische Hydroxycarbonsäuren eingesetzt werden, z.B. Citronensäure, Isocitronensäure, Schleimsäure, Weinsäure, Tartronsäure, oder Äpfelsäure. Als Aminosäuren können in diesem Zusammenhang unter anderem Aminocarbonsäuren (z.B. Glutaminsäure, Cystein), basische Diaminocarbonsäuren (z.B. Lysin, Arginin, Histidin, Aminocaprlactam), neutrale Aminosäuren (z.B. Glycin, Alanin, Valin, Leucin, Isoleucin, Methionin, Cystein, Norleucin, Caprolactam, Asparagin, Isoasparagin, Glutamin, Isoglutamin), Aminosulfonsäuren (z.B. Taurin), Hydroxylarninosäuren (z.B. Hydroxyprolin, Serin, Threonin), Iminocarbonsäuren (z.B. Prolin, Iminodiessigsäure), oder aromatische und heterocyclische Aminosäuren (z.B. Anthranitsäure, Tryptophan, Tyrosin, Histidin) eingesetzt werden, aber nicht Asparaginsäure. Bevorzugte carboxylhaltige Verbindungen (ii) im Zusammenhang mit der Herstellung der erfindungsgemäß einzusetzenden modifizierten Polyasparaginsäuren sind 1,2,3,4-Butantetracarbonsäure, Zitronensäure, Glycin, Glutaminsäure, Itaconsäure, Bernsteinsäure, Taurin, Maleinsäure und Glutarsäure, besonders bevorzugt 1,2,3,4-Butantetracarbonsäure, Zitronensäure, Glycin und Glutaminsäure.The modified polyaspartic acids to be used according to the invention are extremely useful as additives in detergents, in particular detergents for automatic dishwashing, and have very good dispersing, deposit inhibitor and spot inhibiting properties. They are also biodegradable and can be produced with variable molecular weights.
The present invention thus relates to the use of modified polyaspartic acid as an additive - for example, but not limited to dispersants, deposit inhibitors or spot inhibitors - in detergents, in particular detergents for automatic dishwashing,
wherein the modified polyaspartic acid can be prepared by polycondensation of

1. (i) 50 to 99 mol%, preferably 60 to 95 mol%, particularly preferably 80 to 95 mol% aspartic acid; and methanesulfonic acid in a ratio of 200: 1 to 5: 1 and
2. (ii) 1 to 50 mol%, preferably 5 to 40 mol%, particularly preferably 5 to 20 mol% of at least one carboxyl-containing compound,

and subsequent hydrolysis of the cocondensates with the addition of a base, for example sodium hydroxide solution, where (ii) is not aspartic acid.
The present invention also relates to detergent compositions, in particular detergent compositions for automatic dishwashing, comprising modified polyaspartic acids producible as shown and described here. The description of the production of modified polyaspartic acids in connection with the present invention thus relates generally both to the inventive use of such modified polyaspartic acids as an additive in detergents and to their use as a component of detergent compositions according to the invention.
Both L- and D- and DL-aspartic acid can be used as aspartic acid (i) in connection with the preparation of the polyaspartic acid to be used according to the invention. L-aspartic acid is preferably used.
A carboxylic acid (monocarboxylic acid or polycarboxylic acid), a hydroxycarboxylic acid and / or an amino acid (except aspartic acid) can be used as the carboxyl-containing compound (ii) in connection with the preparation of the polyaspartic acid to be used according to the invention. Such carboxylic acids or hydroxycarboxylic acids are preferably polybasic. In this context, polyaspartic acid to be used according to the invention can be prepared using polybasic carboxylic acids, for example oxalic acid, adipic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, succinic acid, malonic acid, suberic acid, azelaic acid, diglycolic acid, glutaric acid, C ₁ -C ₂₆ alkyl succinic acids (e.g. Octylsuccinic acid), C ₂ -C ₂₆ alkenylsuccinic acids (e.g. octenylsuccinic acid), 1,2,3-propane tricarboxylic acid, 1,1,3,3-propane tetracarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,2,3,4- Butanetetracarboxylic acid, 1,2,2,3-propanetetracarboxylic acid, or 1,3,3,5-pentanetetracarboxylic acid. In addition, polybasic hydroxycarboxylic acids can be used in this context, for example citric acid, isocitric acid, mucic acid, tartaric acid, tartronic acid, or malic acid. Amino acids that can be used in this context include aminocarboxylic acids (e.g. glutamic acid, cysteine), basic diaminocarboxylic acids (e.g. lysine, arginine, histidine, aminocaprlactam), neutral amino acids (e.g. glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactamate , Asparagine, isoasparagine, glutamine, isoglutamine), aminosulfonic acids (e.g. taurine), hydroxylamino acids (e.g. hydroxyproline, serine, threonine), iminocarboxylic acids (e.g. proline, iminodiacetic acid), or aromatic and heterocyclic amino acids (e.g. anthranitic acid, tryptophane) are used but not aspartic acid. Preferred carboxyl-containing compounds (ii) in connection with the preparation of the modified polyaspartic acids to be used according to the invention are 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine, glutamic acid, itaconic acid, succinic acid, taurine, maleic acid and glutaric acid, particularly preferably 1,2,3 , 4-butanetetracarboxylic acid, citric acid, glycine and glutamic acid.

The bases used in the hydrolysis of the cocondensates in the production of the modified polyaspartic acids to be used according to the invention include: alkali and alkaline earth metal bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide; Carbonates such as soda and potassium carbonate; Ammonia and primary, secondary or tertiary amines; other bases with primary, secondary or tertiary amino groups. Sodium hydroxide solution or ammonium hydroxide are preferred in connection with the present invention.

The modified polyaspartic acids to be used according to the invention are generally prepared via a polycondensation of aspartic acid with at least one carboxyl-containing compound (not aspartic acid) and subsequent hydrolysis of the cocondensates with the addition of a base as shown and described here above and below. The production of such modified polyaspartic acids is also in DE 4221875.6 described by way of example. The preparation of the modified polyaspartic acids to be used according to the invention is described by way of example below. This description of the manufacture must not be understood as limiting with regard to the modified polyaspartic acids to be used according to the invention. The polyaspartic acids to be used according to the invention include, in addition to those which are produced according to the following description of the production, also those which can be produced by the following process. The modified polyaspartic acids to be used according to the invention can be prepared, for example, by polycondensation of components (i) and (ii), ie aspartic acid and at least one carboxyl-containing compound in the molar ratios as described here. The polycondensation can take place at temperatures from 100 to 270.degree. C., preferably from 120 to 250.degree. C., particularly preferably from 180 to 220.degree. The condensation (tempering) is preferably carried out in vacuo or under an inert gas atmosphere (eg N ₂ or argon). However, the condensation can also take place under increased pressure or in a gas stream, for example carbon dioxide, air, oxygen or water vapor. The reaction times depend on the reaction conditions chosen for the condensation generally between 1 minute and 50 hours, preferably between 5 to 8 hours. The polycondensation can, for example, be carried out in the solid phase by first preparing an aqueous solution or suspension of aspartic acid and at least one carboxyl-containing compound (ii) and evaporating the solution to dryness. Condensation can already set in here. Suitable reaction apparatus for the condensation are, for example, heating bands, kneaders, mixers, paddle dryers, extruders, rotary kilns and other heatable devices in which the condensation of solids can be carried out with removal of the water of reaction. Polycondensates with a low molecular weight can also be produced in pressure-tight sealed vessels by not removing or only partially removing the water of reaction. Polycondensation can also be carried out using infrared radiation or microwave radiation. An acid-catalyzed polycondensation, for example with inorganic acids of phosphorus or sulfur or with hydrogen halides, is also possible. Such acid-catalyzed polycondensations are also in DE 4221875.6 described.
By adding small amounts of methanesulfonic acid during the polycondensation of aspartic acid, the molecular weight of the polyaspartic acid, obtained after hydrolysis of the polysuccinimide intermediate, can be controlled. It is therefore possible in the context of the present invention to produce modified polyaspartic acid to be used according to the invention by using methanesulfonic acid as an additive in addition to aspartic acid (i) and a carboxyl-containing compound (ii) in the polycondensation and then using the cocondensate obtained with a base as described here is hydrolyzed. The molar ratio of aspartic acid (i) and a carboxyl-containing compound (ii) on the one hand to methanesulfonic acid on the other in the condensation step should be 200: 1 to 5: 1, preferably 100: 1 to 10: 1, particularly preferably 50: 1 to 12: 1. In the present invention, 50 to 99 mol%, preferably 60 to 95 mol%, particularly preferably 80 to 95 mol% aspartic acid and 1 to 50 mol%, preferably 5 to 40 mol%, are particularly preferred for preparing the modified polyaspartic acid to be used according to the invention 5 to 20 mol% of a carboxyl-containing compound is polycondensed with methanesulfonic acid in a ratio of 200: 1 to 5: 1, preferably 100: 1 to 10: 1, particularly preferably 50: 1 to 12: 1, as described here. Like polyaspartic acid, methanesulfonic acid is biodegradable. Small amounts of methanesulfonic acid can remain in the polymer product without causing ecological disadvantages and without affecting the performance in the numerous applications. A complex work-up or cleaning is not necessary. Loss of yield due to the work-up is avoided.
In the thermal polycondensation of aspartic acid with one of the carboxyl-containing compounds (ii) (with or without methanesulfonic acid), the polycondensate is generally obtained in the form of the water-insoluble modified polyaspartimides, in a few cases in water-soluble form (e.g. in the polycondensation of L- Aspartic acid with citric acid). The cocondensates of aspartic acid can be purified from the unreacted starting materials, for example, by adding the condensation product crushed and extracted with water at temperatures of 10 to 100 ° C. In the process, the unreacted starting materials are released and any methanesulfonic acid used is washed out. Unreacted aspartic acid can easily be removed by extraction with 1N hydrochloric acid.

The modified polyaspartic acids are preferably obtained from the polycondensates by slurrying or dissolving the polycocondensates in water (if the polycocondensate is already water-soluble, e.g. polycocondensate made from L-aspartic acid and citric acid) and at temperatures preferably in the range from 0 to 90 ° C Adding a base hydrolyzes and neutralizes. The hydrolysis and neutralization take place preferably at pH values of 8 to 10. Alkali and alkaline earth metal bases such as sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide or barium hydroxide come into consideration as bases. Carbonates such as soda and potassium carbonate can also be used as bases. Ammonia and primary, secondary or tertiary amines and other bases with primary, secondary or tertiary amino groups are also suitable as bases. When using amines for the conversion of polyaspartimide, the amines can be bound to the polyaspartic acid in a salt-like or amide-like manner due to their high reactivity. The treatment with bases gives partially or completely neutralized polycocondensates which, according to the use in the previous polycondensation, contain 50 to 99 mol% of aspartic acid according to (i) and 1 to 50 mol% of at least one carboxyl group-containing compound (ii) (with or without methanesulfonic acid in proportions as described here), in the form of the salts corresponding to the bases.

The modified polyaspartic acids to be used according to the invention or their salts can be used as an aqueous solution or in solid form, e.g. be used in powder or granular form. As is known to the person skilled in the art, the powder or granulate form can be obtained, for example, by spray drying, spray granulation, fluidized bed spray granulation, roller drying or freeze drying of the aqueous solution of polyaspartic acids or their salts.

The present invention also relates to detergent compositions, in particular detergent compositions suitable for automatic dishwashing, which, in addition to the modified polyaspartic acids described here and to be used according to the invention, also complexing agents, builders and / or co-builders, nonionic surfactants, bleaching agents and / or bleach activators, enzymes and possibly other additives such as solvents. The modified polyaspartic acids described here and to be used according to the invention can be incorporated directly into the formulations (mixtures) in their various dosage forms by methods known to the person skilled in the art. Solid formulations such as powders, tablets, gel-like formulations and liquid formulations should be mentioned here.
The modified polyaspartic acids described here and to be used according to the invention can be used particularly advantageously in dishwasher detergents. you are characterized above all by their deposit-inhibiting effect on both inorganic and organic deposits. In particular, they inhibit deposits of calcium and magnesium carbonate and calcium and magnesium phosphates and phosphonates. In addition, they prevent deposits from the dirt in the wash liquor, such as grease, protein and starch deposits.

The detergent compositions according to the invention can be provided in liquid, gel-like or solid form, in one or more phases, as tablets or in the form of other dosage units, packaged or unpackaged.

The modified polyaspartic acids described here and to be used according to the invention can be used both in multi-component product systems (separate use of detergent, rinse aid and regeneration substitute) and in detergents in which the functions of detergent, rinse aid and regeneration salt are combined in one product (e.g. 3- in-1 products, 6-in-1 products, 9-in-1 products, all-in-one products).

1. (a) 1-20 Gew%, bevorzugt 1-15 Gew%, besonders bevorzugt 2-12 Gew% mindestens einer hier beschriebenen und erfindungsgemäß einzusetzenden modifizierten Polyasparaginsäure;
2. (b) 0-50 Gew% Komplexbildner;
3. (c) 0,1-80 Gew% Builder und/oder Co-Builder;
4. (d) 0,1-20 Gew% nichtionische Tenside;
5. (e) 0-30 Gew% Bleichmittel, Bleichaktivatoren und Bleichkatalysatoren;
6. (f) 0-8 Gew% Enzyme; und
7. (g) 0-50 Gew% Zusatzstoffe.

The detergent compositions of the invention comprise

1. (a) 1-20% by weight, preferably 1-15% by weight, particularly preferably 2-12% by weight, of at least one modified polyaspartic acid described here and to be used according to the invention;
2. (b) 0-50% by weight complexing agent;
3. (c) 0.1-80% by weight of builder and / or co-builder;
4. (d) 0.1-20% by weight of nonionic surfactants;
5. (e) 0-30% by weight of bleaching agents, bleach activators and bleach catalysts;
6. (f) 0-8 wt% enzymes; and
7. (g) 0-50 wt% additives.

The detergent composition according to the invention is particularly suitable as a detergent composition for automatic dishwashing. In one embodiment, the dishwashing detergent composition according to the invention is therefore an automatic dishwashing detergent composition.

The following can be used as complexing agents (b), for example: nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, as well as their respective ethylenediamine diacetic acid. Preferred complexing agents (b) are methylglycine diacetic acid and glutamic acid diacetic acid and their salts. Particularly preferred complexing agents (b) are methylglycine diacetic acid and its salts. According to the invention, preference is given to 3 to 50% by weight of complexing agents (b).

In particular, water-soluble or water-insoluble substances, the main task of which is to bind calcium and magnesium ions, can be used as builders and / or co-builders (c). These can be low molecular weight carboxylic acids as well as their salts such as alkali citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali succinates, alkali alonates, fatty acid sulfonates, oxydisuccinates, alkyl or alkenyl disuccinates, gluconic acids, tiacoacinate succinate, tiacoacinate, tiacoacinate, tiacoacinacetate, tiacoacinacetate, tiacinoacetate, tiacoylacetate, tiacinoacetate, tiacinate succinate, carboxymethyloyl acetate, carboxymethosuccinate, tiacinate succinate, tiacinoacetate, tiacinoacetate, tiacinacetate, tiacetysuccinate, tiacinoacetate, carboxymethosuccinate, tiacinate succinate, carboxymethyloyl acetate, trisodium citrate dihydrate or trisodium citrate dihydrate.
Another class of substances with co-builder properties which can be contained in the cleaning agents according to the invention are the phosphonates. These are in particular hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. From the class of the phosphonates, HEDP is preferably used as the builder. The aminoalkanephosphonates also have a pronounced shear metal binding capacity. Accordingly, especially if the agents also contain bleach, it can be preferred to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the phosphonates mentioned.
Among other things, silicates can be used as builders. It may contain crystalline layered silicates with the general formula NaMSi _x O _{2x + 1} yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x is 2, 3 or 4 and y is a number from 0 to 33, preferably 0 to 20. In addition, amorphous sodium silicates with an SiO ₂ : Na ₂ O ratio of 1 to 3.5, preferably from 1.6 to 3 and in particular from 2 to 2.8 can be used.
Furthermore, carbonates and hydrogen carbonates can be used as builders and / or co-bullders (c) in connection with the detergent composition according to the invention, among which the alkali salts, in particular sodium salts, are preferred.
Homopolymers and copolymers of acrylic acid or methacrylic acid, which preferably have a weight-average molar mass of 2,000 to 50,000 g / mol, can also be used as co-builders. Particularly suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and their anhydrides such as maleic anhydride. Comonomers containing sulfonic acid groups, such as 2-acrylamido-2-methylpropanesultonic acid, allyl sulfonic acid and vinyl sulfonic acid, are also suitable. Hydrophobic comonomers are also suitable, such as, for example, isobutene, diisobutene, styrene, alpha-olefins having 10 or more carbon atoms. Hydrophilic monomers with hydroxyl function or alkylene oxide groups can also be used as comonomers. Examples include: allyl alcohol and isoprenol and their alkoxylates and methoxypolyethylene glycol (meth) acrylate.

Preferred amounts for builders and / or co-builders in connection with the dishwashing detergent composition according to the invention are 5 to 80% by weight, particularly preferably 10 to 75% by weight, 15 to 70% by weight or 15 to 65% by weight.

• worin R¹ ein linearer oder verzweigter Alkylrest mit 8 bis 22 C-Atomen ist,
• R² und R³ unabhängig voneinander Wasserstoff oder ein linearer oder verzweigter Alkylrest mit 1 bis 10 C-Atomen oder H sind, wobei R² bevorzugt Methyl ist, und
• a und b unabhängig voneinander 0 bis 300 sind. Bevorzugt ist a = 1 - 100 und b = 0 - 30.

Low-foaming or low-foaming nonionic surfactants can be used, for example, as nonionic surfactants (d) in connection with the detergent composition according to the invention. These can be present in proportions of 0.1 to 20% by weight, preferably 0.1 to 15% by weight, particularly preferably 0.25 to 10% by weight or 0.5 to 10% by weight. Suitable nonionic surfactants include, inter alia, surfactants of the general formula (I)

R ¹ -Q- (CH ₂ CH ₂ O) _a - (CHR ² CH ₂ O) _b -R ³ (I),

• wherein R ^{1 is} a linear or branched alkyl radical with 8 to 22 carbon atoms,
• R ² and R ^{3 are,} independently of one another, hydrogen or a linear or branched alkyl radical having 1 to 10 carbon atoms or H, where R ^{2 is} preferably methyl, and
• a and b are independently 0 to 300. Preferably a = 1-100 and b = 0-30.

• worin R⁴ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht,
• R⁵ einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet,
• c und e für Werte zwischen 0 und 40 steht, und
• d für einen Wert von mindestens 15 steht.

Also suitable for the purposes of the present invention are surfactants of the formula (II)

R ⁴ -O- [CH ₂ CH (CH ₃ ) O] _c [CH ₂ CH ₂ O] _d [CH ₂ CH (CH ₃ ) O] _a CH ₂ CH (OH) R ⁵ (II),

• wherein R ^{4 is} a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof,
• R ⁵ denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof,
• c and e stand for values between 0 and 40, and
• d stands for a value of at least 15.

• worin R⁶ ein verzweigter oder unverzweigter Alkylrest mit 8 bis 16 Kohlenstoffatomen ist,
• R⁷, R⁸ unabhängig voneinander H oder ein verzweigter oder unverzweigter Alkylrest mit 1 bis 5 Kohlenstoffatomen sind,
• R⁹ ein unverzweigter Alkylrest mit 5 bis 17 Kohlenstoffatomen ist,
• f, h unabhängig voneinander eine Zahl von 1 bi 5 sind, und
• g eine Zahl von 13 bis 35 ist.

Also suitable for the purposes of the present invention are surfactants of the formula (III)

R ⁶ O- (CH ₂ CHR ⁷ O) _f (CH ₂ CH ₂ O) _g (CH ₂ CHR ⁸ O) _h -CO-R ⁹ (III),

• wherein R ^{6 is} a branched or unbranched alkyl radical having 8 to 16 carbon atoms,
• R ⁷ , R ⁸ independently of one another are H or a branched or unbranched alkyl radical with 1 to 5 carbon atoms,
• R ^{9 is} an unbranched alkyl radical with 5 to 17 carbon atoms,
• f, h are independently a number from 1 to 5, and
• g is a number from 13 to 35.

The surfactants of the formulas (I), (II) and (III) can be both random copolymers and block copolymers; they are preferred as block copolymers.

In connection with the present invention, di- and multiblock copolymers, composed of ethylene oxide and propylene oxide, which are commercially available, for example, under the name Pluronic® (BASF SE) or Tetronic® (BASF Corporation), can also be used. Furthermore, reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used. Amine oxides or alkyl glycosides are also suitable. An overview of suitable nonionic surfactants can be found in EP-A 851 023 as in DE-A 198 19 187 disclosed.
It can also contain mixtures of several different nonionic surfactants. The detergent compositions according to the invention can furthermore contain anionic or zwitterionic surfactants, preferably mixed with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also in EP-A 851 023 as DE-A 198 19 187 called.
Representatives known to the person skilled in the art can be used as bleaching agents and bleach activators (e) in connection with the washing-up liquid compositions according to the invention. Bleaches are divided into oxygen bleaches and chlorine-containing bleaches. Alkali metal perborates and their hydrates and also alkali metal percarbonates are used as oxygen bleaching agents. Preferred bleaching agents are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate. Persulfates and hydrogen peroxide can also be used as oxygen bleaches. Typical oxygen bleaching agents are also organic peracids, such as, for example, perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decanyldiperoxybutic acid. In addition, the following oxygen bleaches can also be used in the detergent composition: Cationic peroxyacids, which are described in the patent applications U.S. 5,422,028 , U.S. 5,294,362 as U.S. 5,292,447 and sulfonyl peroxyacids described in the patent application U.S. 5,039,447 are described. Oxygen bleaches can be used in amounts of generally 0.1 to 30% by weight, preferably 1 to 20% by weight, particularly preferably 3 to 15% by weight, based on the total detergent composition.
Chlorine-containing bleaches and the combination of chlorine-containing bleaches with peroxide-containing bleaches can also be used in connection with the dishwashing detergent compositions according to the invention. Known chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-dimethythydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N, N'-dichlorobenzoylurea, p-toluenesulfone dichloroamide or trichloroethylamine, preferred chlorine-containing bleaches here are sodium hypochlorite, Calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate. Chlorine-containing bleaches can in this context in amounts of 0.1 to 30% by weight, preferably from 0.1 to 20% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.3 to 8% by weight, based on the entire detergent composition can be used.
In addition, small amounts of bleach stabilizers such as phosphonates, borates, metaborates, metasilicates or magnesium salts can be added. In the context of the present invention, bleach activators can be compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid. Among other things, compounds that contain one or more N or. Contain O-acyl groups and / or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides, such as, for example, N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates (nanoylsulfonates or isobenzylsulfonates, such as nanoylsulfonates, such as nano-oxy sulfonates, e.g. iso-NOBS), pentaacetyl glucose (PAG), 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT) or isatoic anhydride (ISA). Also suitable as bleach activators are nitrile quats such as, for example, N-methyl-morpholinium-acetonitrile salts (MMA salts) or trimethylammonium acetonitrile salts (TMAQ salts). Bleach activators from the group consisting of multiply acylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenol sulfonates, particularly preferably n- or iso-NOBS, MMA, and TMAQ, are particularly suitable. Bleach activators can be used in connection with the present invention in amounts of 0.1 to 30% by weight, preferably from 0.1 to 10% by weight, preferably from 1 to 9% by weight, particularly preferably from 1.5 to 8% by weight, based on the entire detergent composition can be used.
In addition to or instead of the conventional bleach activators, so-called bleach catalysts can also be incorporated into rinse aid particles. These substances are bleach-intensifying transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.

The detergent compositions according to the invention can contain 0 to 8% by weight of enzymes as component (f). If the detergent compositions contain enzymes, they preferably contain them in amounts of 0.1 to 8% by weight. Enzymes can be added to the detergent to increase the cleaning performance or to guarantee the cleaning performance of the same quality under milder conditions (e.g. at low temperatures). The enzymes can be used in free form or chemically or physically immobilized on a carrier or in encapsulated form. The most frequently used enzymes in this context include lipases, amylases, cellulases and proteases. Furthermore, esterases, pectinases, lactases and peroxidases can also be used, for example. According to the invention, amylases and proteases are preferably used.

As additives (g) in connection with the detergent compositions according to the invention, for example, anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tablet disintegrants, organic solvents, tabletting aids, disintegrants, thickeners, Solubilizers or water can be used. In addition to the ammonium or alkali metal carbonates, ammonium or alkali metal hydrogen carbonates and ammonium or alkali metal sesquicarbonates, ammonium or alkali metal hydroxides, ammonium or alkali metal silicates and ammonium or alkali metal silicates, as well as mixtures of the aforementioned substances, can be used as alkali carriers.
Corrosion inhibitors that can be used include silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes.
Glass corrosion inhibitors are preferably used to prevent glass corrosion, which is noticeable through cloudiness, iridescence, streaks and lines on the glasses. Preferred glass corrosion inhibitors are, for example, magnesium, zinc and bismuth salts and complexes.
According to the invention, paraffin oils and silicone oils can optionally be used as defoamers and for protecting plastic and metal surfaces. Defoamers are preferably used in proportions of 0.001% by weight to 5% by weight. In addition, colorants such as patent blue, preservatives such as Kathon CG, perfumes and other fragrances can be added to the cleaning formulation according to the invention.
A suitable filler in connection with the detergent compositions according to the invention is, for example, sodium sulfate.
Further possible additives in connection with the present invention are amphoteric and cationic polymers.

In one embodiment, the detergent composition according to the invention is phosphate-free. In this context, the term "phosphate-free" also includes detergent compositions which essentially do not contain phosphate, i. E. Contains phosphate in technically ineffective amounts. This includes in particular compositions with less than 1.0% by weight, preferably less than 0.5% by weight of phosphate, based on the total composition.

The following examples serve to illustrate the present invention and should not be construed as a limitation thereof.

example 1 Production of the modified polyaspartic acids

Molar ratios are given in each case.

Polymers of the Invention

• Polymer 1: Polykondensat aus L-Asparaginsäure/BTC 1,0:0,1
• Polymer 1b: Polykondensat aus L-Asparaginsäure/BTC 1,0:0,1 in Gegenwart von 5 mol% (bez. L-Asp) Methansulfonsäure
• Polymer 2: Polykondensat aus L-Asparaginsäure/BTC 1,0:0,2
• Polymer 3: Polykondensat aus L-Asparaginsäure/Citronensäure 1,0:0,5
• Polymer 4: Polykondensat aus L-Asparaginsäure/Glycin 1,0:0,1
• Polymer 5: Polykondensat aus L-Asparaginsäure/Glutaminsäure 1,0:0,1
• Polymer 5b: Polykondensat aus L-Asparaginsäure/Glutaminsäure 1,0:0,1 in Gegenwart von 5 mol% (bez. L-Asp) Methansulfonsäure

BTC = 1,2,3,4 Butantetracarbonsäure

• Polymer 1: L-aspartic acid / BTC 1.0: 0.1 polycondensate
• Polymer 1b: polycondensate of L-aspartic acid / BTC 1.0: 0.1 in the presence of 5 mol% (relative to L-Asp) methanesulfonic acid
• Polymer 2: L-aspartic acid / BTC 1.0: 0.2 polycondensate
• Polymer 3: L-aspartic acid / citric acid polycondensate 1.0: 0.5
• Polymer 4: L-aspartic acid / glycine polycondensate 1.0: 0.1
• Polymer 5: L-aspartic acid / glutamic acid polycondensate 1.0: 0.1
• Polymer 5b: polycondensate of L-aspartic acid / glutamic acid 1.0: 0.1 in the presence of 5 mol% (relative to L-Asp) methanesulfonic acid

BTC = 1,2,3,4 butanetetracarboxylic acid

Comparative Polymers

• Polymer V1: polyaspartic acid, Na salt, Mw 3000 g / mol
• Polymer V2: polyaspartic acid, Na salt, Mw 5400 g / mol

• Polymer 1:
  In einem 2 I fassenden Reaktor mit Rührer wurden 133,10 g L-Asparaginsäure, 70 g Wasser und 23,42 g 1,2,3,4-Butantetracarbonsäure vorgelegt. Die Reaktionsmischung wurde unter Rühren für 4 h bei einer Temperatur von 210 °C unter gleichzeitiger Abdestillation von Wasser erhitzt. Die entstehende Schmelze des modifizierten Polyaspartimids wurde abgekühlt und anschließend zerkleinert. Um die wässrige Natriumsalzlösung der modifizierten Polyasparaginsäure herzustellen, dispergierte man 100 g der zerkleinerten Reaktionsmasse in 100 g Wasser, erwärmte die Mischung auf 70 °C und fügte bei dieser Temperatur so viel einer 50%igen wässrigen Natronlauge zu, so dass der pH-Wert im Bereich 7-8 lag. Dabei löste sich das in Wasser dispergierte Pulver allmählich auf und man erhielt eine klare wässrige Natriumsalzlösung der modifizierten Polyasparaginsäure. Das gewichtsmittlere Molekulargewicht (Mw) der modifizierten Polyasparaginsäure betrug 2600 g/mol. Erfindungsgemässes Polymer 1b: Die Synthese und Aufarbeitung dieses Polymers erfolgte genau wie in Polymer 1 beschrieben, jedoch wurden 4,81 g Methansulfonsäure zusätzlich in den Reaktor vorgelegt. Das gewichtsmittlere Molekulargewicht (Mw) der modifizierten Polyasparaginsäure betrug 3300 g/mol.
• Polymer 2:
  Analog zur Herstellung des Polymers 1 wurden 133,10 g L-Asparaginsäure und 46,83 g 1,2,3,4-Butantetracarbonsäure in den Reaktor vorgelegt für 2,5 h bei 240 °C polykondensiert. Die resultierende Schmelze des modifizierten Polyaspartimids wurde abgekühlt, zerkleinert und wie in Beispiel 1 beschrieben zu einer wässrigen Natriumsalzlösung der modifizierten Polyasparaginsäure hydrolysiert. Das gewichtsmittlere Molekulargewicht (Mw) der modifizierten Polyasparaginsäure betrug 1870 g/mol.
• Polymer 3:
  Analog zur Herstellung des Polymers 1 wurden 133,10 g L-Asparaginsäure und 96,07 g Zitronensäure in den Reaktor vorgelegt und für 5 h bei 180 °C polykondensiert. Die entstehende Schmelze des modifizierten Polyaspartimids wurde abgekühlt und anschließend zerkleinert. Um die wässrige Natriumsalzlösung der modifizierten Polyasparaginsäure herzustellen, löste man 100 g der abgekühlten und zerkleinerten Reaktionsmasse in 100 g Wasser und fügte unter Eiskühlung so viel einer 50%igen wässrigen Natronlauge zu, dass der pH-Wert im Bereich von 7-8 lag. Das gewichtsmittlere Molekulargewicht (Mw) der modifizierten Polyasparaginsäure betrug 1320 g/mol.
• Polymer 4:
  Analog zur Herstellung des Polymers 1 wurden 133,10 g L-Asparaginsäure, 30.00 g Wasser und 7.51 g Glycin in den Reaktor vorgelegt und 7 h bei 220 °C polykondensiert. Die resultierende Schmelze des modifizierten Polyaspartimids wurde abgekühlt, zerkleinert und wie in Beispiel 1 beschrieben zu einer wässrigen Natriumsalzlösung der modifizierten Polyasparaginsäure hydrolysiert. Das gewichtsmittlere Molekulargewicht (Mw) der modifizierten Polyasparaginsäure betrug 6060 g/mol.
• Polymer 5:
  Analog zu Beispiel 1 wurden 133,10 g L-Asparaginsäure, 30.00 g Wasser und 14.71 g L-Glutaminsäure in den Reaktor vorgelegt und 7,5 h bei 220 °C polykondensiert. Die resultierende Schmelze des modifizierten Polyaspartimids wurde abgekühlt, zerkleinert und wie in Beispiel 1 beschrieben zu einer wässrigen Natriumsalzlösung der modifizierten Polyasparaginsäure hydrolysiert. Das gewichtsmittlere Molekulargewicht (Mw) der modifizierten Polyasparaginsäure betrug 3810 g/mol.

Polymers

• Polymer 1:
  133.10 g of L-aspartic acid, 70 g of water and 23.42 g of 1,2,3,4-butanetetracarboxylic acid were placed in a 2 l reactor with a stirrer. The reaction mixture was heated with stirring for 4 h at a temperature of 210 ° C. with simultaneous distilling off of water. The resulting melt of the modified polyaspartimide was cooled and then comminuted. In order to prepare the aqueous sodium salt solution of the modified polyaspartic acid, 100 g of the comminuted reaction mass were dispersed in 100 g of water, the mixture was heated to 70 ° C. and at this temperature enough 50% aqueous sodium hydroxide solution was added so that the pH was in Range was 7-8. The powder dispersed in water gradually dissolved and a clear aqueous sodium salt solution of the modified polyaspartic acid was obtained. The weight average molecular weight (Mw) of the modified polyaspartic acid was 2600 g / mol. Polymer 1b According to the Invention: This polymer was synthesized and worked up exactly as described in polymer 1, except that 4.81 g of methanesulfonic acid were also placed in the reactor. The weight average molecular weight (Mw) of the modified polyaspartic acid was 3300 g / mol.
• Polymer 2:
  In analogy to the preparation of polymer 1, 133.10 g of L-aspartic acid and 46.83 g of 1,2,3,4-butanetetracarboxylic acid were placed in the reactor and polycondensed at 240 ° C. for 2.5 h. The resulting melt of the modified polyaspartimide was cooled, comminuted and hydrolyzed as described in Example 1 to give an aqueous sodium salt solution of the modified polyaspartic acid. The weight average molecular weight (Mw) of the modified polyaspartic acid was 1870 g / mol.
• Polymer 3:
  In analogy to the preparation of polymer 1, 133.10 g of L-aspartic acid and 96.07 g of citric acid were placed in the reactor and polycondensed at 180 ° C. for 5 h. The resulting melt of the modified polyaspartimide was cooled and then comminuted. To prepare the aqueous sodium salt solution of the modified polyaspartic acid, 100 g of the cooled and comminuted reaction mass were dissolved in 100 g of water and, while cooling with ice, enough of a 50% aqueous sodium hydroxide solution was added so that the pH was in the range of 7-8. The weight average molecular weight (Mw) of the modified polyaspartic acid was 1320 g / mol.
• Polymer 4:
  In a manner analogous to the preparation of polymer 1, 133.10 g of L-aspartic acid, 30.00 g of water and 7.51 g of glycine were placed in the reactor and polycondensed at 220 ° C. for 7 hours. The resulting melt of the modified polyaspartimide was cooled, comminuted and hydrolyzed as described in Example 1 to give an aqueous sodium salt solution of the modified polyaspartic acid. The weight average molecular weight (Mw) of the modified polyaspartic acid was 6060 g / mol.
• Polymer 5:
  Analogously to Example 1, 133.10 g of L-aspartic acid, 30.00 g of water and 14.71 g of L-glutamic acid were placed in the reactor and polycondensed at 220 ° C. for 7.5 hours. The resulting melt of the modified polyaspartimide was cooled, comminuted and hydrolyzed as described in Example 1 to give an aqueous sodium salt solution of the modified polyaspartic acid. The weight average molecular weight (Mw) of the modified polyaspartic acid was 3810 g / mol.

Polymer 5b according to the invention: This polymer was synthesized and worked up exactly as described in polymer 5, except that 4.81 g of methanesulfonic acid were also placed in the reactor. The weight average molecular weight (Mw) of the modified polyaspartic acid was 6100 g / mol.

Comparative Polymers Polymer V1 (polyaspartic acid M):

10 g of maleic acid amide (prepared by reacting maleic anhydride with ammonia) were polycondensed for 2 h at 240 ° C. in a round bottom flask. The reaction mass expanded like a foam and could be easily comminuted after cooling. The comminuted polyaspartimide was hydrolyzed as described in Example 1 to give an aqueous polyaspartic acid sodium salt solution. The weight average molecular weight (Mw) was 3000 g / mol.

Polymer V2 (polyaspartic acid T):

133.10 g of L-aspartic acid were polycondensed for 2 hours at a temperature of 220-240 ° C. in a rotary evaporator. The resulting polyaspartimide was hydrolyzed as described in Example 1 to give an aqueous polyaspartic acid sodium salt solution. The weight average molecular weight (Mw) was 5400 g / mol.

Example 2 Determination of the molecular weight (Mw)

The weight average molecular weight (Mw) of the examples was determined with the aid of GPC (gel permeation chromatography) under the following conditions: pillar Suprema 100 10µ (Polymer Standard Service) Eluent 0.08 mol / l TRIS buffer pH = 7.0 in distilled water + 0.15 mol / l NaCl + 0.01 mol / l NaN ₃ Column temperature 35 ° C Flow rate 0.8 mL / min injection 100 µL concentration 1.5 mg / mL detector DRI Agilent 1100UV GAT-LCD 503 (260nm)

Sample solutions were filtered through Sartorius Minisart RC 25 (0.2 µm). The calibration was carried out with closely distributed Na-PAA standards from Polymer Standard Service with molecular weights from M = 1,250 to M = 193,800. In addition, Na acrylate with a molecular weight of M = 96 and a PEG standard with M = 620, that with Na-PAA M = 150, were equated. The values outside this elution range were extrapolated. The evaluation limit was approx. M = 298 g / mol.

Example 3 Dishwasher tests

The polymers were tested in the following phosphate-free test formulation PF1. The composition of the test formulation PF1 is shown in Table 1 (data in% by weight). <b> Table 1: </b> Test formulation PF1 component PF 1 Protease 2.5 Amylase 1.0 Nonionic surfactant 5 polymer 10 Sodium percarbonate 10.2 Tetraacetyl ethylenediamine 4th Sodium disilicate 2 sodium 19.5 Sodium citrate dihydrate 35 Methylglycine diacetic acid, sodium salt 10 Hydroxyethane (1,1-diphosphonic acid) 0.8 Figures in% by weight based on the total amount of all components

The following test conditions were observed: Dishwasher: Miele G 1222 SCL Program: 65 ° C (with pre-rinse) Wash ware: 3 knives (nickel chrome knife Karina, Solex Germany GmbH, Eisingen / Germany) 3 glass Amsterdam 0.2L 3 BREAKFAST PLATE "OCEAN BLUE" (MELAMINE) 3 porcelain plates: FLAG PLATE 19 CM Arrangement: Knives in the cutlery drawer, glasses in the upper basket, plates in the lower basket Dishwashing liquid: 18 g Dirt addition: 50 g ballast dirt is thawed with the formulation after pre-rinsing, dosed, see below for composition Final rinse temperature: 65 ° C Water hardness: 21 ° dH (Ca / Mg): HCO3 (3: 1): 1.35 Rinsing cycles: 15; 1 hour break in between (10 min closed door, 50 min open door) Evaluation: Visually after 15 rinsing cycles

The items to be washed were assessed after 15 cycles in a darkened chamber under light behind a perforated screen using a rating scale from 10 (very good) to 1 (very poor). Grades from 1 to 10 were awarded for spotting (very many, intense spots = 1, no spots = 10), and for surface (1 = very thick surface, 10 = no surface)

Composition of the ballast dirt:

Strength: 0.5% potato starch, 2.5% gravy Fat: 10.2% margarine Protein: 5.1% egg yolk, 5.1% milk Other: 2.5% tomato ketchup, 2.5% mustard, 0.1% benzoic acid, 71.5% water

Result:

The formulations with modified polyaspartic acid according to the invention were distinguished, in particular, by their very high scale-inhibiting action against inorganic and organic deposits on glass and knives. They also increased cleaning power the dishwashing detergent and facilitated the drainage of the water from the dishes, so that particularly clear glasses and shiny metal cutlery were obtained.
Table 2 below lists the marks for deposit formation (B) and spotting (S) on knives and drinking glasses. <b> Table 2: </b> Test results test formulation 1 (PF 1 polymer Knife (B + S) Glasses (B + S) without polymer 7.0 7.0 Polymer 1 15.3 11.7 Polymer 1b 15.7 12.0 Polymer 2 14.6 11.7 Polymer 3 12.7 10.0 Polymer 4 14.0 10.3 Polymer 5 13.7 10.3 Polymer 5b 14.3 11.1 Polymer V1 8.3 7.7 Polymer V2 11.4 9.0

Claims (10)

1. The use of modified polyaspartic acid as additive in detergents, wherein the modified polyaspartic acid can be prepared by polycondensation of

   (i) 50 to 99 mol% aspartic acid and methanesulfonic acid in a ratio from 200:1 to 5:1; and

   (ii) 1 to 50 mol% of at least one carboxyl-containing compound,

   and subsequent hydrolysis of the co-condensate with addition of a base, wherein (ii) is not aspartic acid.
2. The use according to claim 1, wherein (i) is 50 to 95 mol% aspartic acid and (ii) is 5 to 50 mol% of at least one carboxyl-containing compound.
3. The use according to claim 1 or 2, wherein (i) is 80 to 95 mol% aspartic acid and (ii) is 5 to 20 mol% of at least one carboxyl-containing compound.
4. The use according to claims 1 to 3, wherein (ii) is a monocarboxylic acid, a polycarboxylic acid, a hydroxycarboxylic acid and/or an amino acid.
5. The use according to any of claims 1 to 4, wherein (ii) is selected from the group consisting of 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine and glutamic acid.
6. The use according to any of claims 1 to 5, wherein the base is selected from the group consisting of alkali metal and alkaline earth metal bases; carbonates; ammonia; primary, secondary or tertiary amines; and bases having primary, secondary or tertiary amino groups.
7. The use according to any of claims 1 to 6 in detergents for machine dishwashers.
8. A detergent composition comprising

   (a) 1-20% by weight of at least one modified polyaspartic acid;

   (b) 0-50% by weight chelating agents;

   (c) 0.1-80% by weight builders and/or cobuilders;

   (d) 0.1-20% by weight non-ionic surfactants;

   (e) 0-30% by weight bleaches and bleach activators;

   (f) 0-8% by weight enzymes; and

   (g) 0-50% by weight additives,
   wherein the modified polyaspartic acid can be prepared by polycondensation of

   (i) 50 to 99 mol% aspartic acid and methanesulfonic acid in a ratio from 200:1 to 5:1; and

   (ii) 1 to 50 mol% of at least one carboxyl-containing compound,

   and subsequent hydrolysis of the co-condensate with addition of a base, wherein (ii) is not aspartic acid.
9. The detergent composition according to claim 8, wherein the composition is suitable for machine dishwashers.
10. The detergent composition according to claim 8 or 9, comprising

    (a) 2-12% by weight of at least one modified polyaspartic acid;

    (b) 3-50% by weight methylglycinediacetic acid and salts thereof;

    (c) 15-65% by weight builders and/or cobuilders

    (d) 0.5-10% by weight non-ionic surfactants

    (e) 0-30% by weight bleaches and bleach activators

    (f) 0-8% by weight enzymes; and

    (g) 0-50% by weight additives,
    wherein the modified polyaspartic acid can be prepared by polycondensation of

    (i) 50 to 99 mol% aspartic acid and methanesulfonic acid in a ratio from 200:1 to 5:1; and

    (ii) 1 to 50 mol% of at least one carboxyl-containing compound,

    and subsequent hydrolysis of the co-condensate with addition of a base, wherein (ii) is not aspartic acid.