Dishwashing detergent formulations comprising polyaspartic acid and oligosaccharide- and polysaccharide-based graft polymers as film-inhibiting additives

Abstract

The invention relates to a dishwashing detergent formulation comprising: (a) 1-15% by weight, based on the total composition, of the following components: (a1) at least one polyaspartic acid or modified polyaspartic acid or a salt thereof, wherein the modified polyaspartic acid is obtainable by polycondensation of (i) 50-99 mol % of aspartic acid and (ii) 1-50 mol % of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the cocondensate with addition of a base, (a2) at least one graft copolymer consisting of: (a21) at least one graft base selected from oligosaccharides and polysaccharides, and (a3) ​​at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a4) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a5) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a6) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a7) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a8) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a9) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a10) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a110) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a1211) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a1212) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a10) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a10) at least one graft copolymer selected from oligosaccharides and polysaccharides, and (a10) at least one graft copolymer selected from oligos Side chains obtained by grafting the following substances: (a22) at least one ethylenically unsaturated mono- or dicarboxylic acid, and (a23) at least one ethylenically unsaturated N-containing monomer having a permanent cationic charge, wherein the weight ratio of (a1): (a2) is 20:1 to 1:12; (b) 0-60% by weight of complexing agent; (c) 0.1-80% by weight of builder and / or co-builder; (d) 0.1-20% by weight of nonionic surfactant; (e) 0-30% by weight of bleach and bleach activator; (f) 0-10% by weight of enzyme and enzyme stabilizer; and (g) 0-50% by weight of additives.

Description

[0001] describe

[0002] The present invention relates to dishwashing detergent formulations which comprise polyaspartic acid or modified polyaspartic acid and graft polymers based on oligosaccharides and polysaccharides as film-inhibiting additives, and to the combined use of polyaspartic acid or modified polyaspartic acid and the graft polymers as film-inhibiting additives in dishwashing detergent formulations, in particular in phosphate-free and phosphonate-free automatic dishwashing detergent formulations.

[0003] For many years, polymers of carboxyl-containing monomers obtainable by free-radical polymerization have been important ingredients in phosphate-containing and phosphate-free automatic dishwashing detergents (ADW). Due to their soil-dispersing and film-inhibiting effects, they make an important contribution to the washing and cleaning performance of machine dishwashing detergents. For example, they ensure that no salt deposits of calcium and magnesium ions, which cause hardness, remain on the dishes. Homopolymers and copolymers of acrylic acid are usually used for this purpose.

[0004] A disadvantage of these polymers of carboxyl-containing monomers obtainable by free-radical polymerization is that they are not biodegradable under aerobic conditions such as prevail in public sewage works.

[0005] Due to the growing environmental awareness, there is an increasing demand for biodegradable polymer alternatives to polycarboxylates based on acrylic acid. However, commercially available biodegradable polymers, such as polyaspartic acid or carboxymethylated inulin, have only been accepted with difficulty in terms of commercial significance. The reasons are manifold: insufficient effect in specific applications, excessive costs due to complex preparation methods and / or expensive raw materials.

[0006] WO 2011 / 001170 describes cleaning compositions for machine dishwashing which comprise polyaspartic acid, a liquid nonionic surfactant and at least one solid nonionic surfactant.

[0007] WO 2015 / 036325 describes the use of modified polyaspartic acids in dishwashing detergents, in particular as dispersants, filming inhibitors and stain inhibitors. The application also relates to dishwashing detergent compositions containing modified polyaspartic acids.

[0008] WO 2015 / 197378 claims a dishwashing detergent with low film formation on glass, comprising:

[0009] (A) at least one compound selected from methylglycine diacetate (MGDA) and glutamic acid diacetate (GLDA) and salts thereof,

[0010] (B) at least one graft copolymer consisting of:

[0011] (a) at least one grafting base selected from the group consisting of monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable thereon by grafting:

[0012] (b) at least one ethylenically unsaturated mono- or dicarboxylic acid, and

[0013] (c) at least one ethylenically unsaturated N-containing monomer having a permanent cationic charge, and (C) at least one inorganic peroxide selected from the group consisting of sodium peroxodisulfate, sodium perborate and sodium percarbonate.

[0014] WO 2015 / 197379 claims a dishwashing detergent with low film formation on glass, comprising:

[0015] (A) at least one compound selected from methylglycine diacetate (MGDA) and glutamic acid diacetate (GLDA) and salts thereof,

[0016] (B) at least one graft copolymer consisting of:

[0017] (a) at least one grafting base selected from nonionic monosaccharides, disaccharides, oligosaccharides and polysaccharides

[0018] and side chains obtainable thereon by grafting the following substances:

[0019] (b) at least one ethylenically unsaturated mono- or dicarboxylic acid, and

[0020] (c) at least one compound of the general formula (I):

[0021]

[0022] The symbols are defined as follows:

[0023] R 1 is selected from methyl and hydrogen,

[0024] A 1 Selected from C2-C4 alkylene,

[0025] R 2 are the same or different and are selected from C1-C4 alkyl,

[0026] X - Selected from halides, mono-C1-C4 alkyl sulfates and sulfates.

[0027] It was an object of the present invention to provide improved dishwashing detergent additives for inhibiting filming (soiling) and staining, in particular for use as additives in phosphate-free dishwashing detergent formulations for machine dishwashing, which are biodegradable.

[0028] The object is achieved by the combined use of the following components as film-inhibiting additives in dishwashing detergent formulations, preferably automatic dishwashing detergent formulations:

[0029] (a1) at least one polyaspartic acid or modified polyaspartic acid or a salt thereof, wherein the modified polyaspartic acid is obtainable by polycondensing (i) 50 to 99 mol % of aspartic acid and (ii) 1 to 50 mol % of at least one carboxyl group-containing compound different from aspartic acid, and subsequently hydrolyzing the cocondensate with the addition of a base,

[0030] and

[0031] (a2) at least one graft copolymer consisting of:

[0032] (a21) at least one grafting base selected from oligosaccharides and polysaccharides, and side chains obtainable thereon by grafting:

[0033] (a22) at least one ethylenically unsaturated mono- or dicarboxylic acid, and

[0034] (a23) at least one ethylenically unsaturated N-containing monomer having a permanent cationic charge, wherein the weight ratio of (a1):(a2) is from 20:1 to 1:12.

[0035] In addition, the object is achieved by a combination of the following components:

[0036] (a1) at least one polyaspartic acid or modified polyaspartic acid or a salt thereof, wherein the modified polyaspartic acid is obtainable by polycondensing (i) 50 to 99 mol % of aspartic acid and (ii) 1 to 50 mol % of at least one carboxyl group-containing compound different from aspartic acid, and subsequently hydrolyzing the cocondensate with the addition of a base,

[0037] and

[0038] (a2) at least one graft copolymer consisting of:

[0039] (a21) at least one grafting base selected from oligosaccharides and polysaccharides, and side chains obtainable thereon by grafting:

[0040] (a22) at least one ethylenically unsaturated mono- or dicarboxylic acid, and

[0041] (a23) at least one ethylenically unsaturated N-containing monomer having a permanent cationic charge, wherein the weight ratio of (a1):(a2) is from 20:1 to 1:12.

[0042] Surprisingly, it has been found that the cleaning effect is particularly significantly improved by the combined use of biodegradable polyaspartic acid or modified polyaspartic acid or its salt (a1) and a biodegradable graft polymer (a2) obtained by grafting at least one ethylenically unsaturated mono- or dicarboxylic acid and at least one cationic N-containing monomer onto oligosaccharides and polysaccharides. This combination is particularly effective in preventing film (fouling) formation on glass.

[0043] The weight ratio between aspartic acid or modified aspartic acid (a1) and graft polymer (a2) is preferably 12:1 to 1:6, more preferably 12:1 to 1:3, particularly preferably 12:1 to 1:1, especially 12:1 to 3:1, and particularly 10:1 to 3:1.

[0044] Polyaspartic acid or modified polyaspartic acid (a1) and graft copolymer (a2) can be directly introduced into formulations in various forms thereof (e.g. as aqueous solution, powder or granules) by methods known to those skilled in the art. In this regard, solid formulations such as powders, tablets, gel-like formulations and liquid formulations can be mentioned in particular.

[0045] In general, it is difficult to prepare aqueous solutions of polymers with different chemical properties without phase separation or precipitation, due to the incompatibility of these polymers with each other. Surprisingly, it was found that aqueous mixtures of polyaspartic acid or modified polyaspartic acid (a1) and graft copolymer (a2) do not cause incompatibility problems and form stable solutions. Stable aqueous mixtures of (a1) and (a2) with various concentrations (e.g. 20, 25, 30, 35 or 40% by weight, based on solid matter) can be prepared by methods known to those skilled in the art, and the (a1): (a2) weight ratio is, for example, 12: 1, 6: 1, 3: 1, 1: 1 or 1: 3. From these aqueous solutions, solid mixtures can be obtained by known methods, such as spray drying, spray granulation, fluidized bed spray granulation, roller drying or freeze drying. Solid mixtures of (a1) and (a2) can also be prepared by mixing (a1) and (a2), both already in powder or granular form; by solid / solid mixing methods, for example using a paddle mixer, tumble mixer or rotary drum mixer.

[0046] In a preferred embodiment of the present invention, the mixture of polyaspartic acid or modified polyaspartic acid (a1) and graft copolymer (a2) is introduced into the formulation in its various forms by methods known to those skilled in the art, for example as an aqueous solution, powder or granules. In this regard, solid formulations such as powders, tablets, gel-like formulations and liquid formulations can be mentioned in particular.

[0047] The object is further achieved by a dishwashing detergent formulation comprising:

[0048] (a) 1 to 15% by weight, preferably 2 to 12% by weight, particularly preferably 3 to 10% by weight, of the following components, based on the total composition:

[0049] (a1) polyaspartic acid or modified polyaspartic acid or a salt thereof, wherein the modified polyaspartic acid is obtainable by polycondensing (i) 50 to 99 mol % of aspartic acid and (ii) 1 to 50 mol % of at least one carboxyl group-containing compound different from aspartic acid, and subsequently hydrolyzing the cocondensate with the addition of a base, and

[0050] (a2) at least one graft copolymer consisting of:

[0051] (a21) at least one grafting base selected from the group consisting of monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable thereon by grafting:

[0052] (a22) at least one ethylenically unsaturated mono- or dicarboxylic acid, and

[0053] (a23) at least one ethylenically unsaturated N-containing monomer having a permanent cationic charge, wherein the weight ratio of (a1):(a2) is from 20:1 to 1:12;

[0054] (b) 0-60 wt % of a complexing agent;

[0055] (c) 0.1-80 wt. % of builders and / or co-builders;

[0056] (d) 0.1-20 wt % of a nonionic surfactant;

[0057] (e) 0-30% by weight of bleaching agents and bleach activators;

[0058] (f) 0-10 wt % of enzymes and enzyme stabilizers; and

[0059] (g) 0-50 wt% of additives.

[0060] The sum of components (a1)-(a2) is 1-15% by weight based on the total composition. The sum of components (a1), (a2) and (b), (c), (d), (e), (f) and (g) is 100% by weight of the total composition. When formulating the dishwashing detergent formulation of the present invention, components (a1) and (a2) can be added separately, or can be added as a pre-formulated filming inhibition composition.

[0061] Polyaspartic acid is a well-known biodegradable dispersing and scale inhibiting polymer. Three main processes have been developed for the industrial production of polyaspartic acid and its sodium salt:

[0062] (1) Aspartic acid is subjected to thermal polycondensation, and then the polysuccinimide intermediate is subjected to alkaline hydrolysis;

[0063] (2) aspartic acid is subjected to thermal polycondensation in the presence of an acid catalyst such as phosphoric acid, sulfuric acid or methanesulfonic acid, and then the polysuccinimide intermediate is subjected to alkaline hydrolysis;

[0064] (3) Maleic anhydride is polymerized in the presence of ammonia or an ammonium salt, and then the polysuccinimide intermediate is subjected to alkaline hydrolysis.

[0065] Regardless of the synthetic route, the polysuccinimide intermediate must be hydrolyzed with, for example, sodium hydroxide to obtain an aqueous solution of polyaspartate. The polyaspartate is acidified with a mineral acid, such as hydrochloric acid or sulfuric acid, to thereby obtain polyaspartic acid.

[0066] The modified polyaspartic acid which can be used according to the invention can be prepared by polycondensation:

[0067] (i) 50 to 99 mol %, preferably 60 to 95 mol %, particularly preferably 80 to 95 mol % of aspartic acid; and

[0068] (ii) 1 to 50 mol %, preferably 5 to 40 mol %, particularly preferably 5 to 20 mol % of at least one carboxyl group-containing compound;

[0069] and subsequently hydrolyzing the cocondensate with addition of a base, such as sodium hydroxide solution; wherein (ii) is not aspartic acid.

[0070] For the preparation of the polyaspartic acid used according to the invention, the carboxyl-containing compound (ii) used may be, in particular, a carboxylic acid (monocarboxylic acid or polycarboxylic acid), a hydroxycarboxylic acid and / or an amino acid (other than aspartic acid). The carboxylic acid or hydroxycarboxylic acid is preferably polybasic. Thus, in this context, polybasic carboxylic acids may be used for the preparation of the polyaspartic acid used according to the invention, 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, C1-C 26 Alkyl succinic acid (e.g. octyl succinic acid), C2-C 26Alkenylsuccinic acid (for example octenylsuccinic acid), 1,2,3-propanetricarboxylic acid, 1,1,3,3-propanetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,3-propanetetracarboxylic acid or 1,3,3,5-pentanetetracarboxylic acid. In addition, polyhydroxycarboxylic acids such as citric acid, isocitric acid, mucic acid, tartaric acid, tartronic acid or malic acid can also be used in this context. In this context, amino acids that can be used are, in particular, aminocarboxylic acids (for example glutamic acid, cysteine), basic diaminocarboxylic acids (for example lysine, arginine, histidine, aminocaprolactam), neutral amino acids (for example glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactam, asparagine, isoasparagine, glutamine, isoglutamine), aminosulfonic acids (for example taurine), hydroxyamino acids (for example hydroxyproline, serine, threonine), iminocarboxylic acids (for example proline, iminodiacetic acid) or aromatic and heterocyclic amino acids (for example anthranilic acid, tryptophan, tyrosine, histidine), but not aspartic acid. For the preparation of the modified polyaspartic acid used in the present invention, the carboxyl group-containing compound (ii) is preferably 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.

[0071] The molecular weight (Mw) of (modified) polyaspartic acid can be easily adjusted by changing the reaction conditions. Molecular weights of 1000 g / mol to 100,000 g / mol can be achieved by simply adjusting the process parameters (temperature, catalyst, reaction time).

[0072] The molecular weight of the (modified) polyaspartic acid used according to the present invention is preferably in the range of 1000 g / mol to 20,000 g / mol, preferably 1500 g / mol to 15,000 g / mol, particularly preferably 2000 g / mol to 10,000 g / mol.

[0073] For the preparation of the polyaspartic acid used in the present invention, the aspartic acid (i) used may be L- or D- and DL-aspartic acid. Preference is given to using L-aspartic acid.

[0074] Since the preparation of the (modified) polyaspartic acid described herein is followed by a hydrolysis step with the addition of a base, it is readily apparent to the skilled person that the (modified) polyaspartic acid is first obtained in the form of a salt. The acid form of the (modified) polyaspartic acid can be obtained directly by a further step of acidifying the salt, which acidification can be carried out in a manner known to the skilled person. Suitable acids for this purpose are in particular inorganic acids, such as sulfuric acid or hydrochloric acid. If only a salt of the (modified) polyaspartic acid is desired, for example as an intermediate, the subsequent acidification step can be omitted. Therefore, for the purposes of the present invention, when discussing the (modified) polyaspartic acid, the corresponding salts thereof are also encompassed, which can be obtained by or by the subsequent acidification step described and are known to the skilled person. The optional acidification of the (modified) polyaspartic acid salt can be carried out, for example, by adding a determined amount of a concentrated or dilute inorganic acid, such as sulfuric acid or hydrochloric acid, to an aqueous solution of the sodium salt of the (modified) polyaspartic acid. The acidification can also be carried out by treatment with an acidic ion exchanger, for example Amberlite IR120 (hydrogen form), wherein an aqueous solution of the Na salt of the (modified) polyaspartic acid is passed through a column filled with this ion exchanger.

[0075] In the preparation of the modified polyaspartic acid used in the present invention, the bases that can be used for hydrolyzing the polysuccinimide or cocondensate are: alkali metal and alkaline earth metal bases, such as sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide or barium hydroxide; carbonates, such as sodium carbonate and potassium carbonate; ammonia and primary, secondary or tertiary amines; other bases with primary, secondary or tertiary amino groups. For the purpose of the present invention, sodium hydroxide solution or ammonium hydroxide is preferred.

[0076] The preparation of the (modified) polyaspartic acid used in the present invention is generally carried out as shown and described above and below via aspartic acid, optionally with at least one carboxyl-containing compound (non-aspartic acid) poly (co) condensation and then hydrolyzing the co-condensate under the addition of alkali. The preparation of such (modified) polyaspartic acid is also described in, for example, DE4221875.6. The preparation of the (modified) polyaspartic acid used in the present invention is, for example, as described below. The description of this preparation should not be understood as limiting the (modified) polyaspartic acid used in the present invention. The (modified) polyaspartic acid used in the present invention includes not only those prepared by the following preparation description, but also those that can be prepared by subsequent methods. The (modified) polyaspartic acid used in the present invention can be prepared, for example, by (co) condensing the components (i) and optionally (ii), i.e., aspartic acid and optionally at least one carboxyl-containing compound, according to the molar ratios described herein. Poly (co) condensation can be carried out at a temperature of 100-270 ℃, preferably 120-250 ℃, particularly preferably 180-220 ℃. Condensation (heating) is preferably carried out under vacuum or in an inert gas atmosphere (e.g. N2 or argon). However, condensation can also be carried out under elevated pressure or in a gas stream such as carbon dioxide, air, oxygen or water vapor. The reaction time of condensation is generally 1 minute to 50 hours, preferably 5-8 hours, depending on the selected reaction conditions. Poly (co) condensation can be carried out, for example, in the solid phase by first preparing an aqueous solution or suspension of aspartic acid and optionally at least one carboxyl-containing compound (ii), and evaporating the solution to dryness. During this period, condensation may have begun. Examples of reaction devices suitable for condensation are heating belts, kneaders, mixers, paddle dryers, extruders, rotary kilns, and other heatable devices in which solid condensation can be implemented and reaction water can be removed. Poly (co) condensates with low molecular weight can also be prepared in pressure-resistant closed containers, wherein the reaction water formed is not removed or only partially removed. Poly (co) condensation can also be carried out by infrared radiation or microwave radiation. Acid-catalyzed poly (co) condensation is also possible, for example using mineral acids of phosphorus or sulfur or using hydrogen halides. This acid-catalyzed polycondensation is also described in DE4221875.6.

[0077] By adding a small amount of methane sulfonic acid during the poly(co)condensation of aspartic acid and optionally at least one carboxyl-containing compound, the molecular weight of the polyaspartic acid obtained by the subsequent hydrolysis of the polysuccinimide intermediate or cocondensate can be controlled. Therefore, for the present invention, it is also possible to prepare the (modified) polyaspartic acid used in the present invention by using methane sulfonic acid as an additive in the poly(co)condensation except aspartic acid (i) and the optional carboxyl-containing compound (ii) and the resulting condensate is subsequently hydrolyzed with an alkali as described herein. Like polyaspartic acid, methane sulfonic acid is biodegradable. A small amount of methane sulfonic acid may remain in the polymer product without causing ecological disadvantages and without affecting the performance in many applications. Complicated post-treatment or purification operations are unnecessary. The yield loss caused by post-treatment is avoided.

[0078] During the thermal poly(co)condensation of aspartic acid (with or without methanesulfonic acid), poly(co)condensates are usually obtained in the form of water-insoluble polysuccinimide or polysuccinimide-cocondensate, in a few cases in water-soluble form (for example in the case of polycondensation of L-aspartic acid and citric acid). The condensate of aspartic acid can be purified from the unreacted starting materials, for example, by comminuting the condensation product and extracting it with water at a temperature of 10 to 100° C. During this period, the unreacted starting materials are dissolved out and the methanesulfonic acid used, if any, is washed out. The unreacted aspartic acid can be easily dissolved by extraction with 1N hydrochloric acid.

[0079] The (modified) polyaspartic acid is preferably obtained from the poly(co)condensates by slurrying the poly(co)condensates in water or dissolving them (if the poly(co)condensates are already water-soluble, for example from co-condensates of L-aspartic acid and citric acid), and hydrolyzing and neutralizing them at a temperature of 0-90° C. with the addition of a base. The hydrolysis and neutralization operations are preferably carried out at a pH of 8-10. Suitable bases are, for example, alkali metal and alkaline earth metal bases, such as sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide or barium hydroxide. Suitable bases are also, for example, carbonates, such as sodium carbonate and potassium carbonate. Suitable bases are also ammonia and primary, secondary or tertiary amines, as well as other bases with primary, secondary or tertiary amino groups. If amines are used for the reaction of polysuccinimide or the corresponding polysuccinimide co-condensates, the amines can be bonded to the polyaspartic acid like salts or amides due to their high reactivity.

[0080] In the case of treatment with a base, the neutralized (modified) polyaspartic acid is obtained in the form of a salt corresponding to the base.

[0081] The (modified) polyaspartic acid and / or its salt used in the present invention can be used in aqueous solution or solid form, for example in powder or granule form. As known to those skilled in the art, the powder or granule form can be obtained, for example, by spray drying, spray granulation, fluidized bed spray granulation, roller drying or freeze drying of an aqueous solution of polyaspartic acid or its salt.

[0082] The composition of the present invention further comprises:

[0083] (a2) at least one graft copolymer, which is also referred to as graft copolymer (a2) in the present invention and consists of:

[0084] (a21) at least one graft base selected from oligosaccharides and polysaccharides, which is referred to as graft base (a21) for short, and

[0085] The side chains can be obtained by grafting the following substances onto it:

[0086] (a22) at least one ethylenically unsaturated monocarboxylic acid or dicarboxylic acid, referred to as monocarboxylic acid (a22) or dicarboxylic acid (a22), and

[0087] (a23) at least one ethylenically unsaturated N-containing monomer having a permanent cationic charge, referred to as monomer (a23) for short.

[0088] In the present invention, oligosaccharides may be mentioned as carbohydrates having 3-10 monosaccharide units per molecule, such as polysaccharides. In the present invention, the term "polysaccharide" means carbohydrates having more than 10 monosaccharide units per molecule. Oligosaccharides and polysaccharides may, for example, be linear, cyclic or branched.

[0089] The polysaccharides mentioned are, for example, biopolymers, such as starch and glycogen, as well as cellulose, dextran and exocarpin. In addition, inulin should be mentioned as a polycondensate of D-fructose (fructan), keratin and alginic acid. Other examples of polysaccharides are starch degradation products, such as can be obtained by enzymatic or so-called chemical degradation of starch. Examples of so-called chemical degradation of starch are oxidative degradation and acid-catalyzed hydrolysis.

[0090] Preferred examples of starch degradation products are maltodextrin and glucose syrup. In the present invention, maltodextrin is a term for a mixture of monomers, dimers, oligomers and polymers of glucose. The percentage composition varies depending on the degree of hydrolysis. This is described by glucose equivalents, which in the case of maltodextrin are 3-40.

[0091] Preferably, the graft base (a21) is selected from polysaccharides, in particular starch, which is preferably not chemically modified. In one embodiment of the invention, the starch is selected from those polysaccharides having 20-30% by weight of amylose and 70-80% of amylopectin. Examples are corn starch, rice starch, potato starch and wheat starch.

[0092] The side chains are grafted onto the graft base (a21). For each molecule of the graft copolymer (a2), preferably an average of 1 to 10 side chains can be grafted onto it. Preferably, in this regard, the side chains are connected with the anomeric carbon atoms of the monosaccharide or with the anomeric carbon atoms of the oligosaccharide or polysaccharide chain ends. The number of side chains is limited upward by the number of carbon atoms and the hydroxyl groups of the graft base (a21).

[0093] Examples of monocarboxylic acids (a22) are ethylenically unsaturated C3-C 10 Monocarboxylic acids and their alkali metal or ammonium salts, in particular potassium and sodium salts. Preferred monocarboxylic acids (a22) are acrylic acid and methacrylic acid, and sodium (meth)acrylate. 10 Mixtures of monocarboxylic acids, in particular mixtures of acrylic acid and methacrylic acid, are also preferred as component (a22).

[0094] Examples of dicarboxylic acids (a22) are ethylenically unsaturated C4-C 10 Dicarboxylic acids and their mono- and especially di-alkali metal or ammonium salts, especially dipotassium and disodium salts, and olefinically unsaturated C4-C 10 Anhydrides of dicarboxylic acids. Preferred dicarboxylic acids (a22) are maleic acid, fumaric acid, itaconic acid and maleic anhydride and itaconic anhydride.

[0095] In one embodiment, in at least one side chain, in addition to the monomer (a23), the graft copolymer (a2) also contains at least one monocarboxylic acid (a22) and at least one dicarboxylic acid (a22). In a preferred embodiment of the present invention, in addition to the monomer (a23), the graft copolymer (a2) also contains in its side chain only monocarboxylic acid (a22) in polymerized form, but no dicarboxylic acid (a22).

[0096] Examples of monomers (a23) are ethylenically unsaturated N-containing compounds having a permanent cationic charge, i.e. those ethylenically unsaturated N-containing compounds which can form salts with anions, such as sulfates, C1-C4-alkylsulfates and halides, in particular with chlorides, independently of the pH. Any desired mixtures of two or more monomers (a23) are also suitable.

[0097] Examples of suitable monomers (a23) are corresponding quaternary derivatives of vinyl- and allyl-substituted nitrogen heterocycles, such as 2-vinylpyridine and 4-vinylpyridine, 2-allylpyridine and 4-allylpyridine, and N-vinylimidazoles, such as 1-vinyl-3-methylimidazolium chloride. Also suitable are corresponding quaternary derivatives of N,N-diallylamine and N,N-diallyl-N-alkylamines, such as N,N-diallyl-N,N-dimethylammonium chloride (DADMAC).

[0098] In one embodiment of the invention, monomers (a23) are selected from the group consisting of the corresponding quaternized ethylenically unsaturated amides formed from mono- and dicarboxylic acids and diamines having at least one primary or secondary amino group. Preference is given here to diamines having one tertiary amino group and one primary or secondary amino group.

[0099] In another embodiment of the present invention, monomer (a23) is selected from mono- and dicarboxylic acids and C2-C 12 The amino alcohols form the corresponding quaternized ethylenically unsaturated esters which are mono- or dialkylated on the amine nitrogen atom.

[0100] Suitable examples of the acid component in the above esters and amides are acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate, and mixtures thereof. As the acid component, acrylic acid, methacrylic acid, and mixtures thereof are preferably used.

[0101] Preferred monomers (a23) have the general formula (I):

[0102]

[0103] The symbols are defined as follows:

[0104] Z is O or NR 1 ,

[0105] R 1 is selected from methyl and hydrogen,

[0106] A 1 Selected from C2-C4 alkylene,

[0107] R 2 are the same or different and are selected from C1-C4 alkyl,

[0108] X - Selected from halides, mono-C1-C4-alkyl sulfates and sulfates.

[0109] Particularly preferred monomers (a23) are trialkylaminoethyl (meth)acryloyl chloride or alkyl sulfate, and trialkylaminopropyl (meth)acryloyl chloride or alkyl sulfate, and (meth)acrylamidoethyltrialkylammonium chloride or alkyl sulfate, and (meth)acrylamidopropyltrialkylammonium chloride or alkyl sulfate, wherein the corresponding alkyl group is preferably methyl or ethyl or a mixture thereof.

[0110] Very particular preference is given to (meth)acrylamidopropyltrimethylammonium halides, in particular acrylamidopropyltrimethylammonium chloride (“APTAC”) or methacrylamidopropyltrimethylammonium chloride (“MAPTAC”).

[0111]

[0112] In another preferred embodiment of the present invention, monomer (a23) is selected from C2-C3-alkyl (meth)acrylate trimethylammonium halides, especially 2-(trimethylamino)ethyl (meth)acrylate chloride and 3-(trimethylamino)propyl (meth)acrylate chloride.

[0113]

[0114] The graft copolymer (a2) may comprise in polymerized form in one or more of its side chains at least one further comonomer (a24), for example hydroxyalkyl esters, for example 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate, or esters of alkoxylated fatty alcohols, or comonomers containing sulfonic acid groups, for example 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its alkali metal salts.

[0115] Preferably, the graft copolymer (a2) comprises no further comonomers (a24) in addition to the monomers (a23) and the monocarboxylic acids (a22) or dicarboxylic acids (a22) in one or more of its side chains.

[0116] In one embodiment of the invention, the proportion of the graft base (a21) in the graft copolymer (a2) is in each case from 40 to 95% by weight, preferably from 50 to 90% by weight, based on the entire graft copolymer (a2).

[0117] In one embodiment of the invention, the proportion of monocarboxylic acids (a22) or dicarboxylic acids (a22) is in each case 2 to 40% by weight, preferably 5 to 30% by weight and in particular 5 to 25% by weight, based on the entire graft copolymer (a2).

[0118] The monomers of type (a23) are polymerized in amounts of 5 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 5 to 30% by weight, based in each case on the entire graft copolymer (a2).

[0119] Preferably, the graft copolymer (a2) comprises in polymerized form more monocarboxylic acid (a22) than compound (a23), and specifically based on a molar ratio of, for example, 1.1:1 to 5:1, preferably 2:1 to 4:1.

[0120] In one embodiment of the present invention, the average molecular weight (M w ) is in the range of 2000-200,000 g / mol, preferably 5000-150,000 g / mol, in particular 8000-100,000 g / mol. The average molecular weight Mw is preferably determined by gel permeation chromatography in aqueous KCl / formic acid solution.

[0121] The graft copolymer (a2) is preferably available as an aqueous solution, from which it can be isolated, for example, by spray drying, spray granulation or freeze drying.

[0122] If desired, solutions of graft copolymers (a2) or dried graft copolymers (a2) can be used for preparing the formulations according to the invention.

[0123] Monomer (a23) itself can be polymerized in the graft copolymer (a2) or in a non-quaternized equivalent, for example in the case of APTAC:

[0124]

[0125] And in the case of MAPTAC:

[0126]

[0127] The copolymerization may be followed by an alkylation reaction, for example using a C1-C8 alkyl halide or a di-C1-C4 alkyl sulfate, for example using ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate or diethyl sulfate.

[0128] Preferably, the graft copolymer (a2) is stabilized using at least one biocide. Examples of suitable biocides are isothiazolinones, such as 1,2-benzisothiazolin-3-one ("BIT"), octylisothiazolinone ("OIT"), dichlorooctylisothiazolinone ("DCOIT"), 2-methyl-2H-isothiazolin-3-one ("MIT") and 5-chloro-2-methyl-2H-isothiazolin-3-one ("CIT"), phenoxyethanol, hydroxyphenyl alkyl esters, such as methylparaben, ethylparaben, propylparaben, benzoic acid and its salts, such as sodium benzoate, benzyl alcohol, alkali metal sorbates, such as sodium sorbate, and (substituted) hydantoins, such as 1,3-bis(hydroxymethyl)-5,5-dimethylhydantoin (DMDM hydantoin). Other examples are 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butylcarbamate, iodine and iodophors.

[0129] The scale-inhibiting compositions comprising the polyaspartic acid or modified polyaspartic acid (a1) and the graft copolymer (a2) described herein and to be used according to the invention can be used particularly advantageously in machine dishwashing detergents. They are characterized in particular by a film-inhibiting effect on both inorganic and organic films. In particular, they inhibit the formation of films by calcium and magnesium carbonates and calcium and magnesium phosphates and phosphonates. In addition, they prevent deposits originating from the scale components of the washing liquid, such as grease, protein and starch films.

[0130] The scale inhibition compositions described herein can be used in multi-component product systems (detergent, rinse aid and regeneration salt are used separately), or in those dishwashing 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).

[0131] The present invention also relates to dishwashing detergent formulations, especially dishwashing detergent formulations suitable for machine dishwashing, wherein in addition to the polyaspartic acid or modified polyaspartic acid (a1) and graft copolymer (a2) described herein and to be used according to the present invention, complexing agents, builders and / or co-builders, nonionic surfactants, bleaching agents and / or bleach activators, enzymes and optional other additives, such as solvents. Polyaspartic acid or modified polyaspartic acid (a1) and graft copolymer (a2) can be directly introduced into the formulation in its various forms by methods known to those skilled in the art. In this regard, solid formulations such as powders, tablets, gel-like formulations and liquid formulations can be mentioned in particular.

[0132] The dishwashing detergent formulations according to the invention are particularly suitable for use as dishwashing detergent compositions for machine dishwashing. In one embodiment, therefore, the dishwashing detergent compositions according to the invention are machine dishwashing detergent compositions.

[0133] The dishwashing detergent formulations of the invention may be provided in liquid, gel-like or solid form, as one or more phases, as tablets, or in other dosage units, either packaged or unpackaged.

[0134] Examples of complexing agents (b) which can be used are: nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycine diacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediamine disuccinic acid, aspartic acid diacetic acid, and in each case, the salts thereof. 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 using 1 to 50% by weight of complexing agent (b).

[0135] MGDA and GLDA may be present as racemates or as enantiomerically pure compounds. GLDA is preferably selected from L-GLDA; or an enantiomerically enriched mixture of L-GLDA, wherein at least 80 mol %, preferably at least 90 mol % of L-GLDA is present.

[0136] In one embodiment of the invention, the complexing agent (b) is racemic MGDA. In another embodiment of the invention, the complexing agent (b) is selected from L-MGDA; or a mixture of L- and D-MGDA enantiomers, wherein L-MGDA predominates and wherein the L / D molar ratio is 55:45 to 95:5, preferably 60:40 to 85:15. The L / D molar ratio can be determined, for example, by optical rotation or by chromatographic methods, preferably by HPLC using a chiral column, for example with cyclodextrin as stationary phase or with an optically active ammonium salt fixed on the column. For example, fixed D-penicillamine salts can be used.

[0137] MGDA or GLDA are preferably used as salts. Preferred salts are ammonium salts and alkali metal salts, particularly preferably potassium salts, in particular sodium salts. These may, for example, have the general formula (I) or (II):

[0138] [CH3-CH(COO)-N(CH2-COO)2]Na 3-x-y K x H y (I)

[0139] x is in the range of 0.0-0.5, preferably at most 0.25,

[0140] y is in the range of 0.0-0.5, preferably at most 0.25,

[0141] [OOC-(CH2)2-CH(COO)-N(CH2-COO)2]Na4-x-y K x H y (II)

[0142] x is in the range of 0.0-0.5, preferably at most 0.25,

[0143] y is in the range of 0.0-0.5, preferably at most 0.25.

[0144] Very particular preference is given to the trisodium salt of MGDA and the tetrasodium salt of GLDA.

[0145] The complexing agent (b) may contain a small amount of cations other than alkali metal ions, such as Mg 2+ , Ca 2+ Or iron ions, such as Fe 2+ or Fe 3+ Such ions are present in compound (A) in many cases as a result of the preparation. In one embodiment of the invention, the cation other than the alkali metal ion is present in an amount of 0.01 to 5 mol %, based on the total amount of MGDA or GLDA.

[0146] In another embodiment of the present invention, no cations other than alkali metal ions are present in measurable amounts in the complexing agent (b).

[0147] In one embodiment of the invention, the complexing agent (b) contains a small amount of one or more impurities, which may be a result of the preparation. In the case of MGDA, for example, propionic acid, alanine or lactic acid may be included as impurities. In this regard, the small amount is, for example, a content of 0.01 to 1% by weight based on the complexing agent (b). In the present invention, unless otherwise explicitly stated, such impurities are ignored.

[0148] In one embodiment of the invention, the formulations according to the invention comprise a complexing agent (b), for example only the trisodium salt of MGDA or only the tetrasodium salt of GLDA. In this context, compounds of the formula (I) or (II) in which x or y is not equal to zero should also be referred to as a compound in each case.

[0149] In a further embodiment of the invention, the formulations according to the invention comprise a mixture of two complexing agents (b), for example MGDA trisodium salt and GLDA tetrasodium salt, for example in a molar ratio of 10:1 to 1:10.

[0150] Builders and / or cobuilders (c) which can be used are especially water-soluble or water-insoluble substances whose main task is to bind calcium and magnesium ions. These may be low molecular weight carboxylic acids and their salts, for example alkali metal citrates, especially trisodium citrate anhydrous or trisodium citrate dihydrate, alkali metal succinates, alkali metal malonates, fatty acid sulfonates, oxydisuccinates, alkyl or alkenyl disuccinates, gluconic acid, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates and α-hydroxypropionic acid.

[0151] Another class of substances that can be present in the cleaning agents of the present invention and have the properties of a co-builder is phosphonates. These are especially hydroxyalkanephosphonates or aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a co-builder. It is preferably used in the form of a sodium salt, wherein the disodium salt gives a neutral reaction and the tetrasodium salt gives an alkaline reaction (pH 9). Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of neutral reacting sodium salts, such as the hexasodium salt of EDTMP, or the heptasodium and octasodium salts of DTPMP. Here, the builder used selected from the phosphonate class is preferably HEDP. In addition, aminoalkanephosphonates have a significant heavy metal binding capacity. Therefore, especially when the composition also contains a bleaching agent, it is preferred to use aminoalkanephosphonates, especially DTPMP, or a mixture of the phosphonates.

[0152] Preferably, the dishwashing detergent formulations according to the invention are free of phosphonates.

[0153] Silicates can be used especially as builders. x O 2x+1 Crystalline layered silicates of yH2O, wherein M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, wherein x is particularly preferably 2, 3 or 4; and y is a number from 0 to 33, preferably from 0 to 20. In addition, amorphous sodium silicates having a SiO2:Na2O ratio of 1 to 3.5, preferably 1.6 to 3, in particular 2 to 2.8 can be used.

[0154] Builders and / or cobuilders (c) which can be used for the dishwashing detergent formulations according to the invention are furthermore carbonates and bicarbonates, preference being given to alkali metal salts, in particular sodium salts.

[0155] As co-builders, homopolymers and copolymers of acrylic acid or methacrylic acid can also be used, which preferably have a weight-average molar mass of 2000-50000 g / mol. Suitable comonomers are especially monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and anhydrides thereof such as maleic anhydride. Comonomers containing sulfonic acid groups are also suitable, such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid and vinylsulfonic acid. Hydrophobic comonomers are also suitable, such as isobutylene, diisobutylene, styrene, α-olefins with 10 or more carbon atoms. Hydrophilic monomers with hydroxyl functions or oxyalkylene groups can also be used as comonomers. For example, allyl alcohol and isoprene alcohol and their alkoxylates, and methoxy polyethylene glycol (meth) acrylates can be mentioned. In addition, graft polymers based on degraded starch and the above-mentioned monomers such as (meth) acrylic acid, maleic acid, fumaric acid and 2-acrylamido-2-methylpropanesulfonic acid can be used as co-builders.

[0156] For the dishwashing detergent compositions according to the invention, preferred amounts of builders and / or co-builders are 1 to 80% by weight, particularly preferably 2 to 75% by weight, 3 to 70% by weight or 3 to 65% by weight.

[0157] In the case of the dishwashing detergent compositions of the invention, useful nonionic surfactants (d) are, for example, weakly foaming or low-foaming nonionic surfactants. These may be present in a proportion 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, in particular, surfactants of the general formula (I):

[0158] R 1 -O-(CH2CH2O) a -(CHR 2 CH2O) b -R 3 (I),

[0159] Where R 1 is a straight-chain or branched alkyl group having 8 to 22 carbon atoms,

[0160] R 2 and R 3 are each independently hydrogen or a straight-chain or branched alkyl group having 1 to 10 carbon atoms or H, wherein R 2 Preferably it is methyl, and

[0161] a and b are each independently 0 to 300. Preferably, a=1-100 and b=0-30.

[0162] Also suitable in the present invention are surfactants of formula (II):

[0163] R 4- O-[CH2CH(CH3)O] c [CH2CH2O] d [CH2CH(CH3)O] e CH2CH(OH)R 5 (II),

[0164] Where R 4 is a straight-chain or branched aliphatic hydrocarbon group having 4 to 22 carbon atoms or a mixture thereof,

[0165] R 5 is a straight-chain or branched hydrocarbon group having 2 to 26 carbon atoms or a mixture thereof,

[0166] c and e are values ​​from 0-40, and

[0167] d is a value of at least 15.

[0168] Also suitable in the present invention are surfactants of formula (III):

[0169] R 6 O-(CH2CHR 7 O) f (CH2CH2O) g (CH2CHR 8 O) h -CO-R 9 (III), Where R 6 is a branched or unbranched alkyl radical having 8 to 16 carbon atoms,

[0170] R 7 , R 8 are each independently H or a branched or unbranched alkyl group having 1 to 5 carbon atoms,

[0171] R 9 is an unbranched alkyl group having 5 to 17 carbon atoms,

[0172] f and h are each independently a number from 1 to 5, and

[0173] g is a number from 13 to 35.

[0174] The surfactants of formula (I), (II) and (III) may be random copolymers or block copolymers, preferably in the form of block copolymers. In addition, di- or multi-block copolymers composed of ethylene oxide and propylene oxide may be used in the present invention, which may be referred to, for example, under the name (BASF SE) or (BASF Corporation). In addition, reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used. Also suitable are amine oxides or alkyl glycosides. An overview of suitable nonionic surfactants is disclosed by EP-A 851 023 and DE-A 19819187.

[0175] Mixtures of two or more different nonionic surfactants may also be present. The dishwashing detergent formulations of the present invention may additionally contain anionic or zwitterionic surfactants, preferably in a mixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also mentioned in EP-A 851 023 and DE-A 19819187.

[0176] For the dishwashing detergent formulations according to the invention, the bleaches and bleach activators (e) that can be used are representatives known to those skilled in the art. Bleaches are divided into oxygen bleaches and chlorine-containing bleaches. The oxygen bleaches used are alkali metal perborates and hydrates thereof, as well as alkali metal percarbonates. Here, preferred bleaches are sodium perborate, sodium percarbonate or hydrates of sodium percarbonate in the form of monohydrate or tetrahydrate. Oxygen bleaches that can also be used are persulfates and hydrogen peroxide. Typical oxygen bleaches are also organic peracids, such as perbenzoic acid, peroxy α-naphthoic acid, peroxy lauric acid, peroxy stearic acid, phthalimido peroxy hexanoic acid, 1,12-diperoxy dodecanedioic acid, 1,9-diperoxy azelaic acid, diperoxyisophthalic acid or 2-decyldiperoxybutane-1,4-dioic acid. In addition, the following oxygen bleaches can also be used in the dishwashing detergent composition: the cationic peroxyacids described in patent applications US5,422,028, US5,294,362 and US5,292,447 and the sulfonyl peroxyacids described in patent application US5,039,447. The oxygen bleaches can be used in an amount 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 amount of the dishwashing detergent composition.

[0177] For the dishwashing detergent composition according to the invention, chlorine-containing bleaches and combinations of chlorine-containing bleaches with peroxide-containing bleaches can also be used. Known chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfonamide, chloramine T, dichloramine T, chloramine B, N,N′-dichlorobenzoylurea, dichloro-p-toluenesulfonamide or trichloroethylamine. Preferred chlorine-containing bleaches are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate. In this regard, the chlorine-containing bleaches can generally be used in an amount of 0.1-30% by weight, preferably 0.1-20% by weight, preferably 0.2-10% by weight, particularly preferably 0.3-8% by weight, based on the total amount of the dishwashing detergent composition.

[0178] Furthermore, small amounts of bleach stabilizers such as phosphonates, borates, metaborates, metasilicates or magnesium salts may be added.

[0179] For the purposes of the present invention, bleach activators may be compounds which, under perhydrolysis conditions, form aliphatic peroxycarboxylic acids and / or substituted perbenzoic acids preferably having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms. Suitable compounds in this context are especially those which contain one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, for example substances selected from anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexanediamine (TAHD), N-acylimides, for example N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, for example n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT) or isatoic anhydride (ISA). Suitable bleach activators are also quaternary ammonium nitrile salts, for example N-methylmorpholinoacetonitrile (MMA salt) or trimethylammonium acetonitrile (TMAQ salt). Suitable bleach activators are preferably selected from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimines, particularly preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MMA and TMAQ. For the purposes of the present invention, bleach activators can be used in amounts of 0.1 to 20% by weight, preferably 0.1 to 10% by weight, preferably 0.5 to 9% by weight, particularly preferably 1.0 to 8% by weight, based on the total amount of the dishwashing detergent composition.

[0180] In addition to or instead of the conventional bleach activators, so-called bleach catalysts can also be incorporated into dishwashing detergent formulations. These substances are bleach-enhancing transition metal salts or transition metal complexes such as manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper with nitrogen-containing tripod ligands and cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.

[0181] As component (f), the dishwashing detergent formulation of the present invention can include 0-10% by weight of enzymes and enzyme stabilizers. If the dishwashing detergent formulation includes enzymes and enzyme stabilizers, its content is typically 0.1-8% by weight. Enzymes can be added to the dishwashing detergent to improve cleaning performance or ensure that the same quality of cleaning performance is achieved under milder conditions (e.g., at a lower temperature). Enzymes can be used in free form, or in a form chemically or physically fixed on a carrier, or in an encapsulated form. In this regard, the most commonly used enzymes include lipase, amylase, cellulase and protease. In addition, esterase, pectinase, lactase and peroxidase can also be used. According to the present invention, amylase and protease are preferably used.

[0182] The formulations according to the invention may comprise one or more enzyme stabilizers. Enzyme stabilizers serve to protect the enzymes - in particular during storage - from damage, such as deactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolysis.

[0183] Examples of enzyme stabilizers are reversible protease inhibitors, such as benzamidine hydrochloride, borax, boric acid, borous acid or salts or esters thereof, including in particular derivatives with aromatic groups, such as o-, m- or p-substituted phenylboronic acid, in particular 4-formylphenylboronic acid, or salts or esters of the above compounds. Peptide aldehydes are also used for this purpose, i.e. oligopeptides with a reducing carbon end, in particular those consisting of 2 to 50 monomers. Peptide reversible protease inhibitors include ovomucoid and leupeptin in particular. Specific reversible peptide inhibitors for the protease subtilisin as well as fusion proteins and special peptide inhibitors of proteases are also suitable for this purpose.

[0184] Other examples of enzyme stabilizers are amino alcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic mono- and dicarboxylic acids to C 12 Carboxylic acids, such as succinic acid. End-capped fatty acid amide alkoxylates are also suitable enzyme stabilizers.

[0185] Other examples of enzyme stabilizers are sodium sulfite, reducing sugars and potassium sulfate.Another example of a suitable enzyme stabilizer is sorbitol.

[0186] For the dishwashing detergent formulations according to the invention, further additives (g) which can be used include, for example, anionic or zwitterionic surfactants, alkaline carriers, polymeric dispersants, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tablet disintegrators, organic solvents, tableting aids, disintegrants, thickeners, solubilizers or water. In addition to the ammonium carbonate or alkali metal carbonates, ammonium bicarbonate or alkali metal bicarbonates and ammonium sesquicarbonates or alkali metal sesquicarbonates mentioned for the builder substances, useful alkaline carriers are also, for example, ammonium hydroxide or alkali metal hydroxides, ammonium silicates or alkali metal silicates and ammonium metasilicates or alkali metal metasilicates, and mixtures of the aforementioned substances.

[0187] As corrosion inhibitors, it is possible in particular to use silver protectors selected from the group consisting of triazoles, benzotriazoles, dibenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes.

[0188] In order to prevent glass corrosion, which manifests itself as fogging, iridescence, streaks and lines on glassware, glass corrosion inhibitors are preferably used. Preferred glass corrosion inhibitors are, for example, magnesium, zinc and bismuth salts and complexes, and polyethyleneimines.

[0189] According to the invention, paraffin oil and silicone oil can be used as defoamers and for protecting plastic and metal surfaces. Defoamers are preferably used in a proportion of 0.001-5% by weight. In addition, dyes, such as patent blue, preservatives such as Kathon CG, spices and other aromatic substances can be added to the cleaning formulations of the invention.

[0190] For the dishwashing detergent formulations according to the invention, a suitable filler is, for example, sodium sulfate.

[0191] Further possible additives in the context of the present invention are amphoteric and cationic polymers.

[0192] In a preferred embodiment, the dishwashing detergent formulations according to the invention are phosphate-free. In this context, the term "phosphate-free" also includes those dishwashing detergent formulations which are essentially free of phosphates, i.e. technically ineffective amounts of phosphates. This includes in particular compositions with less than 1.0% by weight, preferably less than 0.5% by weight, of phosphates, based on the total composition.

[0193] In a further preferred embodiment, the dishwashing detergent formulations according to the invention are phosphate-free and phosphonate-free.

[0194] In a particularly preferred embodiment, the dishwashing formulation comprises:

[0195] (a) 1 to 15% by weight, preferably 2 to 12% by weight, particularly preferably 3 to 10% by weight, based on the total weight of the composition, of the following components:

[0196] (a1) at least one polyaspartic acid or modified polyaspartic acid or a salt thereof, wherein the modified polyaspartic acid is obtainable by polycondensing (i) 50 to 99 mol % of aspartic acid and (ii) 1 to 50 mol % of at least one carboxyl group-containing compound different from aspartic acid, and subsequently hydrolyzing the cocondensate with the addition of a base, and

[0197] (a2) at least one graft copolymer consisting of:

[0198] (a21) at least one grafting base selected from the group consisting of monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable thereon by grafting:

[0199] (a22) at least one ethylenically unsaturated mono- or dicarboxylic acid, and

[0200] (a23) at least one ethylenically unsaturated N-containing

[0201] monomer,

[0202] wherein the weight ratio of (a1):(a2) is 12:1 to 1:3, preferably 12:1 to 1:1,

[0203] More preferably, it is 12:1 to 3:1,

[0204] (b) 1-50 wt % of methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA) or their salts as complexing agent;

[0205] (c) 3-65 wt. % of builders and / or co-builders;

[0206] (d) 0.5-12 wt % of a nonionic surfactant;

[0207] (e) 0-30% by weight of bleaching agents and bleach activators;

[0208] (f) 0.1-8 wt % of enzymes and enzyme stabilizers; and

[0209] (g) 0-50 wt% of additives.

[0210] The following examples are provided to illustrate the present invention but should not be construed as limiting the present invention. Example

[0211] Example 1

[0212] Preparation of polyaspartic acid, sodium salt (P1)

[0213] In a rotary evaporator, 133.10 g of L-aspartic acid was polycondensed at 220-240° C. for 2.5 hours. Polysuccinimide was obtained as a dry powder. In order to prepare an aqueous sodium salt solution of polyaspartic acid, 100 g of polysuccinimide was dispersed in 100 g of water, the mixture was heated to 70° C., and a sufficient amount of 50% aqueous sodium hydroxide solution was added at this temperature to keep the pH in the range of 7-8. During this period, the powder dispersed in the water gradually dissolved to obtain a transparent aqueous sodium salt solution of polyaspartic acid. The weight-average molecular weight (Mw) of the modified polyaspartic acid is 5500 g / mol (detected according to the method described in US 2016 / 0222322 A).

[0214] Example 2

[0215] Preparation of graft copolymer (P2)

[0216] Comonomer used:

[0217] (al): Maltodextrin, commercially available as Cargill C*Dry MDO1 955

[0218] (bl):Acrylic acid

[0219] (cl): 2-(Trimethylamino)ethyl methacryloyl chloride ("TMAEMC")

[0220] In a stirred reactor, 220 g of (aI) in 618 g of water were added and heated to 80° C. with stirring. At 80° C., the following solutions were metered in simultaneously and added via a separate feed:

[0221] a) An aqueous solution of 40.6 g of (cl) in 149 g of water over the course of 4 hours.

[0222] b) was metered in simultaneously with a) over the course of 5 hours with an aqueous solution of 9.85 g of sodium peroxodisulphate in 68.0 g of water.

[0223] c) Starting 2 hours after the start of the metered addition of a), over the course of 2 hours, a solution of 32.8 g of (b1) and 36.5 g of sodium hydroxide solution (50% strength in water) diluted with 139 g of water.

[0224] After the addition of solutions a) to c) was complete, the reaction mixture was stirred at 80° C. for 1 hour. Then, a solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred at 80° C. for a further 2 hours. The mixture was then cooled to room temperature and 8 g of biocide were added. This gave a 22.4% by weight solution of the graft copolymer.

[0225] Example 3

[0226] The ASTM D3556 stain / filming test was performed as follows:

[0227] Dirt:

[0228] · Blue Bonnet 53% Vegetable Butter 80% by weight

[0229] Meijer Brans instant skimmed milk powder 20 wt%

[0230] water:

[0231] 300ppm hardness (2:1Ca:Mg)

[0232] Add at 120°F

[0233] Water volume 16.5 liters

[0234] Machine type and washing program:

[0235] Kenmore dishwasher: Model 587.1401

[0236] Washing program: Normal washing

[0237] Washing time: 50 minutes

[0238] Drying time: 14 minutes

[0239] program:

[0240] 6 clean glasses (Libbey #53 10oz stemmed glasses) on the top rack and stay there (plates and silverware on the bottom rack)

[0241] · Perform 5 wash cycles (A, B) (+ heat drying), adding 40 g of fresh dirt each cycle

[0242] · Add detergent in every cycle as well.

[0243] After the 5th cycle, the level of stain and film was visually identified using a light box:

[0244]

[0245]

[0246]

[0247] Table 1: ADW formulation (without phosphate and phosphonate)

[0248]

[0249] MGDA is methylglycine diacetate trisodium salt, 80% by weight, the balance is water

[0250] SLF 180 is a low foaming alcohol alkoxylate surfactant (BASF Corporation)

[0251] EXCELLENZ TM P1000 is a granular detergent protease (DuPont)

[0252] EXCELLENZ TM S1000 is a granular detergent amylase (DuPont)

[0253] TAED = tetraacetylethylenediamine.

[0254] Results for Formulation A:

[0255] Table 2: Average Stain / Film Ratings

[0256]

[0257] *Weight% active substance

[0258]

[0259] *Weight% active substance

[0260] Results for Formulation B:

[0261] Table 3: Average Stain / Film Ratings

[0262]

[0263]

[0264] *Weight% active substance

[0265] Example 4

[0266] Aqueous solutions (20 and 40 wt. %, based on solid matter) of polyaspartic acid, sodium salt (P1) and graft copolymer (P2) were prepared by mixing previously dissolved (P1) and (P2). Different weight ratios of (P1): (P2) were used: 20:1, 12:1, 8:1, 6:1, 4:1, 1:1, 1:3, 1:12.

[0267] Even after storage for 3 months at 22-25 °C, no polymer / polymer incompatibility was observed.

[0268] Washing experiments were performed as follows:

[0269] Dishwasher: Miele G 1222 SCL

[0270] Program: 65°C in the main cycle (with pre-wash), 65°C rinse temperature, no rinse aid, no regeneration salt for the ion exchange resin

[0271] Utensils: 3 knives (WMF Tafelmesser Berlin, single-piece)

[0272] 3 Amsterdam 0.2L drinking glasses

[0273] 3 breakfast plates "OCEANBLUE" (melamine)

[0274] 3 ceramic plates: 19 cm flat plate with rim

[0275] Loading tray 8 tea cups, 8 ceramic plates

[0276] Arrangement: Knife in plate, glass in upper basket, plate in lower basket

[0277] Quantity: 18g of dishwashing detergent

[0278] Loading soil: 50 g of loading soil were metered in after pre-washing together with the formulation, see composition below

[0279] Water hardness: 21° German hardness (Ca / Mg): HCO3 (3:1): 1.35

[0280] Washing cycles: 30; in each case 1 hour pause between each cycle (10 minutes with door open, 50 minutes with door closed)

[0281] Evaluation: Visual evaluation after 30 wash cycles

[0282] After 30 cycles, the dishes were evaluated in a dark room under light behind the well plate using a rating scale of 10 (very good) to 1 (very poor). Filming was given a rating of 1-10 (very severe filming = 1, no filming = 10).

[0283] Composition of dirt load:

[0284] Starch: 0.5% potato starch, 2.5% gravy

[0285] Fat: 10.2% margarine

[0286] Protein: 5.1% egg yolk, 5.1% milk

[0287] Others: 2.5% ketchup, 2.5% mustard, 0.1% benzoic acid, 71.4% water

[0288] The following basic detergent composition was used:

[0289] Table 4

[0290] (weight%) F1 F2 F3 Trisodium citrate dihydrate 35 35 0 MGDA 10 10 45 <![CDATA[Sodium percarbonate 2Na2CO3·3H2O2]]> 10.19 10.19 10.19 Nonionic surfactant 1 4 4 4 Nonionic surfactant 2 1 1 1 Protease 2.5 2.5 2.5 Amylose 1 1 1 <![CDATA[Na2Si2O5]]> 2 2 2 TAED 4 4 4 <![CDATA[Na2CO3]]> 24.5 24.5 24.5 HEDP 0.81 Gap 0.81 0.81 polymer 5 5 5

[0291] MGDA: trisodium methylglycine diacetate, 80% by weight, the rest is water

[0292] Nonionic surfactant 1:

[0293] n-C8H 17 -CH(OH)-CH2-O-(EO) 22 -CH(CH3)-CH2-OnC 10 H 21

[0294] Nonionic surfactant 2:nC 10 H 21 -CH(OH)-CH2-O-(EO) 40 -nC 10 H 21

[0295] Na2Si2O5: as H 265LC Commercial

[0296] HEDP:1-Hydroxyethane-1,1-diphosphonate disodium salt

[0297] TAED:Tetraacetylethylenediamine

[0298] Polymer: P1, P2, M1, M2, M3, M4 (active substances)

[0299] M1 = aqueous mixture of P1 and P2 (40 wt%) (P1:P2 weight ratio = 4:1)

[0300] M2 = Aqueous mixture of P1 and P2 (40 wt%) (P1:P2 weight ratio = 8:1)

[0301] M3 = Aqueous mixture of P1 and P2 (40 wt%) (P1:P2 weight ratio = 12:1)

[0302] M4 = aqueous mixture of P1 and P2 (40 wt%) (P1:P2 weight ratio = 1:1) Film formation results on glass:

[0303] Table 5: Average film scores

[0304]

[0305] *Weight% active substance

[0306]

[0307] *Weight% active substance

[0308]

[0309] *Weight % active substance.

Claims

1. A phosphate-free and phosphonate-free dishwashing detergent formulation comprising: (a) 1 to 15 wt. % in total of the following components (a1) and (a2), based on the total weight of the composition: (a1) at least one polyaspartic acid or modified polyaspartic acid or a salt thereof, wherein the modified polyaspartic acid is obtained by polycondensing (i) 50 to 99 mol % of aspartic acid and (ii) 1 to 50 mol % of at least one carboxyl group-containing compound different from aspartic acid, and subsequently hydrolyzing the cocondensate with the addition of a base, and the molecular weight Mw of the polyaspartic acid or modified polyaspartic acid is from 1500 g / mol to 15,000 g / mol, (a2) at least one graft copolymer consisting of (a21) and side chains obtained by grafting (a22) and (a23) onto (a21): (a21) at least one graft base selected from starch and starch degradation products, (a22) at least one ethylenically unsaturated C3-C 10 Monocarboxylic acids and their alkali metal salts; (a23) at least one ethylenically unsaturated N-containing monomer having a cationic charge selected from trialkylaminoethyl (meth)acryloyloxy chloride, trialkylaminopropyl (meth)acryloyloxy chloride, (meth)acrylamidoethyl trialkylammonium chloride, and (meth)acrylamidopropyl trialkylammonium chloride, wherein the corresponding alkyl group is methyl or ethyl or a mixture thereof, wherein the weight ratio of (a1):(a2) is 12:1 to 3:1; (b) 1-50 wt % of a complexing agent; (c) 0.1 to 80% by weight of builders and / or co-builders; (d) 0.1-20 wt % of a nonionic surfactant; (e) 0.1 to 30% by weight of bleaching agents and bleach activators; (f) 0.1-10 wt % of enzymes and enzyme stabilizers; and (g) 0-50 wt % of additives, wherein the additives are selected from anionic or zwitterionic surfactants, alkaline carriers, polymer dispersants, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents, tableting aids, disintegrants, thickeners, solubilizers or water.

2. The dishwashing detergent formulation according to claim 1, characterized in that The dishwashing detergent formulation contains modified polyaspartic acid or a salt thereof which is obtained by polycondensation of (i) 80 to 95 mol % of aspartic acid and (ii) 5 to 20 mol % of at least one carboxyl group-containing compound different from aspartic acid.

3. The dishwashing detergent formulation according to claim 2, characterized in that The at least one carboxyl group-containing compound (ii) is selected from 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine, glutamic acid or a mixture thereof.

4. Dishwashing detergent formulation according to any one of claims 1 to 3, characterised in that The monomer (a23) is trimethylaminoethyl acryloyloxy chloride, trimethylaminoethyl methacryloyloxy chloride or methacrylamidopropyl trimethylammonium chloride.

5. Dishwashing detergent formulation according to any one of claims 1 to 3, characterised in that The complexing agent (b) comprises methylglycine diacetic acid and / or glutamic acid diacetic acid, or a salt thereof.

6. Dishwashing detergent formulation according to any one of claims 1 to 3, characterised in that The contents of components (b) to (f) are respectively: (b) 1 to 50% by weight of methylglycine diacetic acid, glutamic acid diacetic acid or a salt thereof; (c) 3-65 wt. % of builders and / or co-builders; (d) 0.5-10 wt % of a nonionic surfactant; and (f) 0.1-8 wt % of enzymes and enzyme stabilizers.

7. The dishwashing detergent formulation according to claim 4, characterized in that The contents of components (b) to (f) are respectively: (b) 1 to 50% by weight of methylglycine diacetic acid, glutamic acid diacetic acid or a salt thereof; (c) 3-65 wt. % of builders and / or co-builders; (d) 0.5-10 wt % of a nonionic surfactant; and (f) 0.1-8 wt % of enzymes and enzyme stabilizers.

8. The dishwashing detergent formulation according to claim 5, characterized in that The contents of components (b) to (f) are respectively: (b) 1 to 50% by weight of methylglycine diacetic acid, glutamic acid diacetic acid or a salt thereof; (c) 3-65 wt. % of builders and / or co-builders; (d) 0.5-10 wt % of a nonionic surfactant; and (f) 0.1-8 wt % of enzymes and enzyme stabilizers.

9. Use of the following components (a1) and (a2) as filming-inhibiting additives in phosphate-free and phosphonate-free automatic dishwashing detergent formulations, (a1) at least one polyaspartic acid or modified polyaspartic acid or a salt thereof, wherein the modified polyaspartic acid is obtained by polycondensing (i) 50 to 99 mol % of aspartic acid and (ii) 1 to 50 mol % of at least one carboxyl group-containing compound different from aspartic acid, and subsequently hydrolyzing the cocondensate with the addition of a base, and the molecular weight Mw of the polyaspartic acid or modified polyaspartic acid is from 1500 g / mol to 15,000 g / mol, (a2) at least one graft copolymer consisting of (a21) and side chains obtained by grafting (a22) and (a23) onto (a21): (a21) at least one graft base selected from starch and starch degradation products, (a22) at least one ethylenically unsaturated C3-C 10 Monocarboxylic acids and alkali metal salts thereof, and (a23) at least one ethylenically unsaturated N-containing monomer having a cationic charge selected from trialkylaminoethyl (meth)acryloyloxy chloride, trialkylaminopropyl (meth)acryloyloxy chloride, (meth)acrylamidoethyl trialkylammonium chloride, and (meth)acrylamidopropyl trialkylammonium chloride, wherein the corresponding alkyl group is methyl or ethyl or a mixture thereof, The weight ratio of (a1):(a2) is 12:1 to 3:1.

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