EP3047003A1

EP3047003A1 - Use of modified polyaspartic acids in dishwashing detergents

Info

Publication number: EP3047003A1
Application number: EP14758978.2A
Authority: EP
Inventors: Jürgen Detering; Gazi TÜRKOGLU; Dietrich Fehringer; Heike Weber
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2013-09-16
Filing date: 2014-09-05
Publication date: 2016-07-27
Anticipated expiration: 2034-09-05
Also published as: CA2923744A1; US9796951B2; US20160222322A1; WO2015036325A1; PL3047003T3; CN105555931B; ES2851207T3; MX2016003438A; CN105555931A; JP2016536430A; KR20160055917A; RU2016114687A; RU2016114687A3; RU2665581C2; EP3047003B1

Abstract

The present invention relates to the use of modified polyaspartic acids in dishwashing detergents, more particularly as dispersants, encrustation inhibitors and spot inhibitors. The invention also relates to dishwashing detergent compositions containing modified polyaspartic acids.

Description

Use of modified polyaspartic acids in dishwashing detergents

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

Polymers obtainable by free-radical polymerization from monomers containing carboxyl groups have been an important constituent of phosphate-containing and phosphate-free automatic dishwashing detergents for many years. Their dirt-dispersing and deposit-inhibiting action make a significant contribution to the cleaning and rinsing performance of automatic dishwashing detergents. In this way, they ensure that no salt deposits of the hardness-forming calcium and magnesium ions remain on the items to be washed. Frequently, homo- and copolymers of acrylic acid are used for this purpose.

A disadvantage of these polymers obtainable by free-radical polymerization from carboxyl group-containing monomers is that they can be used under aerobic conditions, as described, for example, in US Pat. prevail in a municipal sewage treatment plant, are not biodegradable.

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

WO 201 1/001 170 describes automatic dishwashing detergent compositions comprising polyaspartic acid, a liquid nonionic surfactant and at least one solid nonionic surfactant, wherein the preparation of the polyaspartic acid is not described. WO 2009/095645 describes detergent compositions which contain subsequently modified polyaspartic acids with polyaspartic acid as backbone as coating inhibitor. The modified polyaspartic acids are obtained by reacting the polyaspartic acid or the polysuccinimide with PO / EO block copolymers, polyethyleneimine or adenosine triphosphate. Such a polyaspagrainic backbone is not difficult to adjust in molecular weight. The object of the invention was therefore to provide polymers as rinse aid additives, in particular as an additive to phosphate-free rinse aid formulations for machine dishwashing, which can be used to inhibit scale in water-bearing systems, are variably adjustable in their polymer structure and their molecular weight and biodegradable. The molecular weight of the polymers can ideally be set between 1 000 and 10 000 g / mol.

This object has been achieved by the present invention according to the claims and the following description and examples.

The present invention relates to the use of modified polyaspartic acids as an additive in dishwashing detergents, as well as a dishwashing detergent composition comprising modified polyaspartic acids. The modified polyaspartic acids used in connection with the present invention can be prepared by polycondensation of

(i) 50 to 99 mol% aspartic acid; and

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

and subsequent hydrolysis of the cocondensates with the addition of a base, wherein (ii) is not aspartic acid. In addition to the modified polyaspartic acids described and to be used according to the invention, the dishwashing 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 optionally further additives.

By the production method described here for polyaspartic acid, the polyaspartic acid in salt form is first obtained after the hydrolysis step with addition of a base, as the person skilled in the art readily recognizes. The acid form of the polyaspartic acid can be easily obtained by a further step of acidification of the salt, which can be carried out in a manner known to the person skilled in the art. Suitable acids for this purpose include mineral acids, for example sulfuric acid or hydrochloric acid. If only the salt of polyaspartic acid is desired, for example as an intermediate, the step of subsequent acidification can be dispensed with. Whenever polyaspartic acid is mentioned in the context of the present invention, its corresponding salts, as obtainable or obtained by the said subsequent acidification step, are also correspondingly included and as recognized by the person skilled in the art.

The optional acidification of the salt of the modified polyaspartic acid can be carried out, for example, by adding a defined amount of a concentrated or dilute mineral acid such as, for example, sulfuric acid or hydrochloric acid to an aqueous sodium salt solution of the modified polyaspartic acid. Acidification can also be accomplished by treatment with an acidic ion exchanger, such as Amberlite IR 120 (Hydrogen Form), by flowing the aqueous Na salt solution of the modified polyaspartic acid over a column packed with the ion exchanger. The modified polyaspartic acids to be used according to the invention have extremely good usability as additives in dishwashing detergents, in particular automatic dishwashing dishwashing detergents, and have very good dispersing, pad inhibiting and spot inhibiting properties. Furthermore, they are biodegradable and can be made 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, scale inhibitor or spot inhibitors - in dishwashing detergents, in particular dishwasher detergents, wherein the modified polyaspartic acid can be prepared by polycondensation of

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

(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, where (ii) is not aspartic acid.

The present invention also relates to detergent compositions, particularly automatic dishwashing detergent compositions, comprising modified polyaspartic acids preparable as illustrated and described herein. The description of the preparation of modified polyaspartic acids in connection with the present invention therefore generally relates both to the use according to the invention of such modified polyaspartic acids as additives in dishwashing detergents and to their use as constituents of dishwashing detergent compositions according to the invention.

As aspartic acid (i) in connection with the preparation of the polyaspartic acid to be used according to the invention, it is possible to use both L- and D-aspartic acid and DL-aspartic acid. Preference is given to using L-aspartic acid. Carboxylic acid (monocarboxylic acid or polycarboxylic acid), a hydroxycarboxylic acid and / or an amino acid (except aspartic acid) may be used as 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 connection, polybasparaginic acid to be used according to the invention can therefore 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, C1-C26 alkylsuccinic acids (eg Octylsuccinic acid), C2-C26 alkenylsuccinic acids (eg 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-Propantetracarbonsäure, or 1, 3,3, 5-Pentantetracarbonsäure. In addition, polybasic hydroxycarboxylic acids can be used in this context, for example citric acid, isocitric acid, mucic acid, tartaric acid, tartronic acid, or apple juice. acid. Amino acids in this context include, inter alia, aminocarboxylic acids (eg glutamic acid, cysteine), basic diaminocarboxylic acids (eg lysine, arginine, histidine, aminocaprlactam), neutral amino acids (eg glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine , Caprolactam, asparagine, isoasparagine, glutamine, isoglutamine), aminosulphonic acids (eg taurine), hydroxylamino acids (eg hydroxyproline, serine, threonine), iminocarboxylic acids (eg proline, iminodiacetic acid), or aromatic and heterocyclic amino acids (eg anthranilic acid, tryptophan , Tyrosine, histidine), 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 preparation of the modified polyaspartic acids to be used according to the invention may include, but are not limited to: alkali and alkaline earth metal bases such as caustic soda, 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. Preferred in the context of the present invention are sodium hydroxide or ammonium hydroxide.

The modified polyaspartic acids to be used according to the invention are generally prepared by 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 described above and below. The preparation of such modified polyaspartic acids is also described by way of example in DE 4221875.6. 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 production 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 prepared according to the following preparation description, also those which can be prepared 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 herein. The polycondensation can be carried out at temperatures of 100 to 270 ° C, preferably at 120 to 250 ° C, more preferably at 180 to 220 ° C. The condensation (annealing) is preferably carried out in vacuo or under an inert gas atmosphere (eg N 2 or argon). The condensation can also be carried out under elevated pressure or in a gas stream, for example carbon dioxide, air, oxygen or water vapor. Depending on the chosen reaction conditions, the reaction times for the condensation are generally between 1 minute and 50 hours, preferably between 5 and 8 hours. The polycondensation can be carried out, for example, in solid phase, in which first an aqueous solution or suspension of aspartic acid and preparing at least one carboxyl-containing compound (ii) and evaporating the solution to dryness. This can already use a condensation. For example, as reactors, heating tapes, kneaders, mixers, paddle dryers, extruders, rotary kilns and other heatable devices in which the condensation of solids can be carried out with removal of water of reaction are suitable for the condensation. Low molecular weight polycondensates can be prepared in pressure-tight vessels by not or only partially removing the resulting water of reaction. The polycondensation can also be carried out by infrared radiation or microwave radiation. Also possible is an acid-catalyzed polycondensation, for example with inorganic acids of phosphorus or sulfur or with hydrogen halides. Such acid-catalyzed polycondensations are also described in DE 4221875.6.

By adding small amounts of methanesulfonic acid in the polycondensation of aspartic acid, the molecular weight of the polyaspartic acid obtained after hydrolysis of the polysuccinimide intermediate can be controlled. In the context of the present invention, it is thus possible to prepare modified polyaspartic acid to be used according to the invention by also using methanesulfonic acid as additive in the polycondensation in addition to aspartic acid (i) and a carboxyl-containing compound (ii) and then the resulting cocondensate 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 hand in the condensation step should ideally be 200: 1 to 5: 1, preferably 100: 1 to 10: 1, particularly preferably 50 : 1 to 12: 1. In this embodiment of 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 therefore used to prepare the modified polyaspartic acid to be used according to the invention, particularly preferably 5 to 20 mol% of a carboxyl-containing compound 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 polycondensed as described herein. Methanesulfonic acid, like polyaspartic acid, is biodegradable. Small amounts of methanesulfonic acid can remain in the polymer product without environmental disadvantages and without affecting performance in the numerous applications. A complex workup or cleaning is not necessary. Yield losses due to the workup are avoided.

In the case of the thermal polycondensation of aspartic acid with one of the suitable carboxyl-containing compounds (ii) (with or without methanesulfonic acid), the polycondensate generally accumulates in the form of the water-insoluble modified polyaspartimides, in a few cases in water-soluble form (for example in US Pat Polycondensation of L-aspartic acid with citric acid). The co-condensates of aspartic acid can be purified from the unreacted starting materials, for example, by the crushed product and extracted with water at temperatures of 10 to 100 ° C. The unreacted starting materials are dissolved out and any methanesulfonic acid used is dissolved washed out. Unreacted aspartic acid can be easily dissolved 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, for example polycondensate of L-aspartic acid and citric acid) and at temperatures preferably in the range from 0 to 90 ° C. Addition of a base hydrolyzed and neutralized. The hydrolysis and neutralization preferably takes place at pH values of 8 to 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. As bases, for example, carbonates such as soda and potassium carbonate in question. Also suitable as the base are ammonia and primary, secondary or tertiary amines and other bases having primary, secondary or tertiary amino groups. When amines are used for the reaction of polyaspartimide, the amines can be bound to the polyaspartic acid both salt-like and amide-like due to their high reactivity. In the treatment with bases obtained partially or completely neutralized polycocondensates, according to the use in the preceding polycondensation 50 to 99 mol% aspartic acid according to (i), and 1 to 50 mol% of at least one carboxyl-containing compound (ii) (with or without methanesulfonic acid in proportions as described herein) in the form of the salts corresponding to the bases.

The modified polyaspartic acids to be used according to the invention or their salts may be in the form of 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 granule form can be obtained, for example, by spray drying, spray granulation, fluidized-bed spray granulation, drum drying or freeze-drying of the aqueous solution of the polyaspartic acids or their salts.

The present invention furthermore relates to detergent compositions, in particular dishwashing detergent compositions which, in addition to the modified polyaspartic acids described and to be used according to the invention, also include complexing agents, builders and / or co-builders, nonionic surfactants, bleaching agents and / or bleach activators, enzymes and optionally other additives such as solvents include. 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. These include, inter alia, solid formulations such as powders, tablets, gelatinous formulations and liquid formulations.

The modified polyaspartic acids described and to be used according to the invention which are used according to the invention can be used particularly advantageously in automatic dishwashing detergents. They are characterized mainly by their deposit-inhibiting effect against both inorganic and organic coatings. In particular, they inhibit deposits of calcium and magnesium carbonate and calcium and magnesium phosphates and phosphonates. In addition, they prevent deposits that come from the dirt components of the rinse, such as fat, protein and starch coverings. The detergent compositions of the invention may be provided in liquid, gel or solid form, single or multi-phase, as tablets or in the form of other dosage units, packaged or unpackaged.

The modified polyaspartic acids described and to be used according to the invention can be used both in multicomponent product systems (separate use of cleaner, rinse aid and regenerating salt) and in rinse aids in which the functions of cleaner, rinse aid and regenerating salt are combined in one product (eg 3-in-1 products, 6-in-1 products, 9-in-1 products, all-in-one products).

The rinse-aid compositions according to the invention comprise

(a) 1 to 20% by weight, preferably 1 to 15% by weight, more preferably 2 to 12% by weight of at least one modified polyaspartic acid described herein and to be used according to the invention;

(b) 0-50% by weight of complexing agent;

(c) 0.1-80% by weight builder and / or co-builder;

(d) 0.1-20% by weight of nonionic surfactants;

(e) 0-30 wt% bleaches, bleach activators and bleach catalysts;

(f) 0-8 wt% enzymes; and

(g) 0-50% by weight of additives.

The detergent composition according to the invention is particularly suitable as a dishwashing detergent composition for machine dishwashing. Thus, in one embodiment, the rinse aid composition of the present invention is a machine dishwashing detergent composition.

As complexing agent (b) it is possible to use, for example: nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetire, methylglycinediacetic acid, glutamic acid diacid, iminodisuccinic acid, hydroxyminodisuccinic acid, ethylenediamine disuccinic acid, aspartic acid diacetic acid, and in each case their salts. Preferred complexing agents (b) are methylglycinediacetic acid and glutamic acid diacetic acid and their salts. Particularly preferred complexing agents (b) are methylglycinediacetic acid and its salts. According to the invention, preference is given to 3 to 50% by weight of complexing agent (b). As builder and / or co-builder (c) it is possible in particular to use water-soluble or water-insoluble substances whose main task is the binding of calcium and magnesium ions. These can be low-molecular-weight carboxylic acids and their salts, such as alkali in particular, anhydrous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, alkali metal malates, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate and α-hydroxypropionic acid.

Another class of substances with cobuilder properties which may be present in the cleansing compositions according to the invention are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkanophosphonates, the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkane phosphonates also have a pronounced shear metal binder deficiency. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

Among others, as builders silicates can be used. Contain may be crystalline layered silicates having the general formula NaMSi _x O 2x + i y H 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 2, 3 or 4 and y is a number from 0 to 33, preferably 0 to 20. In addition, amorphous sodium silicates with a 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, builders and / or co-builders (c) in connection with the rinsing agent composition according to the invention can be used carbonates and bicarbonates, among which the alkali metal salts, in particular sodium salts, are preferred.

It is also possible to use as co-builders homopolymers and copolymers of acrylic acid or of methacrylic acid, which preferably have a weight-average molar mass of from 2,000 to 50,000 g / mol. Suitable comonomers are in particular monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and their anhydrides such as maleic anhydride. Also suitable are sulfonic acid-containing comonomers such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid and vinylsulfonic acid. Hydrophobic comonomers are also suitable, for example isobutene, diisobutene, styrene, alpha-olefins having 10 or more carbon atoms. Hydrophilic monomers having hydroxy functionality or alkylene oxide groups can also be used as comonomers. Examples which may be mentioned are: allyl alcohol and isoprenol and their alkoxylates and methoxypolyethylene glycol (meth) acrylate.

Preferred amounts for builder and / or co-builder in connection with the inventive detergent composition is 5 to 80% by weight, more preferably 10 to 75% by weight, 15 to 70% by weight or 15 to 65% by weight. As nonionic surfactants (d) in connection with the rinse aid composition according to the invention, it is possible to use, for example, weakly or low foaming nonionic surfactants. These may be present in proportions of from 0.1 to 20% by weight, preferably from 0.1 to 15% by weight, more preferably from 0.25 to 10% by weight, or from 0.5 to 10% by weight. Suitable nonionic surfactants include, inter alia, surfactants of the general formula (I)

R ¹ -0- (CH 2 CH ₂ 0) a (CHR ² CH ₂ 0) b R ³ (I) wherein R ¹ is a linear or branched alkyl radical having 8 to 22 C atoms,

R ² and R ^{3 are} independently hydrogen or a linear or branched alkyl radical having 1 to 10 C atoms or H, wherein R ^{2 is} preferably methyl, and

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

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

R ⁴ - [CH ₂ CH (CH 3) O] c [CH ₂ CH ₂ O] d [CH ₂ CH (CH 3) O] e CH ₂ CH (OH) R ⁵ (II) wherein R ^{4 is} a linear or branched aliphatic hydrocarbon radical of 4 to 22 Carbon atoms or mixtures thereof,

R ⁵ denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof,

c and e are values between 0 and 40, and

d is a value of at least 15. 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 of 8 to 16 carbon atoms, R ⁷ , R ⁸ are independently H or a branched or unbranched alkyl radical having 1 to 5 carbon atoms,

R ^{9 is} an unbranched alkyl radical having 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 formulas (I), (II) and (III) may be both random copolymers and block copolymers, preferably as block copolymers.

Furthermore, in connection with the present invention di- and multi-block copolymers composed of ethylene oxide and propylene oxide, are used, the examples game, under the name Pluronic ^® (BASF SE) or Tetronic ^® (BASF Corporation) are commercially available. Furthermore, reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used. Also suitable are amine oxides or Alkylglycosides. An overview of suitable nonionic surfactants are disclosed in EP-A 851 023 and in DE-A 198 19 187.

It may also contain mixtures of several different nonionic surfactants. The inventive detergent compositions may further contain anionic or zwitterionic surfactants, preferably in admixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also mentioned in EP-A 851 023 and DE-A 198 19 187.

As bleaching agents and bleach activators (e), representatives known to the person skilled in the art can be used in connection with the dishwashing detergent compositions according to the invention. Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaching agents. Use as oxygen bleach find alkali metal perborates and their hydrates and alkali metal per- carbonate. Preferred bleaching agents here are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate. Also usable as oxygen bleaching agents are persulfates and hydrogen peroxide. Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid. In addition, the following oxygen bleaching agents can also be used in the detergent composition: Cationic peroxyacids described in patent applications US Pat. Nos. 5,422,028, 5,294,362 and 5,292,447, and sulfonyl peroxyacids described in US Pat. No. 5,039,447. Oxygen bleaching agents can be used in amounts of generally from 0.1 to 30% by weight, preferably from 1 to 20% by weight, particularly preferably from 3 to 15% by weight, based on the total detergent composition.

Chlorine-containing bleaching agents and the combination of chlorine-containing bleaching agents with peroxide-containing bleaching agents can also be used in connection with the dishwashing detergent compositions according to the invention. Known chlorine-containing bleaching agents are for example 1, 3-dichloro-5,5-dimethylhydantoin, N-Chlorosulfamid, chloramine T, dichloramine T, chloramine B, Ν, Ν ^{'-Dichlorbenzoylharnstoff,} p-Toluolsulfondichloroamid or Trichlorethylamin. Preferred chlorine-containing bleaching agents are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate. Chlorine-containing bleaches may in this context in amounts of from 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 the entire detergent composition are used.

Furthermore, bleach stabilizers such as phosphonates, borates, metaborates, metasilicates or magnesium salts can be added in small amounts.

In the context of the present invention, bleach activators may be compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid. Among others, compounds containing one or more N- or O-acyl groups and / or optionally substituted benzoyl groups are suitable. For example, substances from the class of anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides such as N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates such as n-nonanoyl or isononanoyloxybenzenesulfonates (n- or n-nonanoyl) iso-NOBS), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT) or isatoic anhydride (ISA). Likewise 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 are preferably suitable from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenolsulfonates, particularly preferably n- or iso-NOBS, MMA, and TMAQ. Bleach activators may be used in the context of the present invention in amounts of from 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 to 5% by weight, based on the entire detergent composition can be used.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into rinse aid particles. These substances are bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene 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.

As component (f), the rinse-aid compositions according to the invention may contain from 0 to 8% by weight of enzymes. If the detergent compositions contain enzymes, they preferably contain them in amounts of from 0.1 to 8% by weight. Enzyme may be added to the rinse to enhance cleaning performance or to maintain cleaning performance of equal quality under milder conditions (e.g., at low temperatures). The enzymes can be used in free or on a carrier chemically or physically immobilized form or in encapsulated form. Among the most commonly used enzymes in this context are lipases, amylases, cellulases and proteases. Furthermore, for example, esterases, pectinases, lactases and peroxidases can be used. According to the invention, amylases and proteases are preferably used.

As additives (g) in connection with the rinse aid compositions according to the invention, for example anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tablet detonation agents, organic solvents, tableting aids, disintegrating agents, thickeners, solubilizers, or water are used. As alkali carriers, for example, in addition to the ammonium or alkali metal carbonates already mentioned in the case of the builder substances, ammonium or alkali metal hydrogencarbonates and ammonium or alkali metal sesquicarbonates, it is also possible to use ammonium or alkali metal hydroxides, ammonium or alkali metal silicates and ammonium or alkali metal silicates and mixtures of the aforementioned substances are used.

As corrosion inhibitors, inter alia, silver protectants from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used.

Glass corrosion inhibitors are preferably used to prevent glass corrosion, which is manifested by clouding, iridescence, streaks and lines on the glasses. Preferred glass corrosion inhibitors are, for example, magnesium-zinc and bismuth salts and complexes.

Paraffin oils and silicone oils can be used according to the invention optionally as defoamers and for the protection of plastic and metal surfaces. Defoamers are preferably used in proportions of 0.001% by weight to 5% by weight. In addition, dyes such as patent blue, preservatives such as Kathon CG, perfumes and other perfumes may be added to the cleaning formulation of 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 encompasses those detergent compositions which essentially contain no phosphate, ie phosphate in industrially ineffective amounts, in particular compositions with less than 1.0% by weight, preferably less than 0.5% by weight. Phosphate based on the total composition.

The following examples are illustrative of the present invention and should not be construed as limiting it thereto. example 1

Preparation of the modified polyaspartic acids

Indicated are in each case molar ratios. Inventive polymers

Polymer 1: polycondensate of L-aspartic acid / BTC 1, 0: 0.1

Polymer 1 b: polycondensate of L-aspartic acid / BTC 1, 0: 0.1 in the presence of 5 mol%

(L-Asp) methanesulfonic acid

Polymer 2: polycondensate of L-aspartic acid / BTC 1, 0: 0.2

Polymer 3: polycondensate of L-aspartic acid / citric acid 1, 0: 0.5

Polymer 4: polycondensate of L-aspartic acid / glycine 1, 0: 0.1 Polymer 5: polycondensate of L-aspartic acid / glutamic acid 1, 0: 0.1

Polymer 5b: polycondensate of L-aspartic acid / glutamic acid 1, 0: 0.1 in the presence of 5 mol% (or 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

Inventive 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 stirrer. The reaction mixture was heated with stirring for 4 hours at a temperature of 210 ° C while distilling off water. The resulting melt of the modified polyaspartimide was cooled and then comminuted. To prepare the aqueous sodium salt solution of the modified polyaspartic acid, dispersed 100 g of the comminuted reaction mass in 100 g of water, heated the mixture to 70 ° C and added at this temperature as much of a 50% aqueous sodium hydroxide solution, so that the pH Value was in the range 7-8. At this time, the powder dispersed in water gradually dissolved to give a clear aqueous sodium salt solution of the modified polyaspartic acid. The weight-average molecular weight (Mw) of the modified polyaspartic acid was 2600 g / mol.

Polymer 1 b:

The synthesis and workup of this polymer was carried out exactly as described in Polymer 1, but 4.81 g of methanesulfonic acid were additionally introduced into the reactor. The weight-average molecular weight (Mw) of the modified polyaspartic acid was 3300 g / mol.

Polymer 2:

Analogously to the preparation of the polymer 1, 133.10 g of L-aspartic acid and 46.83 g of 1,2,3,4-butanetetracarboxylic acid were initially charged to the reactor for 2.5 hours at 240 ° C polycondensed. The resulting melt of the modified polyaspartimide was cooled, crushed and hydrolyzed as described in Example 1 to 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:

Analogously to the preparation of the polymer 1, 133.10 g of L-aspartic acid and 96.07 g of citric acid were introduced into the reactor and polycondensed at 180 ° C. for 5 h. The resulting melt of the modified polyaspartimide was cooled and then comminuted. Around To prepare the aqueous sodium salt solution of the modified polyaspartic acid, dissolved 100 g of the cooled and crushed reaction mass in 100 g of water and added under ice-cooling as much of a 50% aqueous sodium hydroxide solution 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:

Analogously to the preparation of the polymer 1, 133.10 g of L-aspartic acid, 30.00 g of water and 7.51 g of glycine were introduced into the reactor and polycondensed at 220 ° C. for 7 h. The resulting melt of the modified polyaspartimide was cooled, comminuted and hydrolyzed as described in Example 1 to 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 introduced into the reactor and polycondensed at 220 ° C. for 7.5 h. The resulting melt of the modified polyaspartimide was cooled, comminuted and hydrolyzed as described in Example 1 to 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:

The synthesis and workup of this polymer was carried out exactly as described in Polymer 5, but 4.81 g of methanesulfonic acid were additionally introduced into the reactor. The weight-average molecular weight (Mw) of the modified polyaspartic acid was 6100 g / mol.

Comparative Polymer Polymer V1 (Polyaspartic Acid M):

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

Polymer V2 (polyaspartic acid T):

In a rotary evaporator 133.10 g of L-aspartic acid were polycondensed for 2 h at a temperature of 220-240 ° C. The resulting polyaspartimide was hydrolyzed as described in Example 1 to 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 by GPC (gel permeation chromatography) under the following conditions:

Sample solutions were filtered over Sartorius Minisart RC 25 (0.2 μηη). The calibration was carried out with narrowly distributed Na-PAA standards from the company Polymer Standard Service with molecular weights of 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, which was equated with Na-PAA M = 150. 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 given in Table 1 (in% by weight). Table 1: Test formulation PF1

Component PF 1

Protease 2.5

Amylase 1, 0

Nonionic surfactant 5

Polymer 10

Sodium percarbonate 10.2

Tetraacetylethylenediamine 4

Sodium disilicate 2

Sodium carbonate 19.5

Sodium citrate dihydrate 35

Methylglycinediacetic acid, 10

Na salt

Hydroxyethane (1, 1 - 0.8

diphosphonic acid) Data 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)

Washware: 3 knives (Nickel Chrome Knife Karina, Solex Germany GmbH, Eisingen / Germany)

3 drinking glasses Amsterdam 0.2L

3 BREAKFAST "OCEAN BLUE" (MELAMINE)

3 porcelain plates: FLAG FLAT 19 CM

Arrangement: knife in the cutlery drawer, glasses in the upper basket, plates in the lower basket sorted

Dishwashing detergent: 18 g

Dirt addition: 50 g ballast dirt is thawed with the formulation dosed after pre-rinsing, for composition see below

Rinse temperature: 65 ° C

Water hardness: 21 ° dH (Ca / Mg): HC03 (3: 1): 1 .35

Rinsing cycles: 15; between each 1 h break (10 min closed door, 50 min open door)

Evaluation: Visually after 15 rinsing cycles

Scouring was evaluated after 15 cycles in a darkened chamber under light behind a pinhole using a grading scale from 10 (very good) to 1 (very poor). Grades from 1 to 10 were given for spotting (very many, intensive spots = 1, no spots = 10), as well as for surfacing (1 = very strong surfacing, 10 = no surfacing)

Composition of ballast dirt:

Starch: 0.5% potato starch, 2.5% gravy

Fat: 10.2% margarine

Protein: 5.1% egg yolks, 5.1% milk

Others: 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 deposit-inhibiting action against inorganic and organic deposits on glass and knives. Furthermore, they increased the cleaning power of the dishwashing detergent and favored the drainage of the water from the dishes, so that particularly clear glasses and shiny metal cutlery were obtained.

In the following Table 2 the grades for deposit formation (B) and spotting (S) on brass and drinking glasses are listed. Table 2: 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

claims

1 . Use of modified polyaspartic acid as an additive in dishwashing detergents, wherein the modified polyaspartic acid can be prepared by polycondensation of

(i) 50 to 99 mol% aspartic acid; and

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

and subsequent hydrolysis of the cocondensates with the addition of a base,

where (ii) is not aspartic acid.

2. Use according to claim 1, wherein (i) 50 to 95 mol% aspartic acid and (ii) 5 to 50 mol% of at least one carboxyl-containing compound.

3. Use according to claim 1 or 2, wherein (i) is 80 to 95 mol% aspartic acid and (ii) 5 to 20 mol% of at least one carboxyl-containing compound.

4. Use according to any one of claims 1 to 3, wherein (ii) is a monocarboxylic acid, a polycarboxylic acid, a hydroxycarboxylic acid and / or an amino acid.

5. Use according to any one of the claims, wherein (ii) is selected from the group consisting of 1, 2,3,4-butanetetracarboxylic acid, citric acid, glycine and glutamic acid.

6. Use according to any one of claims 1 to 5, wherein the base is selected from the group consisting of alkali and alkaline earth metal bases; carbonates; Ammonia; primary, secondary or tertiary amines; and bases with primary, secondary or tertiary amino groups.

7. Use according to one of claims 1 to 6 in dishwashing detergents for machine dishwashers.

8. Use according to one of claims 1 to 7, wherein the modified polyaspartic acid can be prepared by polycondensation of

(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, preferably 100: 1 to 10: 1, particularly preferably 50 : 1 to 12: 1; and

and subsequent hydrolysis of the cocondensates with the addition of a base,

where (ii) is not aspartic acid.

9. A detergent composition comprising

(a) 1 -20% by weight of at least one modified polyaspartic acid according to any one of claims 1 to 8; (b) 0-50% by weight of complexing agent;

(c) 0.1-80% by weight builder and / or co-builder;

(d) 0.1-20% by weight of nonionic surfactants;

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

(f) 0-8 wt% enzymes; and

(g) 0-50% by weight of additives.

A detergent composition according to claim 9, wherein the composition is suitable for machine dishwashers.

1 . A detergent composition according to claim 9 or 10, comprising

(a) 2-12% by weight of at least one modified polyaspartic acid according to any one of claims 1 to 8;

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

(c) 15-65% by weight builder and / or co-builder

(d) 0.5-10% by weight of nonionic surfactants

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

(f) 0-8 wt% enzymes; and

(g) 0-50% by weight of additives.