ES2738320T3 - Automatic dishwashing detergent compositions comprising N-Acylglucamine - Google Patents

Abstract

Automatic dishwashing detergent composition comprising a) one or more N-Acylglucamines of formula (I) ** Formula ** or mixtures thereof, wherein R1 is a linear or branched unsaturated alkenyl group with one or more double bonds and which it comprises 15 to 17 carbon atoms, wherein 50% by weight or more of the linear or branched unsaturated alkenyl groups comprise 17 carbon atoms, R2 is hydrogen or a linear or branched saturated alkyl group comprising 1 to 4 atoms carbon, and b) one or more enhancing substances, and c) a bleaching system, and d) one or more enzymes.

Description

d e s c r ip c io n

Automatic dishwashing detergent compositions comprising N-Acylglucamine

The present invention relates to automatic dishwashing detergent compositions comprising specific N-Acylglucamines, a method of washing dishes in an automatic dishwashing machine using the inventive automatic dishwashing detergent compositions. The use of one or more of the specific N-Acylglucamines to improve the rinse performance of an inventive automatic dishwashing detergent composition, to improve the wetting of the dishes or to reduce staining and the protective film of the dishes is further described.

The automatic dishwasher, especially the domestic dishwasher, has undergone continuous changes and improvements as the format advances in the direction of all-in-one dosing systems such as tablets, bags and even dosing units, which require new surfactant systems that are effective as a rinse of surfactants against stains and film formation and show a good rinse performance while they are present throughout the wash cycle. In addition, environmental trends, such as washing at lower temperatures and with less water, reducing or even prohibiting phosphates such as sodium tripolyphosphate (STPP) and the demand for using raw materials from renewable resources (represented by the index of renewable carbon = RCI) instead of petroleum-based chemicals challenge the formulator in his choice of surfactant system. On the other hand, there is a unique requirement of very low foaming compositions, which is incompatible with most common surfactant systems that are typically used in other cleaning compositions, for example, manual dishwashing liquids, where stable foam is considered desirable. As effective and well established rinse surfactants, nonionic surfactants are used regularly, such as, for example, alkyl alcohols or alkoxylated alkyl alcohols such as ethoxylated alkyl alcohols. However, these surfactants often have the disadvantage of being based on petroleum-derived chemicals and having a low RCI. In addition, these surfactants are often not effective enough as the rinse surfactants in phosphate-free automatic dishwashing detergents.

WO 98/17759 describes detergent compositions comprising a mixture of cationic quaternary ammonium surfactant and anionic alkyl sulfate surfactant. WO 97/25397 describes detergent compositions that have beneficial skin conditioning and skin touch properties. GB-A 2292564 teaches various washing detergent compositions for cleaning dirt, particularly oily dirt and bleachable dirt. WO 97/00936 describes compositions for removing clay dirt residues. US 5,691,30o describes a process for rinsing surfaces where a composition comprising N-alkyl fatty acid N-alkylglucamides can be used.

An object of the present invention is to provide automatic dishwashing detergent compositions containing environmentally friendly rinse surfactant systems and which, in addition to a favorable cleaning performance, in particular also show improved rinse performance.

Surprisingly, it has now been found, as a general description, that this objective is achieved with automatic dishwashing detergent compositions comprising:

a) one or more N-Acylglucamines of formula (I)

or mixtures thereof, where

R1 is a linear or branched saturated alkyl group comprising 11 to 21 carbon atoms (not according to the present invention) or a linear or branched unsaturated alkenyl group with one or more double bonds and comprising 11 to 21 carbon atoms ( general description),

R2 is hydrogen or a linear or branched saturated alkyl group comprising 1 to 4 carbon atoms, and b) one or more enhancing substances, and

c) a bleaching system, and

d) one or more enzymes.

The present invention provides automatic dishwashing detergent compositions comprising a) one or more N-Acylglucamines of formula (I)

or mixtures thereof,

R1 is a linear or branched unsaturated alkenyl group with one or more double bonds and comprising 15 to 17 carbon atoms, wherein 50% by weight or more of the linear or branched unsaturated alkenyl groups comprise 17 carbon atoms,

R2 is hydrogen or a linear or branched saturated alkyl group comprising 1 to 4 carbon atoms, and b) one or more enhancing substances, and

c) a bleaching system, and

d) one or more enzymes.

Due to the presence of one or more surfactants of the formula (I), the inventive automatic dishwashing detergent compositions show improved tableware wetting, a reduction of stains and film formation of the dishes, a favorable rinse performance and a favorable cleaning performance. The surfactants of the formula (I) do not impart considerable foam and to the extent that the inventive compositions are also poorly foaming. The surfactants of formula (I) are aerobic and anaerobic biodegradable, based, due to their RICO acyl component and glucamine component, on renewable primary products with a high renewable carbon index (RCI) of 93% to 96%. Common rinse surfactants such as fatty alcohol alkoxylates generally have a renewable carbon index of less than 50%. In addition, the surfactants of formula (I) provide low aquatic toxicity and, therefore, are applicable surfactants for ecolabel products. As for the inventive automatic dishwashing detergent compositions, they are also environmentally friendly.

The inventive automatic dishwashing detergent compositions also have the advantage that one or more surfactants of formula (I) contained therein reveal their advantageous properties and, in particular, provide favorable rinse performance also in phosphate free compositions. In comparison with common low-foaming non-ionic surfactants, one or more surfactants of formula (I) lead to a similar or improved rinse performance while increasing the renewable carbon index of inventive automatic dishwashing detergent compositions.

Low-foaming non-ionic surfactants belonging to the group of rinse surfactants and which are regularly used in automatic dishwashers, for example alkyl alcohols or alkoxylated alkyl alcohols. Typical examples of such non-ionic surfactants are fatty alcohol alkoxylates, covered end fatty alcohol alkoxylates, block copolymers of propylene oxide and ethylene oxide, alkoxylated fatty acids, polyglycol ethers of fatty acids, polyglycol ethers of amide polyglycol. fatty acids, polyglycol ethers of fatty amines, ethoxylated triglycerides, mixed ethers, poly (oxyalkylated) alcohols with epoxy coating, alkyl polyglycosides, sugar esters, sorbitan esters and polysorbates. Particularly, fatty alcohol ethoxylates, fatty alcohol ethoxylate propoxylates and extreme fatty alcohol alkoxylates are used as low-foaming rinse surfactants in automatic dishwashing detergent compositions.

US 3,382,176 discloses low foaming compositions particularly for use in mechanical dishwashers containing among other alkylene oxide adducts including fatty alcohol alkoxylates, alkoxylated fatty acids, fatty acid amide polyglycol ethers, and amine polyglycol ethers of fatty acids. US 4,272,394 describes automatic dishwashing detergents containing mixtures of low-foaming nonionic surfactants composed of low-foaming nonionic surfactants based on polyoxyalkylene, including block copolymers of propylene oxide and ethylene oxide, alkoxylated fatty acids, ethers of polyglycol of fatty acid amides and polyglycol ethers of fatty amines and a second non-ionic surfactant having a low cloud point.

US 6,593,287 describes the non-ionic surfactants with an alkyl end cap and the automatic dishwashing compositions containing them.

WO 94/22800 discloses low-foaming poly (oxyalkylated) alcohols with automatic dishwasher compositions containing them.

WO 88/09369 describes a low foaming detergent composition suitable for automatic dishwashers containing alkyl polyglycosides.

N-Acylglucamines are a group of nonionic surfactants well known in the art. Typically, N-Acylglucamines are used as non-ionic surfactants in laundry detergents, personal care formulations or rinse aid formulations for machine washing. Commercial brighteners are liquid mixtures of low-foaming nonionic surfactants, organic acids such as, for example, citric acid and solvents such as, for example, ethanol and other additives such as hydrotropes, thickeners and / or foam inhibitors. Brightener formulations are typically liquid at 20 ° C and have an acidic pH value of 6 or less. Typically, brighteners are added to the dishwasher during the final rinse cycle of the dishwasher cycle. The function of the brightener is to influence the interfacial tension of the water in the final rinse cycle so that it is capable of drying from the rinsed surfaces in the form of a thin film, so that no water drops, traces or films remain during the subsequent drying process.

WO 92/06154 describes laundry detergent compositions containing N-Aeylgiucamines, detersive enzymes and anionic surfactant, non-ionic surfactant or mixtures thereof.

WO 92/06155 describes laundry detergent compositions comprising N-Acylglucamines and bleach.

WO 93/07246 describes alkaline detergents containing N-Acylglucamines, inorganic alkaline agent, complexing agent and chlorine free bleaching agent.

WO 95/02666 describes brightener formulations containing N-Acylglucamines.

The inventive automatic dishwashing detergent compositions may comprise more than one compound of formula (I). In this case, the inventive automatic dishwashing detergent compositions may comprise, for example, more than one compound of formula (I) which differ in group R1 and / or which differ in group R2.

In general, it is described that the N-Acylglucamines contained in the automatic dishwashing detergent compositions, also known as N-1-deoxysorbityl fatty acid amides or glucamides, have the formula (I)

wherein R1 is a linear or branched saturated alkyl group comprising 11 to 21 carbon atoms (not according to the present invention) or a linear or branched unsaturated alkenyl group with one or more double bonds and comprising 11 to 21 atoms of carbon (general description) and R2 is hydrogen or a linear or branched saturated alkyl group comprising 1 to 4 carbon atoms.

Preferably, in the one or more N-Acylglucamines of formula (I), R2 is a methyl group. In general, it is described that, in one or more N-Acylglucamines of formula (I), R 1 may be a linear or branched saturated alkyl group comprising 11 to 17 carbon atoms (not according to the present invention) or an alkenyl group linear or branched unsaturated with one or more double bonds and comprising 11 to 17 carbon atoms (general description). According to the present invention, in the one or more N-Acylglucamines of formula (I), R 1 is a linear or branched unsaturated alkenyl group with one or more double bonds and comprising 15 to 17 carbon atoms, wherein 50% by weight or more of the linear or branched unsaturated alkenyl groups comprise 17 carbon atoms. It is also generally described that, alternatively and not according to the present invention, the one or more N-Acylglucamines of formula (I) R 1 may be a linear or branched saturated alkyl group comprising 15 to 17 carbon atoms. It is generally described that 50% by weight or more, more preferably 60 to 99% by weight and even more preferably 70 to 98% by weight of the R1 groups in one or more N-Acylglucamines of formula (I) may be saturated linear or branched alkyl groups comprising 17 carbon atoms (not according to the present invention).

In general, it is described that at most 50% by weight, preferably 0.1 to 50% by weight, more preferably 0.5 to 40% by weight and even more preferably 1.0 to 30% by weight of the R 1 groups in the one or more N-Acylglucamines of formula (I) may be linear or branched saturated alkyl groups comprising 15 carbon atoms (not according to the present invention).

It is described that 50% by weight or more, preferably 80% by weight or more and more preferably 90% by weight or more of the R1 groups in the one or more N-Acylglucamines of formula (I) may be linear or branched unsaturated alkenyl groups with one or more double bonds.

In a particularly preferred embodiment of the invention, 50% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more of the R1 groups in the one or more N-Acylglucamines of formula (I) are linear or branched unsaturated alkenyl groups with one or more double bonds and comprising 17 carbon atoms.

Particularly preferably, in the one or more N-Acylglucamines of formula (I), R1 is a linear group.

In general, it is described that in the one or more N-Acylglucamines of formula (I) RICO can be derived from lauric acid (not according to the present invention), palmitic acid (not according to the present invention), stearic acid (not according to present invention), oleic acid, linoleic acid and / or linolenic acid. In a more preferred embodiment of the invention, in the one or more N-Acylglucamines of formula (I) RICO is derived from oleic acid, linoleic acid and / or linolenic acid and in an extraordinarily preferred embodiment of the invention, in one or more plus N-Acylglucamines of formula (I) RICO is derived from oleic acid.

The inventive automatic dishwashing detergent compositions comprise the one or more N-Acylglucamines of formula (I) preferably in amounts of 0.1 to 15% by weight, more preferably in amounts of 0.2 to 10% by weight and even more preferably in amounts of 0.2 to 5% by weight, in each case based on the total weight of the composition of the automatic dishwashing detergent.

N-methyl-N-Acylglucamines, also known as glucamides, can, as described in EP-A 0550637 and EP-A 0285768, be produced by reacting the corresponding fatty acid ester mixtures or ester mixtures of fatty acids with N-methyl-glucamine in the presence of a solvent having hydroxyl groups or alkoxy groups. Suitable solvents are, for example, C1-C4 monohydric alcohols, ethylene glycol, propylene glycol, glycerol and alkoxylated alcohols. 1,2-Propylene Glycol is preferred. N-methyl glucamine can, as also described in EP 0 550 637, be produced by reductive amination of glucose with methylamine. Suitable fatty acid esters that are converted with the N-methyl glucamines into glucamides according to formula (I) are in general the methyl esters that are obtained by transesterification of natural fats and oils, for example triglycerides.

The inventive automatic dishwashing detergent compositions further comprise one or more enhancer substances.

Enhancement substances, as well as other ingredients usable in the inventive automatic dishwashing detergent compositions, for example are described in US 2010/0160204 A1 and EP 1757676 A1.

Preferably, the inventive automatic dishwashing detergent compositions comprise one or more enhancer substances selected from the group consisting of carbonates, hydrogencarbonates, organic enhancers, preferably methyl glycosylacetic acid (MGDA), silicates, phosphates, phosphonates and alkali metal hydroxides.

It is preferred to use carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate. These substances are preferably used in amounts of 2 to 50% by weight, preferably 10 to 30% by weight, and in particular 10 to 25% by weight, based on the total weight of the inventive automatic dishwashing detergent composition.

Organic adjuvants include polycarboxylates, polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins.

Usable organic enhancers include polycarboxylic acids, which can be used in the form of free acid and / or their sodium salts, "polycarboxylic acids" being understood as those carboxylic acids that carry more than one acidic function. Examples are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids and nitrilotriacetic acid (NTA), as well as mixtures thereof. Free acids also typically have an acidifying component in addition to their enhancing effect, and therefore also serve to establish a lower and softer pH for inventive automatic dishwashing detergent compositions. In this context, they are worth mentioning, in particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, tartaric acid and any of their mixtures.

The aminocarboxylic acids that are commonly used and preferred in the context of the present invention are, for example, ethylenediaminetetraacetic acid (EDTA), methylglycacetic acid (MGDA) and glutaminediacetic acid (GLDA). It is also possible to use mixtures.

Additional preferred enhancing substances are polymeric aminodicarboxylic acids, salts thereof or precursor substances thereof. Particularly preferred polyaspartic acids, salts thereof or derivatives thereof are used.

Preferred inventive automatic dishwashing detergent compositions contain citrate as one of their enhancers. Inventive automatic dishwashing detergent compositions containing from 2 to 40% by weight, preferably from 5 to 30% by weight, and particularly preferably from 10 to 30% by weight of citrate, based on the total weight of the composition are preferred. inventive automatic dishwashing detergent.

In another preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions contain MGDA as one of their enhancers. The inventive automatic dishwashing detergent compositions preferably contain from 0.5 to 25% by weight and particularly preferably from 2 to 25% by weight of MGDA, based on the total weight of the inventive automatic dishwashing detergent composition.

Polymeric carboxylates are also suitable as organic enhancers. These are, for example, alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a relative molecular weight of 500 to 70,000 g / mol.

Suitable polymeric carboxylates are, in particular, polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Due to their higher solubility, short chain polyacrylates having molar weights of 2000 to 10,000 g / mol, and particularly preferably 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric carboxylates. Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. In particular, copolymeric carboxylates of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid and / or fumaric acid are suitable. Copolymers of acrylic acid with maleic acid containing 50 to 90% by weight of acrylic acid and 10 to 50% by weight of maleic acid have proven to be particularly suitable. Its relative molecular weight, based on free acids, is preferably from 2000 to 70,000 g / mol, more preferably from 20,000 to 50,000 g / mol, and in particular from 30,000 to 40,000 g / mol.

It is also possible to use copolymers of at least one monomer of the group consisting of C3-Cio-mono- or C4-C10-dicarboxylic monoethylenically unsaturated acids or anhydrides thereof, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilically or hydrophobically modified monomer, as indicated below.

Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butane, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, such as, for example, 1-decene, 1-dodecene, 1 -tetradecene, 1-hexadecene, 1-octahexene, 1-eicosen, 1-docosine, 1-tetracosine and 1-hexacosine, C22-a-olefin, a mixture of C2o-C24-a-oIefins and polyisobutene that have, on average , from 12 to 1O0 carbon atoms per molecule.

Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups, and also non-ionic monomers with hydroxyl function or alkylene oxide groups. Examples of the above-mentioned hydrophilic monomers are allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxy polybutylene glycol (meth) acrylate, methoxy ethylene oxide (meth) acrylate (methoxy) , (meth) ethoxypolyethylene glycol acrylate, (meth) ethoxypolypropylene glycol acrylate, (meth) ethoxy polybutylene glycol acrylate and ethoxypoly (meth) acrylate (propylene oxide-ethylene oxide). The polyalkylene glycols here may comprise from 3 to 50, in particular from 5 to 40 and especially from 10 to 30 units of alkylene oxide per molecule.

Particular preferred monomers containing sulfonic acid groups herein are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid, 2-methyl acrylamido-2-methylpropanesulfonic acid, methacrylamide , 3-methacrylamido-2-hydroxypropanesulfonic acid, aliisulfonic acid, metalylsulfonic acid, allyloxybenzenesulfonic acid, metalyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, viniIsulfonic acid, 3-suIphopropyl acrylate, 2-suIfoethio methacrylate, 3-suIphopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and salts of such acids, such as their sodium salts, potassium or ammonium salts.

Particular preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.

In addition, amphoteric polymers can be used as enhancers.

In the event that the inventive automatic dishwashing detergent compositions comprise one or more (co) polymeric carboxylates, the amount of these (co) polymeric carboxylates in the inventive automatic dishwashing detergent compositions is preferably 0.5 to 20% by weight. and in particular from 3 to 1O% by weight, based on the total weight of the inventive automatic dishwashing detergent composition.

Oxydisuccinates and other disuccinate derivatives, preferably ethylenediamine diisuccinate, are also additional preferred organic enhancers that are often also called co-potentiators. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. In addition, in this regard, preference is also given to glyceryl disuccinates and glyceryl trisuccinates as adjuvants or co-potentiators.

The inventive automatic dishwashing detergent compositions may preferably contain, as enhancers, sodium silicates in the form of a crystalline sheet of the general formula NaMSix02x + r and H20 wherein M is sodium or hydrogen; x is a number from 1.9 to 22, preferably from 1.9 to 4, with values being particularly preferred for x 2, 3 or 4; ey is a number from O to 33, preferably from O to 20.

Amorphous sodium silicates having a Na20: S02 modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8, and in particular 1: 2 to 1: 2, are also usable, 6, which are preferably delayed solution and exhibit secondary washing properties.

In case the inventive automatic dishwashing detergent compositions comprise one ^or more silicates, the amount of these silicates in the inventive compositions is preferably 5 to 30% by weight and more preferably 10 to 25% by weight, based on weight Total inventive automatic dishwashing detergent composition.

Phosphates have been shown to be effective enhancers in terms of cleaning performance. Among the many commercially available phosphates, alkali metal phosphates have the greatest importance in the washing and cleaning agents industry, particularly pentasodium triphosphate or penTapotasium (sodium ^or potassium tripolyphosphate).

"Alkali metal phosphates" is the summarized designation of the alkali metal salts (particularly sodium and potassium) of the various phosphoric acids, in whose context a distinction can be made between metaphosphoric acids (HPO3) ^m and orthophosphoric acid H3PO4, in addition to representatives of greater molecular weight. L phosphates ^will have a combination of advantages: they act as alkali carriers, prevent lime deposits on machine parts and contribute to the cleaning performance.

T ^he phosphates that are technically important are especially pentasodium triphosphate NasPaO-io (sodium tripolyphosphate) and salt of pentapotassium triphosphate corresponding K5P3O10 potassium (potassium tripolyphosphate). Additional preferred phosphates are potassium and sodium tripolyphosphates.

If phosphates are used in the inventive automatic dishwashing detergent compositions, the preferred compositions contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in amounts of 2 at 50% by weight, preferably from 2 to 30% by weight, more preferably from 3 to 25% by weight, and particularly preferably from 3 to 15% by weight, based in each case on the total weight of the detergent composition for inventive automatic dishwashers.

As additional enhancers, the inventive automatic dishwashing detergent compositions may contain one ^or more phosphonates which are often also called co-potentiators. The weight ratio of phosphonate, based on the total weight of the inventive automatic dishwashing detergent composition, is preferably 0.5 to 20% by weight, and more preferably 1.0 to 10% by weight.

L complexes ^will include several different phosphonates, diphosphonic compounds such as hydroxyethane-1,1--acid 1 (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Particularly preferred are hydroxyalkane and aminoalkanophosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance, preferably as an enhancer. It is preferably used as the sodium salt, the disodium salt reacts in a neutral manner and the tetrasodium salt in alkaline form (pH 9). Suitable aminoalkane phosphonates include ethylenediaminetetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and their higher counterparts. They are preferably used in the form of neutral reaction sodium salts (for example, as a hexasodium salt of EDTMP or as a hepta- and octasodium salt of DTPMP). From the class of phosphonates, hedp is preferred.

The inventive automatic dishwashing detergent compositions may contain additional alkali metal hydroxides as builders. These alkaline vehicles are preferably used only in small amounts, preferably in amounts of 10% by weight ^or less, more preferably 6% by weight ^or less, preferably 5% by weight or less, particularly preferably from 0.1 to 5. % by weight, and in particular from 0.5 to 5% by weight, based on the total weight of the inventive automatic dishwashing detergent composition.

In a further preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions comprise one or more enhancer substances selected from the group consisting of organic enhancers. In a particularly preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions comprise one ^or more enhancer substances selected from the group consisting of citrate, methylglycine diacetic acid (MGDA) and ethylenediamine-N, N'-disuccinate (EDDS). In an even more preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions comprise Mg DA.

The inventive automatic dishwashing detergent compositions may contain the enhancers mentioned both individually and in mixtures of two, three, four or more enhancers.

In a preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions do not comprise phosphate enhancers.

The inventive automatic dishwashing detergent compositions comprise the one or more enhancer substances preferably in amounts of 5 to 90% by weight and more preferably in amounts of 5 to 80% by weight, in each case based on the total weight of the detergent composition for inventive automatic dishwasher.

The inventive automatic dishwashing detergent compositions comprise a bleaching system.

The bleaching system of the inventive automatic dishwashing detergent compositions preferably comprises one or more substances selected from the group consisting of bleaching agents, bleaching activators and bleaching catalysts.

As a bleaching agent, the inventive automatic dishwashing detergent compositions may contain an oxygen bleaching agent. Among the compounds that serve as oxygen bleaching agents and produce H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly significant. Other usable bleaching agents include peroxypyrophosphates, citrate perhydrates and peracid or peracid salts that produce H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid, or diperdodecanedioic acid. Organic bleaching agents can also be used. Typical organic bleaching agents are diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, such as alkylperoxy acids and arylperoxy acids.

Preferably, the inventive automatic dishwashing detergent compositions comprise one or more bleaching agents selected from the group consisting of oxygen bleaching agents, preferably selected from the group consisting of peroxypyrophosphates, citrate perhydrates, peracid salts or peracids that produce H2O2 and bleaching agents organic

Particularly preferably, the inventive automatic dishwashing detergent compositions contain, based on the total weight of the composition, from 1.0 to 20% by weight, preferably from 4.0 to 18% by weight, and more preferably from 8 to 15% by weight of an oxygen bleaching agent, preferably sodium percarbonate.

In order to achieve an improved bleaching effect when cleaning at temperatures of approximately 60 ° C and below, the inventive automatic dishwashing detergent compositions may additionally comprise one or more bleach activators. Preferably, the one or more bleach activators are selected from the group consisting of compounds that, under perhydrolysis conditions, produce aliphatic peroxycarboxylic acids preferably having 1-10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances bearing O- and / or N-acyl groups having the mentioned number of carbon atoms, and / or optionally substituted benzoyl groups are suitable. Polycylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) has proven to be particularly suitable.

Bleaching activators, in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1 to 8% by weight, particularly 2 to 8% by weight, and particularly preferably 2 6% by weight, based in each case on the total weight of the bleach activator containing an inventive automatic dishwashing detergent composition.

In addition to or instead of conventional bleach activators, so-called bleach catalysts can also be used. These substances are salts of transition metals or metal complexes that improve the transition bleach such as, for example, Mn, Fe, Co, Ru or Mo complexes of salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes having tripod ligands containing nitrogen, as well as Co, Fe, Cu and Ru amine complexes, can also be used as bleaching catalysts.

It is particularly preferred to use manganese complexes in oxidation states II, III, IV or V, which preferably contain one or more macrocyclic blinding (s) having the donor functions N, NR, PR, O and / or S. Ligands having nitrogen donor functions are preferred. It is particularly preferred to use bleach catalyst (s) containing 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9- trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN), and / or 2-methyl-1 , 4,7-triazacyclononane (Me / TACN) as macromolecular ligands. Suitable manganese complexes include [M n ^ jO M jO A c MTACNMC ^, [MnmMnlv (| j-0) 2 (| J-OAc) i (TACN) 2KBPh4) 2, [Mn'V p -0) 6 (TACN) 4] (C l04) 4, [Mnm2 (j- 0) i (j-0 A c) 2 (Me-TACN) 2] (C l04) 2, [MnINMnlv (j- 0) i (j -0 A c) 2 (Me-TACN) 2] (C l04) a, [Mnlv2 (jO) 3 (Me-TACN) 2] (PF6) 2, and [MnIV2 (j- 0) 3 (Me / Me -TACN) 2] (PF6) 2 (0Ac = 0C (O) CHa).

In a further preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions comprise one or more bleach catalysts selected from the group consisting of transition metal salts and transition metal complexes that improve bleaching, preferably manganese complexes. with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN) and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me4-TACN), since the results of Cleaning can be significantly improved with these bleaching catalysts.

Preferably, the bleaching system comprises one or more bleaching agents and one or more substances selected from the group consisting of bleaching activators and bleaching catalysts. By way of particularly preferable, the bleaching system comprises one or more bleaching agents, one or more bleaching activators and one or more bleaching catalysts.

The inventive automatic dishwashing detergent compositions comprise the bleaching system preferably in amounts of 0.1 to 40% by weight, more preferably in amounts of 0.5 to 30% by weight and particularly preferably in amounts of 3 to 25% by weight, in each case based on the total weight of the inventive automatic dishwashing detergent composition.

The inventive automatic dishwashing detergent compositions also comprise one or more enzymes, preferably one or more enzymes selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases and oxidoreductases, as well as preferably mixtures thereof. These enzymes are, in principle, of natural origin. Improved variants based on natural molecules are available for use in detergent compositions for automatic dishwashers and are correspondingly preferred for use. The inventive automatic dishwashing detergent compositions comprise one or more enzymes, preferably in amounts of 1x10-6 to 5% by weight, based on active protein and, in addition, based on the total weight of the inventive automatic dishwashing detergent composition. The protein concentration can be determined by known processes, such as the BCA process or the biuret process.

A protein and / or enzyme can be protected, especially during storage, from damage such as inactivation, denaturation or decomposition (for example, the result of physical influences, oxidation or proteolytic cleavage). Proteolysis inhibition is particularly preferred in the microbial recovery of proteins and / or enzymes, particularly when the inventive automatic dishwashing detergent compositions also contain proteases. The inventive automatic dishwashing detergent compositions may contain stabilizers for this purpose; the provision of such agents in inventive automatic dishwashing detergent compositions represents a preferred embodiment of the present invention.

Particularly preferred are those inventive automatic dishwashing detergent compositions containing, based on the total weight of the composition, 0.1 to 12% by weight, preferably 0.2 to 10% by weight, and in particular 0.5 8% by weight enzyme preparation.

The inventive automatic dishwashing detergent compositions can be prepared in solid or liquid form, as well as a combination of solid and liquid forms of presentation.

The inventive automatic dishwashing detergent compositions may comprise other ingredients commonly used in automatic dishwashing detergent compositions. In a further preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions comprise one or more compounds selected from the group consisting of complexing agents, glass corrosion inhibitors, water, organic solvents, thickening agents, additional surfactants (in addition to the one or more compounds of formula (I)), suds suppressors, color spots, silver care, anti-slip agents, anti-corrosion agents, colorants, fillers, germicides, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, solubilizing agents, vehicles, processing aids, pigments and pH control agents.

Glass corrosion inhibitors are additional preferred ingredients of the inventive automatic dishwashing detergent compositions. Glass corrosion inhibitors prevent the appearance of turbidity, stains and scratches, as well as iridescence, on the glass surface of the glass that is automatically cleaned. Preferred glass corrosion inhibitors include magnesium and zinc salts and magnesium and zinc complexes.

The cleaning performance of the inventive automatic dishwashing detergent compositions can be improved by the addition of organic solvents. A preferred embodiment of the present invention is therefore detergent compositions for automatic dishwashers containing at least one organic solvent. Preferred inventive liquid automatic dishwashing detergent compositions contain, based on the total weight of the composition, an organic solvent in amounts of 0.2 to 15% by weight, preferably 0.5 to 12% by weight, and so particularly preferable from 1.0 to 10% by weight.

These organic solvents are, for example, monoalcohols, diols, triols, polyols, ethers, esters and / or amides. Organic solvents that are water soluble are particularly preferred in this context, "water soluble" solvents for the purposes of the present application are solvents that are completely miscible with water (ie, without miscibility gap) at room temperature.

Organic solvents of organic amines and / or alkanolamines are effective in cleaning performance, and particularly in regard to cleaning performance in bleachable spots, in particular tea stains.

In order to achieve the desired viscosity for inventive liquid automatic dishwashing detergent compositions, thickening agents can be added thereto. Thickening agents commonly used in detergent compositions for automatic dishwashers can also be used in inventive compositions.

It is advantageous if the respective inventive liquid automatic dishwashing detergent compositions contain the thickening agent in amounts preferably from 0.1 to 8% by weight, more preferably from 0.2 to 6% by weight, and particularly preferably from 0.4 4% by weight, based on the total weight of the inventive automatic dishwashing detergent composition.

Additional surfactants are preferably selected from the group consisting of zwitterionic surfactants, anionic surfactants and mixtures thereof.

The zwitterionic surfactant is preferably chosen from the group consisting of Ce to C-ia amine oxides (preferably C12 to Cie) and sulfo and hydroxy betaines, such as N-alkyl-N, N-dimethylamino-1-propane sulfonate wherein the alkyl group may be Cg to C18, preferably C10 to C14.

The anionic surfactant is preferably chosen from alkylethoxysulfates, with a degree of ethoxylation greater than 3, preferably from 4 to 10, and more preferably from 6 to 8, and a chain length in the range of Ce to C16 and preferably C11 to C15. Furthermore, it has been found that branched alkylcarboxylates are useful for the purpose of the present invention when branching occurs in the medium and the average total chain length is 10 to 18, preferably 12 to 16, with the lateral branching having 2 to 4 carbons in length. An example is 2-butyloctanoic acid. The anionic surfactant is typically of a type that has good solubility in the presence of calcium. Said anionic surfactants are further illustrated with sulfobetaines, alkyl (polyethoxy) sulfates (AES) and C6-C10 short chain alkyl sulfates and sulphonates. It has been shown that linear chain fatty acids are ineffective due to their sensitivity to calcium.

In a further preferred embodiment of the present invention, the inventive automatic dishwashing detergent compositions do not comprise other surfactants in addition to the one or more compounds of formula (I).

Soap suppressants, colored spots, silver care, anti-slip and / or anti-corrosive agents, dyes, fillers, germicides, hydrophores, antioxidants, enzyme stabilizing agents, perfumes, solubilizing agents, vehicles, processing aids, pigments and pH control agents can be chosen from the respective substances commonly used in automatic dishwashing detergent compositions.

In a further preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions do not comprise phosphate enhancers and, more preferably, the inventive automatic dishwashing detergent compositions do not comprise phosphates, that is, they are phosphate free.

In a further preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions are liquid at 200C. Liquid forms of presentation, preferably based on water and / or organic solvents, may exist in thick form as gels. The capsules are especially suitable as a liquid presentation form, in a single phase or in several phases. Preferably, the inventive liquid compositions comprise up to 60% by weight of water, more preferably from 10 to 60% by weight of water and even more preferably from 25 to 60% by weight of water, in each case based on the total weight of The inventive automatic dishwashing liquid detergent composition.

In a further preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions are solid at 20 oc. Powders, granulated, extruded or compacted, particularly compressed, in a single phase or in several phases, are especially suitable as solid presentation forms. The tablets are formulated for single dose applications. Preferably, the inventive solid compositions comprise less than 20% by weight of water, more preferably 0.1 to 20% by weight of water and even more preferably 0.5 to 5% by weight of water, in each case based in the total weight of the solid inventive automatic dishwashing detergent composition. In another preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions are free of water.

In an even more preferred embodiment of the invention, the inventive automatic dishwashing detergent compositions are present in the form of a tablet.

Because the high alkalinity of the inventive automatic dishwashing detergent compositions contributes to the cleaning performance of these compositions, but also the corrosive and irritating effect of these compositions, the preferred inventive automatic dishwashing detergent compositions have an alkaline pH at 20 oc of 8 to 14 oc. preferably from 9 to 11.5, and more preferably from 9.5 to 11.5, measured as a solution of 10% by weight of the inventive automatic dishwashing detergent composition, liquid or solid, in water.

The inventive automatic dishwashing detergent compositions are advantageously suitable for washing dishes in automatic dishwashing machines, whereby dirty dishes are treated in an automatic dishwashing machine with an aqueous alkaline composition comprising an inventive automatic dishwashing detergent composition.

Therefore, the present invention also provides a method for washing the dishes in an automatic dishwashing machine, which comprises treating the dirty dishes in an automatic dishwashing machine with an aqueous alkaline composition comprising an inventive automatic dishwashing detergent composition.

In the inventive method for washing dishes, the pH value of the aqueous alkaline composition is preferably 8 or more and more preferably 9 or greater.

The one or more N-Acylglucamines of formula (I) are advantageously suitable for improving the rinse performance of an inventive automatic dishwashing detergent composition, for improving the wetting of the dishes or for reducing staining and film formation of the dishes , preferably in an inventive method of washing dishes in an automatic dishwashing machine.

Therefore, the present application also further describes the use of one or more N-Acylglucamines of formula (I)

or mixtures thereof, where

R1 is a linear or branched saturated alkyl group comprising 11 to 21 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and comprising 11 to 21 carbon atoms,

R2 is hydrogen or a linear or branched saturated alkyl group comprising from 1 to 4 carbon atoms to improve the rinse performance of an automatic dishwashing detergent composition, to improve tableware wetting or to reduce staining and formation of tableware films, preferably in a method for washing the dishes in an automatic dishwashing machine.

The preferred embodiments given above for the inventive automatic dishwashing detergent compositions are also applied according to the inventive method of dishwashing in an automatic dishwashing machine. The following examples are intended to illustrate the invention in detail without, however, limiting it thereto. Unless explicitly stated otherwise, all percentages are percentages by weight (% by weight or% by weight).

Examples: Rinse performance of automatic dishwashing detergents:

The rinse performance of the F1 formulation containing N-methyl-N-oleoylglucamine was investigated. The rinse yields of formulations F2 and F3 containing N-methyl-N-C8 / io-acylglucamine or a fatty alcohol alkoxylate were tested as comparative examples.

Test conditions:

Dishwasher: Miele G 1222 SC GSL

Test plates (8 groups): 6 glasses (higher quality)

6 glasses (inferior quality)

3 polypropylene bowls

3 melamine plates

3 butters 4 knives (stainless steel; lower quality)

4 knives (stainless steel; higher quality)

3 porcelain plates (higher quality)

3 porcelain plates (lower quality)

Dishwasher program: Program 4, R = 2 without prewash

Main wash at 50 ° C

Rinse cycle at 65 ° C

Water hardness: 375.9 mg / L (21 ° dH)

Water softening: none

Detergent dosage: 18 g added in the dosing chamber before starting the test Soil: 100 g of frozen dirt added immediately after opening the dosing chamber

Brightener: None

n.0 of cleaning cycles: 4

All items, in addition to polypropylene bowls, were previously treated once with deminerated water, Neodisher A 8, citric acid and again demineralized water.

Evaluation:

The evaluation of the test dishes began earlier 30 minutes after opening the dishwasher door after completing the dishwasher cycle. In each test, the dishwasher cycles 2 - 4 were evaluated. Each test plate was evaluated according to the following classification:

Rinsing effects considered for visual qualification:

Stains Stains of different size and intensity

Contact spots Stains from contact points between dishes and parts of the dishwasher

Traces Rinse Traces

Film formation Continuous film spread evenly on the test plate Film formation Film dispersed, broken

structured

Solid waste Solid or crystalline powder residue

Fatty wastes Fatty drops or film formation

Visual rating:

10 Perfect

9 perfect to almost visible

8 almost visible

7 almost visible to visible

6 visible

5 visible to interfering

4 interfering

3 interfering to not acceptable

2 not acceptable

1 absolutely not acceptable

The combination of the seven rinsing effects mentioned above results in a score of 1 to 10 according to the previous visual rating for each test plate, a position score 1 for the worst performance, a score of 10 for the best performance. For each of the 8 groups of test dishes listed above, the average score of all the dishes in the group and the three dishwashing cycles evaluated 2 - 4 was formed. To compare the different F1 - F3 formulations, the sum of the average scores for each group of test dishes was used as general rinse performance. This leads to a theoretical maximum value with the best rinse performance of 80.0 and a theoretical minimum value with the worst rinse performance of 8.0. Compositions

The compositions of formulations F1-F3 and the values for the general rinse performance are given in the following Table A.

Table A: Composition values and general rinse performance for F1 - F3

From the results of Table A above it can be seen that the use of the inventive automatic dishwashing detergent composition F1 results in better values for rinse performance compared to the use of comparative formulations F2 and F3.

In addition, in the previous example, the inventive automatic dishwashing detergent composition F1 shows a very good overall cleaning performance.

Claims (24)

re iv in d ic ac io nes 1. Automatic dishwashing detergent composition comprising a) one or more N-Acylglucamines of formula (I)

^or mixtures thereof, where R1 is a linear or branched unsaturated alkenyl group with one or more double bonds and comprising 15 to 17 carbon atoms, wherein 50% by weight ^or more of the linear ^or branched unsaturated alkenyl groups comprise 17 carbon atoms, R2 is hydrogen or a linear or branched saturated alkyl group comprising 1 to 4 carbon atoms, and b) one or more enhancing substances, and c) a bleaching system, and d) one ^or more enzymes. 2. Automatic dishwashing detergent composition according to claim 1, characterized in that R2 in the one ^or more N-Acylglucamines of formula (I) is a methyl group. 3. Automatic dishwashing detergent composition according to claim 1 or 2, characterized in that in one or more N-Acylglucamines of formula (I) 80% by weight or more and preferably 90% by weight or more of the R1 groups are linear ^or branched unsaturated alkenyl groups with one ^or more double bonds and comprising 17 carbon atoms. 4. Automatic dishwashing detergent composition according to one ^or more of claims 1 to 3, characterized in that in the one ^or more N-Acylglucamines of formula (I), R1 is a linear group. 5. Automatic dishwashing detergent composition according to one or more of claims 1 to 4, characterized in that RICO is derived from oleic acid 6. Automatic dishwashing detergent composition according to one or more of claims 1 to 5, characterized in that it comprises one or more N-Acylglucamines of formula (I) in amounts of 0.1 to 15% by weight, preferably in amounts of 0 , 2 to 10% by weight and more preferably in amounts of 0.2 to 5% by weight, in each case based on the total weight of the automatic dishwashing detergent composition. 7. Automatic dishwashing detergent composition according to one or more of claims 1 to 6, characterized in that it comprises one ^or more enhancing substances selected from the group consisting of carbonates, hydrogen carbonates, organic enhancers, silicates, phosphates, phosphonates and alkali metal hydroxides . 8. Automatic dishwashing detergent composition according to one or more of claims 1 to 7. characterized in that it comprises one or more enhancer substances selected from the group consisting of organic enhancers. 9. Automatic dishwashing detergent composition according to one or more of claims 1 to 8, characterized in that it comprises one or more enhancer substances selected from the group consisting of citrate, methylglycine diacetic acid and ethylenediamine-N, N'-disuccinate. 10. Automatic dishwashing detergent composition according to one or more of claims 1 to 9. characterized in that it comprises one or more enhancing substances in amounts of 5 to 90% by weight and preferably in amounts of 5 to 80% by weight, in each case based on the total weight of the automatic dishwashing detergent composition. 11. Automatic dishwashing detergent composition according to one or more of claims 1 to 10, characterized in that the bleaching system comprises one or more substances selected from the group consisting of bleaching agents, bleaching activators and bleaching catalysts. 12. Automatic dishwashing detergent composition according to claim 11, characterized in that it comprises one or more bleaching agents selected from the group consisting of oxygen bleaching agents. 13. Automatic dishwashing detergent composition according to claim 11, characterized in that it comprises one or more bleaching agents selected from the group consisting of peroxypyrophosphates, citrate perhydrates, peracid or peracid salts that produce H2O2 and organic bleaching agents. 14. Automatic dishwashing detergent composition according to claim 11 to 13, characterized in that it comprises one or more bleach activators selected from the group consisting of compounds which, under perhydrolysis conditions, produce aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular from 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. 15. Automatic dishwashing detergent composition according to one or more of claims 11 to 14, characterized in that it comprises one or more bleaching catalysts selected from the group consisting of transition metal salts and transition metal complexes that improve bleaching. 16. Automatic dishwashing detergent composition according to one or more of claims 1 to 15, characterized in that it comprises the bleaching system in amounts of 0.1 to 40% by weight, preferably in amounts of 0.5 to 30% by weight and more preferably in amounts of 3 to 25% by weight, in each case based on the total weight of the inventive automatic dishwashing detergent composition. 17. Automatic dishwashing detergent composition according to one or more of claims 1 to 16, characterized in that it comprises one or more enzymes selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases and oxidoreductases. 18. Automatic dishwashing detergent composition according to one or more of claims 1 to 17, characterized in that it comprises one or more enzymes in amounts of 1x10-6 to 5% by weight, based on active proteins and also based on the total weight of The detergent composition for automatic dishwashers. 19. Automatic dishwashing detergent composition according to one or more of claims 1 to 18, characterized in that it comprises one or more compounds selected from the group consisting of complexing agents, glass corrosion inhibitors, water, organic solvents, thickening agents, additional surfactants, suds suppressants, color spots, silver care, anti-slip agents, anti-corrosion agents, dyes, fillers, germicides, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes, solubilizing agents, vehicles, processing aids , pigments and pH control agents. 20. Automatic dishwashing detergent composition according to one or more of claims 1 to 19, characterized in that it does not comprise phosphate enhancers and is preferably phosphate free. 21. Automatic dishwashing detergent composition according to one or more of claims 1 to 20, characterized in that it is solid at 20 ° C and is present as a tablet. 22. Automatic dishwashing detergent composition according to one or more of claims 1 to 21, characterized in that it has an alkaline pH at 20 ° C of 8 to 14, preferably 9 to 11.5, and more preferably 9.5 to 11.5, measured as a solution of 10% by weight of the liquid or solid composition of the automatic dishwashing detergent in water. 23. Dishwashing method in an automatic dishwasher. characterized in that the dirty dishes are treated in an automatic dishwashing machine with an aqueous alkaline composition comprising a detergent composition for automatic dishwashers according to one or more of claims 1 to 22. 24. Method according to claim 23, characterized in that the pH value of the aqueous alkaline composition is 8 or greater and preferably 9 or greater.