DE102019219861A1 - Nonionic surfactant to improve the rinsing performance in automatic dishwashing - Google Patents

Abstract

The present invention relates to dishwashing detergents with improved rinsing performance, the use of these dishwashing detergents and a method for machine dishwashing using these dishwashing detergents.

Description

The present invention relates to dishwashing detergents with improved, the use of these dishwashing detergents and a method for machine dishwashing using these dishwashing detergents.

Today, machine-washed dishes are often subject to higher requirements than manually-washed dishes. Crockery that has been completely cleaned of food residues is also rated as not flawless if, after automatic dishwashing, it still has whitish stains based on water hardness or other mineral salts, which come from dried water droplets due to a lack of wetting agent. Such formation of spots and streaks can in principle be observed on all types of surfaces (porcelain, glass, plastic, stainless steel), but in particular on glass surfaces. The use of phosphates, which act as complexing agents in dishwashing detergents, can remedy the formation of spots and streaks, but modern cleaners for automatic dishwashers are now largely phosphate-free for environmental reasons.

In order to still obtain glossy and spotless dishes, rinse aid agents are used in dishwashing formulations. As a result of the film formation on the dishes mediated by these agents, the water should run off the items to be washed as completely as possible, so that the surfaces are free of residues and have a flawlessly shiny finish at the end of the wash program.

An example of common rinse agents are non-ionic surfactants that are carried over into the rinse cycle during the rinsing process. However, such surfactants are often not compatible with liquid or solid detergent formulations. In liquid gels, for example, segregation often occurs, whereas in compressed powders the adhesive properties of the particles suffer and as a result the powders can no longer be compressed into tablets.

For this reason, there is still a need for dishwashing detergents which are distinguished by improved rinsing performance.

It has now surprisingly been found that an automatic dishwashing detergent containing at least one nonionic surfactant, as defined herein, has an excellent rinse aid performance, in particular with regard to the formation of stains on porcelain.

A first aspect of the present invention therefore relates to a phosphate-free automatic dishwashing agent, comprising at least one nonionic surfactant of the formula R ¹ O [C ₂ H ₄ O] X [C ₄ H ₈ O] _y R ² , where
R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 8 to 20 carbon atoms, in particular 10 to 18 carbon atoms, or mixtures thereof;
R ^{2 represents} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures of such hydrocarbon radicals, preferably H;
x represents values between 5 and 40, preferably between 8 to 36, in particular between 12 to 35; and
y stands for values between 1 and 20, preferably between 2 to 18, in particular between 3 to 16;

Optionally, at least one further surfactant, preferably at least one further nonionic surfactant, can be included.

The present invention also relates to the use of a dishwashing agent according to the invention in an automatic dishwashing process, in particular its use to improve the rinsing performance when cleaning dishes in an automatic dishwasher.

Yet another subject matter of the invention is an automatic dishwashing method in which a dishwashing agent according to the invention is used in particular for the purpose of improving the rinsing performance.

Finally, the use of a nonionic surfactant, as defined herein, for improving the rinsing performance of an automatic dishwashing agent is also the subject matter of the present invention.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but do not limit these and in particular the invention is not limited to these examples. Unless otherwise stated, all percentages are percentages by weight. Numeric ranges specified in the format “from x to y” include the stated values. If several preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also recorded.

"At least one" as used herein means 1 or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In relation to an ingredient, the specification refers to the type of ingredient and not to the absolute number of molecules. “At least one surfactant” thus means, for example, at least one type of surfactant, i.e. that one type of surfactant or a mixture of several different surfactants can be used. Together with weight information, the information relates to all compounds of the specified type that are contained in the composition / mixture, i.e. that the composition does not contain any further compounds of this type beyond the specified amount of the corresponding compounds.

All percentages given in connection with the compositions described herein relate, unless explicitly stated otherwise, to% by weight, in each case based on the mixture in question.

“About” or “approximately”, as used herein in connection with a numerical value, refers to the numerical value ± 10%, preferably ± 5%.

In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or derivatives thereof obtainable, for example, by ROELEN's oxo synthesis, can also be used accordingly.

Whenever alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient to balance the charge - as the anion.

A machine dishwashing agent according to the invention can be a one-component dishwashing agent or a multicomponent dishwashing agent. In the context of the present invention, the term “one-component dishwashing agent” denotes a dishwashing agent which consists of only one single component. The term “multi-component dishwashing detergent” as used herein, on the other hand, denotes a dishwashing detergent which is composed of at least two components.

In this context, the term “component” denotes a part of the dishwashing detergent which can be distinguished from any further component of the dishwashing detergent on the basis of one or more features, for example the type and / or amount of its ingredients, physical properties, external appearance, etc. Individual components of a dishwashing detergent can be in liquid or solid form.

“Liquid”, as used in the context of the present invention, denotes all flowable compositions (at 20 ° C., 1.013 bar), including gels and paste-like compositions, and also non-Newtonian liquids that have a flow limit. A “solid” composition or component, as used herein, can be a powder, granulate, or compact composition.

For example, a multicomponent dishwashing detergent as defined above can comprise one or more liquid components as defined herein and one or more solid components as defined herein. A multicomponent dishwashing detergent according to the invention can, however, also consist exclusively of two or more liquid components, or consist exclusively of two or more solid components, whereby these can be pressed together in the form of a compacted tablet, for example.

In various embodiments, the individual components of a multicomponent dishwasher detergent are spatially separated from one another, such a spatial separation being achieved, for example, by wrapping one or more individual components with a preferably water-soluble or water-dispersible packaging, so that the individual pre-portioned ones are thoroughly mixed Components are avoided with each other before the dishwashing detergent according to the invention comes into contact with water. According to some embodiments of the present invention, the automatic dishwashing agent is accordingly in particular in the form of a multi-chamber pouch.

In preferred embodiments, the inventive automatic dishwashing agent comprises at least one liquid component and is consequently either in the form of a liquid one-component dishwashing agent or in the form of a multi-component dishwashing agent comprising at least one liquid component.

According to a particularly preferred embodiment, the automatic dishwashing agent comprises at least two liquid, spatially separate components. For example, the at least two liquid components are in a water-insoluble packaging with separate chambers.

The viscosity of a liquid dishwashing agent according to the invention or one or more liquid components of the dishwashing agent according to the invention is, in some embodiments, above 230 mPa * s-1 (Brookfield instrument LVDV II +, spindle 31, 30 rpm, 20 ° C), in particular between 240 mPa * s-1 and 1000 mPa * s-1, preferably between 250 mPa * s-1 and 1000 mPa * s-1 and between 250 mPa * s-1 and 350 mPa * s-1.

According to the invention, the phosphate-free automatic dishwasher detergent is characterized in that it contains at least one nonionic surfactant of the formula R ¹ O [C ₂ H ₄ O] _x [C ₄ H ₈ O] _y R ² , where, in the above formula, R ¹ for a linear or branched aliphatic hydrocarbon radical having 8 to 20 carbon atoms, in particular 10 to 18 carbon atoms, for example 10, 12, 14, 16 or 18 carbon atoms, or mixtures thereof; R ^{2 represents} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures of such hydrocarbon radicals, preferably H; x for values between 5 and 40, preferably between 8 to 36, in particular between 12 and 35, for example 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26 , 27, 28, 29, 30, 31, 32, 33, 34, or 35; and y for values between 1 and 20, preferably between 2 to 18, in particular between 3 and 16, such as, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14.15, or 16, stands.

In various embodiments, such a nonionic surfactant, as defined above, is preferably in an amount of about 0.01 to about 15% by weight, preferably in an amount of about 0.5 to about 3.5% by weight, in each case based on the total weight of the dishwashing detergent composition, contained therein.

According to the invention, the phosphate-free automatic dishwashing agent furthermore optionally comprises at least one further surfactant, preferably at least one further surfactant from the group of nonionic surfactants.

Further nonionic surfactants which are suitable in this context for use in the automatic dishwashing agents described herein are known in the prior art.

Generally suitable, for example, without restriction, are alkyl glycosides of the general formula RO (G) _x in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms and G. is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of usable nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half that.

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

However, preference is given to using low-foaming nonionic surfactants, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The automatic dishwashing detergents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols, preferably alkoxylated fatty alcohols. Although this also includes the above-described nonionic of the formula R ¹ O [C ₂ H ₄ O] _x [C ₄ H ₈ O] _y R ² , the following definitions of further nonionic surfactants are to be understood to mean exclusively such nonionic surfactants which are different from those of the formula R ¹ O [C ₂ H ₄ O] _x [C ₄ H ₈ O] _y R ^2.

In this context, nonionic surfactants which have a melting point above room temperature are particularly preferred. Nonionic surfactants with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C., is / are particularly preferred.

Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) non-ionic surfactants are also characterized by good foam control.

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃, -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.Further preferred nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are again preferred, one to ten EO or AO groups being bonded to one another before a block from the other groups follows. Here are nonionic surfactants of the general formula

preferably in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 -alkyl or -alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another stand for whole numbers from 1 to 6.

Thus, nonionic surfactants are particularly preferred which have a C _9-15 -alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.

• - R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• - R² für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• - A, A', A'' und A''' unabhängig voneinander für einen Rest aus der Gruppe -CH₂CH₂, -CH₂CH₂-CH₂, -CH₂-CH(CH₃), -CH₂-CH₂-CH₂-CH₂, -CH₂-CH(CH₃)-CH₂-, - CH2-CH(CH2-CH3) stehen
• - w, x, y und z für Werte zwischen 0,5 und 120 stehen, wobei x, y und/oder z auch 0 sein können.

Preferred nonionic surfactants here are those of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A''O) _y - (A '''O) _z -R ² ,
in the

• - R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 -alkyl or -alkenyl radical;
• - R ^{2 represents} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• - A, A ', A "and A"' independently of one another for a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, - CH2-CH (CH2-CH3)
• - w, x, y and z stand for values between 0.5 and 120, where x, y and / or z can also be 0.

Particularly preferred are those end-capped, poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² with 1 to 30 carbon atoms, where x stands for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Also preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical with 4 up to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x stands for values between 0.5 and 1.5 and y stands for a value of at least 15.

The group of these nonionic surfactants includes, for example, the C _2-26 fatty alcohol (PO) ₁ - (EO) _{15 40} -2-hydroxyalkyl ethers, in particular also the C _8-10 fatty alcohol (PO) ₁ - (EO) ₂₂ -2- hydroxydecyl ether.

End-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O ([CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R 2 are also suitable ² independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , _{-CH 2} CH ₃ , -CH ₂ CH ₂ -CH ₃ , —CH (CH ₃ ) ₂ , but preferably represents —CH ₃ , and x and y independently of one another represent values between 1 and 32, nonionic surfactants with R ³ = —CH ₃ and values for x from 15 to 32 and y of 0.5 and 1.5 are particularly preferred.

Further nonionic surfactants which can be used with preference are the end group-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2- Butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O], [CH ₂ ] kCH (OH) [CH ₂ ] _j OR ² can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. For the R ³ radical, H, —CH ₃ or —CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units, which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen as an example and can be larger, the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .

Preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula results in R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ³ stands for H and x assumes values of 6 to 15.

• - R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht;
• - R² für einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht;
• - A für einen Rest aus der Gruppe CH₂CH₂, CH₂CH₂CH₂, CH₂CH(CH₃), vorzugsweise für CH₂CH₂ steht, und
• - w für Werte zwischen 1 und 120, vorzugsweise 10 bis 80, insbesondere 20 bis 40 steht

Finally, the nonionic surfactants of the general formula have also proven to be effective R ¹ -CH (OH) CH ₂ O- (AO) _w -R ² proven in the

• - R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 -alkyl or -alkenyl radical;
• - R ^{2 represents} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
• - A represents a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ), preferably CH ₂ CH ₂ , and
• - w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40

The group of these non-ionic surfactants are the C, especially the C _4-22 fatty alcohol include, for example (EO) -2-hydroxyalkyl ether _{10-80 8-12} fatty alcohol (EO) ₂₂ -2-hydroxydecylether and the C _4-22 fatty alcohol (EO) _40-80 -2-hydroxyalkyl ethers.

In various embodiments of the invention, instead of the end-capped hydroxy mixed ethers defined above, it is also possible to use the corresponding non-end-capped hydroxy mixed ethers. These can satisfy the above formulas, but where R ² is hydrogen and R ¹ , R ³ , A, A ', A ", A"', w, x, y and z are as defined above.

The agents described herein contain, in various embodiments, the at least one further nonionic surfactant, as defined above, in an amount of at least about 0.01% by weight, preferably at least about 0.05% by weight, based in each case on the Total weight of the agent. In various embodiments, an agent as described herein contains at least one further nonionic surfactant, in particular in an amount of approximately 0.01 to approximately 15% by weight, preferably in an amount of approximately 0.5 to approximately 3.5% by weight, each based on the total weight of the dishwashing detergent composition. The absolute amounts of surfactant used per application can, for example, be in the range from 0.1-5 g / job, preferably in the range from 0.2-0.8 g / job.

According to the invention, the automatic dishwashing agent described herein is phosphate-free. In the context of the present invention, the term “phosphate-free” means that the corresponding agents are essentially free of phosphate, ie that, in the context of the present invention, phosphate in amounts of less than 1% by weight, preferably less than 0.1 % By weight, is contained in the agents, in each case based on the total weight of the respective dishwashing detergent composition. Most preferably, the dishwashing detergent according to the invention is completely free from phosphate. This means that no phosphate is deliberately added.

In various embodiments, the dishwashing detergent according to the invention also contains at least one builder selected from the group consisting of aminocarboxylic acids and their salts, preferably selected from the group consisting of methylglycine diacetic acid (MGDA) and its salts, glutamine diacetic acid (GLDA) and its salts, ethylene diamine diacetic acid (EDDS) and its salts, iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). The content of these aminocarboxylic acids or their salts can, in some embodiments, for example between approximately 0.1 and approximately 30% by weight, preferably between approximately 1 and approximately 25% by weight and in particular between approximately 5 and approximately 20% by weight. - Make up%, each based on the total weight of the dishwashing detergent composition.

In some embodiments, the at least one builder is preferably selected from the group consisting of methylglycine diacetic acid (MGDA) and glutamine diacetic acid (GLDA).

In various embodiments, the agents according to the invention can contain further constituents, ie at least one further constituent, preferably at least two further constituents, which are usually used in dishwasher detergents, preferably selected from the group consisting of further surfactants, further builders, enzymes, thickeners, Sequestrants, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances and antimicrobial agents.

All anionic surface-active substances are suitable as anionic surfactants in the detergents or cleaning agents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups.

Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group.

Preferred anionic surfactants in the detergents or cleaning agents are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Instead of the aforementioned anionic surfactants or in conjunction with them, cationic and / or amphoteric surfactants can also be used.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and ^iv and R ^v denote identical or different alkyl radicals with 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyldimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -alkylamidopropyl-d-imethylcarboxymethylbetaine.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix represent} four identical or different types, in particular two long and two short-chain, alkyl radicals and X- stand for an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.

In machine dishwashing detergents, the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight . Machine dishwashing detergents which do not contain any cationic or amphoteric surfactants are particularly preferred.

In some embodiments, the dishwashing detergent according to the invention contains at least one dye.

Preferred dyes, the choice of which does not present any difficulty to the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the dishwashing detergent according to the invention and to light.

In some embodiments, the dishwashing detergent according to the invention furthermore contains at least one further builder.

Since the agent described herein is free of phosphates according to the invention, as defined above, suitable alternative builders are generally in particular silicates, aluminum silicates (especially zeolites), carbonates, organic di- and polycarboxylic acids and aminocarboxylic acids or their salts. Mixtures of these substances can of course also be used.

It is possible, for example, to use crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} · y H ₂ O, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particular preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} · y H ₂ O are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ · x H ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ · x H ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ · x H ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ · x H ₂ O, Makatite). _{Crystalline sheet silicates of the formula NaMSi x} O _{2x + 1} · y H ₂ O, in which x is 2, are particularly suitable for the purposes of the present invention. In particular, both ß- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ · y H ₂ O and, furthermore, above all Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , Natrosilit), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3 H ₂ O, Kanemite), Na-SKS-11 ( t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) is preferred.

Machine dishwashing detergents typically contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} · y H ₂ O of 0.1 to 20% by weight, preferably 0.2 to 15% by weight and in particular 0, 4 to 10% by weight, based in each case on the total weight of these agents.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are preferably delayed in dissolution and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be achieved in various ways, for example by surface treatment, Compounding, compaction / densification or caused by overdrying. In the context of this invention, the term “amorphous” is understood to mean that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays that have a width of several degree units of the diffraction angle , cause.

In the context of the present invention, it is preferred that this (s) silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali metal disilicates, in the agents in amounts of 1 to 40% by weight, preferably from 2 to 35% by weight. -%, each based on the weight of the automatic dishwashing detergent, are included.

The dishwashing detergents can in particular also contain phosphonates as a further builder. A hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. Phosphonates are contained in the agents preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, based in each case on the total weight of the dishwashing detergent.

Other builders are the alkali carriers. Alkali carriers include, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the mentioned alkali silicates, alkali metasilicates, and mixtures of the aforementioned substances, whereby for the purposes of this invention the alkali carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate can preferably be used. Due to their low chemical compatibility with the other ingredients of automatic dishwashing detergents in comparison with other builder substances, the optional alkali metal hydroxides are preferably only used in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 % By weight and in particular below 2% by weight, based in each case on the total weight of the automatic dishwashing agent, are used. Agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides are particularly preferred.

The use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular, is particularly preferred from 7.5 to 30% by weight, based in each case on the weight of the automatic dishwashing agent. Agents which, based on the weight of the automatic dishwashing detergent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate (e ) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.

Organic builders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and the phosphonates already mentioned above as builders. These substance classes are described below.

Organic builder substances which can be used are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, as well as mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for automatic dishwashing detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.

The use of citric acid and / or citrates in these agents has proven to be particularly advantageous for the cleaning and rinsing performance of the agents described herein. Automatic dishwashing agents are therefore preferred, characterized in that the automatic dishwashing agent contains citric acid or a salt of citric acid.

The dishwashing detergents according to the invention can also contain a sulfopolymer. The proportion by weight of the sulfopolymer in the total weight of the dishwashing detergent according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably 1.0 to 15% by weight, in particular from 4 to 14% by weight, especially 6 up to 12% by weight. The sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70% by weight, in particular 30 to 50% by weight, preferably about 35 to 40% by weight, sulfopolymers.

A copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfopolymer.

The copolymers can have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain, in addition to monomer (s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.

The unsaturated carboxylic acid (s) used is / are with particular preference unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH, in which R ¹ to R ³ independently of one another represent -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or for -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenyl acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. The unsaturated dicarboxylic acids can of course also be used.

The monomers containing sulfonic acid groups are those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H preferred, in which R ⁵ to R ⁷ independently of one another for -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, with - NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - , -C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Preferred among these monomers are those of the formulas H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX- (R ¹ ) C = C (R ¹ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ and -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) n- with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ -, - C (O) -NH-C (CH ₃ ) ₂ -CH ₂ - and -C (O) -NH-CH (CH ₃ ) -CH ₂ -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3 -sulphatosulphonyl, vinylsulphopropyl, styrenesulphonate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.

In the polymers, the sulfonic acid groups can be completely or partially in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers used with preference is, in the case of copolymers which only contain monomers containing carboxylic acid groups and monomers containing sulphonic acid groups, preferably in each case from 5 to 95% by weight; the proportion of the monomer containing sulphonic acid groups is particularly preferably 50 to 90% by weight. and the proportion of the monomer containing carboxylic acid groups is 10 to 50% by weight, the monomers here being preferably selected from those mentioned above.

The molar mass of the preferably used sulfo copolymers can be varied in order to adapt the properties of the polymers to the desired use. Preferred dishwashing detergents are characterized in that the copolymers have molecular weights from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

The dishwashing detergents can also contain other polymers. The group of suitable polymers includes, in particular, the cleaning-active polymers, for example the rinse aid polymers and / or polymers that act as softeners.

Preferred polymers that can be used come from the group of the alkyl acrylamide / acrylic acid copolymers, the alkyl acrylamide / methacrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid copolymers, the alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

Other polymers that can be used come from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine / methacrylate copolymers.

Cationic polymers which can be used originate from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, the copolymers of vinylpyrrolidino with quaternylated derivatives of dialkylamino-acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as builders.

In liquid dishwashing detergents, preference is given to using soluble builders, such as citric acid, or acrylic polymers with a molar mass of 1,000 to 5,000 g / mol.

In some embodiments, the agent described herein, as defined above, furthermore contains at least one enzyme, in particular in the form of an enzyme preparation.

In some embodiments, the enzyme preparations or enzyme compositions of the dishwashing detergents according to the invention contain at least one protease and optionally one or more further enzymes. Further suitable enzymes include, but are not limited to, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in cleaning agents, which are accordingly preferred. ^{Cleaning agents according} to the invention preferably contain enzymes in total amounts of 1 × 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined with the aid of known methods, for example the BCA method or the biuret method.

Proteases are among the technically most important enzymes of all. For detergents and cleaning agents, they are the longest established enzymes and are contained in practically all modern, high-performance washing and cleaning agents. They cause the breakdown of protein-containing soiling on the Items to be cleaned. Among these, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are serine proteases due to the catalytically active amino acids. They act as non-specific endopeptidases and hydrolyze any acid amide bonds that are inside peptides or proteins. Their pH optimum is usually in the clearly alkaline range. The article, for example, provides an overview of this family “Subtilases: Subtilisin-like Proteases” by R. Siezen, pages 75-95 in “Subtilisin enzymes”, edited by R. Bott and C. Betzel, New York, 1996 . Subtilases are naturally produced by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species should be mentioned as the most important group within the subtilases.

Examples of the proteases of the subtilisin type preferably used according to the invention are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the subtilases, not but rather the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which can be assigned to the subtilisins in the narrower sense, as well as variants of the proteases mentioned, which have a modified amino acid sequence compared to the starting protease. Proteases are modified in a targeted or random manner by methods known from the prior art and thus optimized for use in detergents and cleaning agents, for example. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. For most of the proteases known from the prior art, correspondingly optimized variants are known.

Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the improved further developments of the aforementioned amylases for use in cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized.

According to the invention, lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid substitution D96L.

It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

According to the invention, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.

A protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and / or enzymes, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes as are enclosed in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.

It is also possible to pack two or more enzymes together so that a single granulate has several enzyme activities.

As can be seen from the previous statements, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.

Dishwashing detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations are particularly preferred.

As can be seen from the previous statements, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention contain from 1 to 40% by weight, preferably from 2 to 30% by weight, particularly preferably from 3 to 25% by weight, of the enzyme protein. Particularly preferred cleaning agents are those which, based in each case on their total weight, 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of the respective enzyme preparations contain.

The compositions described herein can also include enzyme stabilizers. One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are often used for this purpose, including, in particular, derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Peptide aldehydes, that is to say oligopeptides with a reduced C-terminus, in particular those made from 2 to 50 monomers, are also used for this purpose. The peptide reversible protease inhibitors include ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are also suitable for this purpose.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as, for example, succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are capable of, as in WO 97/18287 discloses additionally stabilizing a contained enzyme.

Further enzyme stabilizers are known to the person skilled in the art from the prior art.

In various embodiments, the dishwashing detergent as described herein comprises at least one bleaching agent.

Bleaching agents are substances that are active in washing or cleaning. Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H ₂ O _{2 in water.} Further bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates and _{peracid salts or peracids which provide H 2} O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. All other inorganic or organic peroxy bleaches known to the person skilled in the art from the prior art can also be used. According to the invention, the percarbonates and here in particular sodium percarbonate are particularly preferred bleaching agents.

According to the invention, automatic dishwashing agents are preferred which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight and in particular 5 to 15% by weight of bleaching agent, preferably sodium percarbonate , contain.

In various embodiments of the invention, the automatic dishwashing agents additionally contain at least one bleach activator. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the art from the prior art, multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferred. Combinations of conventional bleach activators can also be used. According to the invention, TAED, in particular in combination with a percarbonate bleach, preferably sodium percarbonate, is very particularly preferred as the bleach activator.

These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and particularly preferably 2 to 6% by weight, each based on the total weight of the bleach activator-containing agents used.

In general, the pH value of the cleaning agent can be adjusted by means of conventional pH regulators, the pH value being selected depending on the intended use. In various embodiments, the pH is in a range from 5.5 to 10.5, preferably 5.5 to 9.5, even more preferably 7 to 9, in particular greater than 7, especially in the range 7.5 to 8.5 . Acids and / or alkalis, preferably alkalis, are used as pH adjusting agents. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, the mineral acids, hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred. However, volatile alkali is particularly preferred, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and propanolamine and mixtures thereof. The alkanolamine is contained in agents according to the invention preferably in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight.

To adjust and / or stabilize the pH, the agent according to the invention can contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents). Particularly preferred buffer substances are citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate · 2H ₂ O and tripotassium citrate H ₂ O.

In the dishwashing detergents according to the invention it is also possible to use glass corrosion inhibitors which prevent the occurrence of cloudiness, streaks and scratches, but also the iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of the magnesium and zinc salts and the magnesium and zinc complexes. In the context of the present invention, the content of zinc salt in automatic dishwashing detergents is preferably between 0.05 to 5% by weight, preferably between 0.2 to 4% by weight and in particular between 0.4 to 3% by weight, or the content of zinc in oxidized form (calculated as Zn ²⁺ ) between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight .-%, each based on the total weight of the agent.

In the context of the present invention, individual odoriferous compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type can be used as perfume oils or fragrances. However, it is preferred to use mixtures of different fragrances which together produce an appealing fragrance note. Such perfume oils can also contain natural odorant mixtures, such as those obtainable from vegetable sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

Preservatives can also be contained in the agents. For example, preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surfactants Compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) -bis- (1-octanamine) -dihydrochloride, N, N'-bis- (4- Chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surface-active compounds, guanidines. Particularly preferred preservatives, however, are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

In some embodiments, a dishwasher detergent according to the invention, in particular a liquid dishwasher detergent according to the invention, as defined herein, can contain water. However, the dishwashing detergents according to the invention are preferably low-water to water-free dishwashing detergents, the water content being less than 20% by weight and preferably less than 15% by weight, even more preferably less than 10% by weight, based in each case on the total dishwashing detergent.

In addition, non-aqueous solvents can be added to the dishwashing detergent. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ether, ethylene glycol propyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, 1-butoxyethoxy-2-propanol, propylene-butoxyethoxy-2-propanol, propylene-butoxy-3-butyl ether, and mixtures of these n-butoxyethoxy-2-propanol, 3-butyl-3-butylether, propylene, propylene-octanol, propylene-octanolether, propylene-butyl-3-ethanol, propylene-butoxyethoxy-2-propanol, propylene-butoxyethoxy-2-propanol, propylene-butoxy-3-butylether, propylene-butoxyethoxy-2-propanol, propylene-butoxyethoxy-2-propanol, propylene-butoxy-3-ether, propylene-butoxy-3-ether, propylene glycol propylether, dipropylene glycol monomethylether, 3-butyl-3-meth Solvent.

The automatic dishwashing detergents described herein can be in pre-portioned form, i.e. they are pre-packaged into dosage units. These metering units preferably comprise the amount of cleaning-active substances necessary for a cleaning cycle. Preferred dosing units have a weight between 8 and 30 g, preferably between 10 and 26 g and in particular between 12 and 22 g. The volume of the aforementioned metering units and their spatial shape are particularly preferably selected so that the pre-assembled units can be metered via the metering chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

In correspondingly preferred embodiments, the automatic dishwashing agent is pre-portioned in a water-soluble or water-dispersible package.

The water-soluble or water-dispersible packaging is preferably formed by a water-soluble or water-dispersible film material.

Such packaging can be produced either by vertical form fill sealing (VFFS) or thermoforming processes.

The thermoforming process generally includes forming a first layer of a water-soluble sheet material to form bulges for receiving a composition therein, pouring the respective composition into the bulges, covering the bulges filled with the composition with a second layer of a water-soluble sheet material and sealing the first and second layers with one another at least around the bulges.

The water-soluble or water-dispersible packaging is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. This covering can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if any, can be the same or different. Particularly preferred are foils which, for example, can be glued and / or sealed to form packaging such as tubes or pillows after they have been filled with an agent. In various embodiments, the foils are in the form of Multi-chamber pouches, with individual components of the automatic dishwashing agent, as defined herein, being spatially separated in different chambers of a pouch made of a water-soluble film.

According to some embodiments it is preferred that the water-soluble or water-dispersible packaging comprises polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble casings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility.

Suitable water-soluble films for producing such coverings are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol ^-1 , preferably from 20,000 to 500,000 gmol ^-1 , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol is usually done by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

A polyvinyl alcohol-containing film material suitable for producing the water-soluble envelope can additionally contain a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers may be added. A preferred additional polymer are polylactic acids.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include vinyl alcohol as well as an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof in addition to vinyl alcohol.

It can be preferred that the film material contains further additives. The film material can for example contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerine, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-stick agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble envelopes of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The water-soluble packaging can have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.

The corresponding use of the dishwashing detergent according to the invention is also an object of the invention. The invention also relates to an automatic dishwashing method in which a dishwashing agent according to the present invention is used. The present application therefore also relates to a method for cleaning dishes in a dishwasher, in which the agent according to the invention is metered into the interior of a dishwasher while a dishwasher program is running before the start of the main wash cycle or during the main wash cycle. The metering or introduction of the agent according to the invention into the interior of the dishwasher can take place manually, but the agent is preferably metered into the interior of the dishwasher by means of the metering chamber.

Finally, the present invention is also directed to the use of a nonionic surfactant to improve the rinsing performance of an automatic dishwasher detergent, characterized in that the nonionic surfactant is a nonionic surfactant of the formula R ¹ O [C ₂ H ₄ O] _x [C ₄ H ₈ O ] _{y is} R ² , where
R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 8 to 20 carbon atoms, in particular 10 to 18 carbon atoms, or mixtures thereof; R ^{2 represents} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures of such hydrocarbon radicals, preferably H;
x represents values between 5 and 40, preferably between 8 to 36, in particular between 12 to 35; and
y stands for values between 1 and 20, preferably between 2 and 18, in particular between 3 and 16.

The preferred embodiments described in connection with the compositions according to the invention can consequently be transferred to the dishwashing detergents and the uses and methods described herein, and vice versa.

Examples

Example 1: rinse aid with different additives

Of the freshly prepared formulations, 35.5 g plus 0.5 g of additive were used per wash cycle. The rinse aid tests were carried out in a Miele GSL 2 with the program R50 ° C / 8 min / KI65 ° C with a water hardness of 21 ° dH in the presence of 100 g ballast dirt (4 g margarine, 4 g potato starch, 1.6 g NaCl, 16 g whole egg, 74.4 g water). The items to be washed were evaluated visually by comparing them with a reference scale (5 = no stains or deposits; 1 = very strong stains or deposits). The arithmetic mean values (n = 3) are shown. Table 1 V1 V2 V3 V4 V5 V6 E1 E2 Wt% MGDA, trisodium salt 6.4 6.4 6.4 6.4 6.4 6.4 6.4 6.4 Polycarboxylate (Acusol 810) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Sorbitol (70% in water) 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Polymer containing sulfonic acid groups (Acusol 590) 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Mirapol Surf S 480PF 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Protease (% by weight of active enzyme) 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 Amylase (% by weight of active enzyme) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 HEDP (60% in water) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 NaOH (45%) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Sodium citrate 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 soda 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 water Ad 100 Additive g / rinse Lutensol AO 3 - 0.5 - - - - - - Lutensol TO 3 - - 0.5 - - - - - Lutensol XP 30 - - - 0.5 - - - - Lutensol ON 30 - - - - 0.5 - - - Genapol EP 2464 - - - - - 0.5 - - Plurafac LF 221 - - - - - - 0.5 - Nonionic surfactant, which falls under the formula R ¹ O [C ₂ H ₄ O] _5-40 [C ₄ H ₈ O] _1-20 H, with R ¹ = aliphatic C _10-18 hydrocarbon radical - - - - - - - 0.5 Staining Glass 1.4 0.8 0.1 1.7 0.9 2.0 2.2 2.2 stainless steel 1.2 1.2 1.7 1.6 1.8 1.8 2.0 3.4 porcelain 1.6 1.9 1.1 1.0 1.9 1.7 2.7 4.1 plastic 1.4 1.3 1.4 1.7 1.5 1.2 2.1 1.9 Film formation Glass 1.2 1.1 1.9 1.9 1.3 2.0 2.5 2.5 stainless steel 1.7 2.8 3.7 3.2 3.2 4.0 3.7 3.2 porcelain 1.0 1.0 1.8 2.1 1.2 2.7 1.6 2.9 plastic 3.4 3.7 3.2 4.4 3.7 4.1 4.0 5.0

These comparative tests show that nonionic surfactants can improve the rinsing performance selectively, but only with the inventive examples E1 and E2, in particular with the inventive example E2, does a satisfactory picture emerge for all materials (glass, stainless steel, porcelain, plastic). In particular, there is a particularly low level of staining on porcelain.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• WO 9718287 [0109]

Non-patent literature cited

• “Subtilases: Subtilisin-like Proteases” by R. Siezen, pages 75-95 in “Subtilisin enzymes”, edited by R. Bott and C. Betzel, New York, 1996 [0095]

Claims (9)

Phosphate-free automatic dishwashing agent, comprising at least one nonionic surfactant of the formula R ¹ O [C ₂ H ₄ O] X [C ₄ H ₈ O] _y R ² , where R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 8 to 20 carbon atoms, in particular 10 to 18 carbon atoms, or mixtures thereof; R ^{2 represents} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures of such hydrocarbon radicals, preferably H; x represents values between 5 and 40, preferably between 8 to 36, in particular between 12 to 35; and y stands for values between 1 and 20, preferably between 2 to 18, in particular between 3 to 16. Add the dishwashing detergent Claim 1 , characterized in that the at least one nonionic surfactant of the formula R ¹ O [C ₂ H ₄ O] X [C ₄ H ₈ O] _y R ² , as in Claim 1 defined, in an amount of about 0.01 to about 15 wt .-%, preferably in an amount of about 0.5 to about 3.5 wt .-%, each based on the total weight of the dishwashing detergent composition contained therein. Add the dishwashing detergent Claim 1 or Claim 2 , characterized in that it further contains at least one builder selected from the group consisting of aminocarboxylic acids and their salts, preferably from the group consisting of methylglycine diacetic acid (MGDA) and its salts, glutamine diacetic acid (GLDA) and its salts, ethylenediamine diacetic acid (EDDS) and their salts, iminodisuccinic acid (IDS) and iminodiacetic acid (IDA). Add the dishwashing detergent Claim 3 , characterized in that the content of the at least one builder in the dishwashing detergent is between 0.1 and 30% by weight, preferably between 1 and 25% by weight and in particular between 5 and 20% by weight, in each case based on the Total weight of dishwashing detergent. Dishwashing detergent according to one of the Claims 1 to 4th , characterized in that the dishwashing detergent has at least one further component, preferably at least two further components, selected from the group consisting of further surfactants, further builders, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances , Bitter substances and antimicrobial agents. Dishwashing detergent according to one of the Claims 1 to 5 , characterized in that it contains at least one further surfactant, preferably at least one further nonionic surfactant. Use of a dishwashing detergent according to one of the Claims 1 to 6th in a machine dishwashing process. Automatic dishwashing method, characterized in that a dishwashing agent according to one of the Claims 1 to 6th is used. Use of a nonionic surfactant to improve the rinsing performance of a machine dishwashing agent, characterized in that the nonionic surfactant is a nonionic surfactant of the formula R ¹ 0 [C ₂ H ₄ O] _x [C ₄ H ₈ O] _y R ² , where R ¹ represents a linear or branched aliphatic hydrocarbon radical having 8 to 20 carbon atoms, in particular 10 to 18 carbon atoms, or mixtures thereof; R ^{2 represents} H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures of such hydrocarbon radicals, preferably H; x represents values between 5 and 40, preferably between 8 to 36, in particular between 12 to 35; and y stands for values between 1 and 20, preferably between 2 to 18, in particular between 3 to 16.