EP3842510A1 - Rinse aid for automatic dishwashers - Google Patents

Abstract

The invention relates to a rinse aid for machine dishwashing containing at least one nonionic surfactant and at least one polyol. The invention also relates to an automatic dishwashing process using the claimed agent. The invention also relates to the use of nonionic surfactant and polyol in automatic dishwashing processes to improve the rinsing performance.

Description

The present invention relates to a rinse aid for automatic dishwashers which comprises at least one nonionic surfactant and at least one polyol. The present invention also relates to the use of nonionic surfactants and polyol to improve the rinsing performance. The present invention also relates to an automatic dishwashing method using an agent of the present invention.

Today, machine-washed dishes are often subject to higher requirements than manually-washed dishes. After machine cleaning, the dishes should not only be free of food residues, but should also not have any whitish stains due to water hardness or other mineral salts, which come from dried water droplets due to the lack of wetting agents. Such spots and streaks can in principle be observed on surfaces of all types (porcelain, glass, plastic, stainless steel). Particularly with dishes that are not used in everyday life but are used for festive occasions, consumers pay great attention to shine and freedom from stains. This tableware in particular is post-treated by the consumer - often by hand - which is not very user-friendly.

At the same time, the formulation of agents for automatic dishwashing regularly presents the person skilled in the art with challenges, since high-performance ingredients often cannot be incorporated into existing formulations in a stable manner. Possible phase separations during storage lead to an unattractive appearance and reduce the performance of the agents immensely. In addition, the consumer perceives clear agents to be more powerful in terms of rinsing performance than opaque agents.

There is therefore a need for agents for machine dishwashing which reduce the formation of so-called spotting and / or filming stains and / or deposits and at the same time are storage-stable and appealing to the consumer.

It was surprisingly found that the joint use of nonionic surfactant and polyol leads to a significantly improved rinse aid performance.

The object on which the present invention is based has therefore been achieved by a rinse aid for machine dishwashing containing at least one nonionic surfactant and at least one polyol.

A first subject of the present application is therefore a rinse aid for machine dishwashing containing at least one nonionic surfactant and at least one polyol.

The present application also relates to the use of nonionic surfactants and polyol to improve the rinsing performance.

Yet another subject matter of the present application is an automatic dishwashing process using an agent according to the 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 not to restrict it, and in particular the invention is not limited to these examples. Unless otherwise stated, all percentages are percentages by weight. Numeric ranges given 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 meant. 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.

The agent according to the invention is preferably phosphate-free; this means that the agents according to the invention are preferably essentially phosphate-free, i.e. contain phosphate in amounts less than 1% by weight, preferably less than 0.1% by weight, and / or contain no deliberately added phosphate.

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 having 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.

All surfactants of this type known to those skilled in the art can be used as the nonionic surfactant. The agent according to the invention preferably contains 10 to 60% by weight of nonionic surfactant, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight.

A preferred subject of the present application is therefore a rinse aid which contains 10 to 60% by weight of nonionic surfactant, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight, based on the total amount of rinse aid, having.

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.

Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants. The rinsing agents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols, preferably alkoxylated fatty alcohols.

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.

Alkoxylated alcohols, in particular ethoxylated primary alcohols, particularly preferably ethoxylated and additionally otherwise alkoxylated primary alcohols, are preferably used as nonionic surfactants in the rinse aid according to the invention. It can be, for example, ethoxylated and propoxylated primary alcohols and / or ethoxylated and butoxylated primary alcohols.

According to the invention, the rinse aid is characterized in that it preferably contains a 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 aforementioned formula, R ^{1 is} a linear one 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 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 from 10 to approximately 60% by weight, preferably in an amount from 20 to approximately 55% by weight, particularly preferably in an amount from 30 to approximately 50% by weight, based in each case on the total weight of the rinse aid composition, contained therein.

A preferred subject of the present application is therefore a rinse aid which contains 10 to 60% by weight of nonionic surfactant of the formula R ¹ O [C ₂ H ₄ O] _x [C ₄ H ₈ O] _y R ² , in which case, in the aforementioned Formula, R ^{1 represents} 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 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, is particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight, based on the total amount of rinse aid.

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 residue 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 -, - CH ₂ -CH (CH ₂ -CH ₃ ),
• 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.

, Especially the C (EO) -2-hydroxyalkyl ether _{15-40 8-10} fatty alcohol (PO) ₁ - - to the group of these nonionic surfactants include the C _2-26 fatty alcohol, for example (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} 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 _{stands for -CH 3} , and x and y independently of one another stand for values between 1 and 32, nonionic surfactants with R ³ = -CH ₃ and values for x from 15 to 32 and y from 0.5 and 1.5 are very 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] _x [CH ₂ ] _k CH (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 nonionic surfactants includes, for example, the C _4-22 fatty alcohol (EO) _10-80 -2-hydroxyalkyl ethers, in particular also the C _8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ethers 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, the corresponding non-end-capped hydroxy mixed ethers can also be used. 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.

Anionic, cationic and / or amphoteric surfactants can be used in the rinse aid according to the invention.

All anionic surface-active substances are suitable as anionic surfactants in the rinse aid. 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 as well as 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 -alkyl-dimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -alkylamidopropyl-dimethylcarboxymethylbetaine.

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. Through the use of quaternary surface-active compounds with an antimicrobial effect, the agent can with an antimicrobial effect or whose antimicrobial effect, which may already be present due to other ingredients, can be improved.

In machine rinse aids, the content of antionic, cationic and / or amphoteric surfactants is preferably less than 6% by weight, more preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. -%. Rinse aids which do not contain any anionic, cationic or amphoteric surfactants are particularly preferred.

One or more polyols can be used in the composition according to the invention. Polyols are organic compounds that contain several hydroxyl groups. Several here means that there are more than one and thus at least two hydroxyl groups per molecule. Likewise, polyols can have more than two, that is to say three or four or more, hydroxyl groups.

The rinse aid according to the invention preferably contains ethylene glycol, propane-1,2-diol, propane-1,3-diol, dipropylene glycol or mixtures thereof as polyol. In this application, dipropylene glycol denotes a mixture of the isomers 1,1'-oxydi-2-propanol, 2,2'-oxydi-1-propanol and 2- (2-hydroxypropoxy) -1-propanol, 1,1'-oxydi -2-propanol is the dominant isomer in terms of quantity in this mixture. The agent according to the invention particularly preferably contains propane-1,2-diol and / or propane-1,3-diol, very particularly preferably it contains propane-1,2-diol.

A preferred subject of the present application is therefore a rinse aid in which the polyol is selected from the group of ethylene glycol, propane-1,2-diol, propane-1,3-diol, dipropylene glycol or mixtures thereof, particularly preferably from propane-1 , 2-diol and / or propane-1,3-diol, very particularly preferably it contains propane-1,2-diol.

The agent according to the invention contains at least one nonionic surfactant and at least one polyol. In a preferred embodiment, nonionic surfactant and polyol are present in the agent according to the invention in a weight ratio of 4: 1 to 1: 4, preferably 3: 1 to 1: 3, particularly preferably 3: 2 to 2: 3, to one another.

A preferred article is therefore a rinse aid in which nonionic surfactant and polyol are present in a weight ratio of 4: 1 to 1: 4, preferably 3: 1 to 1: 3, particularly preferably 3: 2 to 2: 3, to one another.

Another preferred subject is also a rinse aid in which the polyol is selected from the group of ethylene glycol, propane-1,2-diol, propane-1,3-diol, dipropylene glycol or mixtures thereof, particularly preferably from propane-1,2 -diol and / or propane-1,3-diol, very particularly preferably the at least one polyol is propane-1,2-diol, and / or in which nonionic surfactant and polyol are present in a weight ratio of from 4: 1 to 1: 4, preferably from 3: 1 to 1: 3, particularly preferably from 3: 2 to 2: 3, to one another.

The agent according to the invention preferably contains 10 to 60% by weight of polyol, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight.

A preferred subject of the present application is therefore a rinse aid which has 10 to 60% by weight of polyol, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight, based on the total amount of rinse aid .

Another preferred object is therefore a rinse aid which has 10 to 60% by weight of polyol, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight and / or which has 10 to 60% by weight. % nonionic surfactant, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight, based in each case on the total amount of rinse aid.

In addition, a preferred item is a rinse aid which has 10 to 60% by weight of polyol, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight and / or which has 10 to 60% by weight nonionic surfactant, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight, in each case based on the total amount of rinse aid, and in which the polyol is selected from the group of ethylene glycol, propane-1, 2-diol, propane-1,3-diol, dipropylene glycol or mixtures thereof, particularly preferably from propane-1,2-diol and / or propane-1,3-diol, very particularly preferably the at least one polyol propane-1, 2-diol.

Automatic dishwashing detergents usually contain builders. Builders that can be contained in these agents include, in particular, silicates, aluminum silicates (especially zeolites), carbonates, phosphonates, organic (co) builders, such as salts of organic di- and polycarboxylic acids, and mixtures of these substances.

For example, crystalline layered silicates of the general formula NaMSixO2x + 1 · y H2O, in which M represents sodium or hydrogen, x a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values, can be used in automatic dishwashing detergents for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Particularly noteworthy are both ß- and δ-sodium disilicates Na2Si2O5 y H2O as well as above all Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (β-Na2Si2O5, Natrosilit), Na-SKS-9 ( NaHSi2O5 H2O), Na-SKS-10 (NaHSi2O5 3 H2O, Kanemite), Na-SKS-11 (t-Na2Si2O5) and Na-SKS-13 (NaHSi2O5), but especially Na-SKS-6 (δ-Na2Si2O5 ).

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.

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, with the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used.

The agents can also contain phosphonates as builders, which according to the invention are not subsumed under the phosphates. 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. Preferred aminoalkanephosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues.

Organic (co) builders include, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other 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 dishwashing detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.

Another important class of phosphate-free builders are aminocarboxylic acids and / or their salts. Particularly preferred representatives of this class are methylglycine diacetic acid (MGDA) and / or its salts and also glutamine diacetic acid (GLDA) and / or its salts or ethylenediamine diacetic acid (EDDS) and / or its Salts.

In one possible embodiment, the agent according to the invention preferably contains up to 5% by weight, particularly preferably up to 2% by weight, of builders, based on the total amount of rinse aid.

In a preferred embodiment, the rinsing agents according to the invention do not contain any of the builders mentioned. This means that the agents according to the invention are preferably essentially free from silicates and / or aluminum silicates and / or carbonates and / or phosphonates and / or organic (co) builders, ie the agents according to the invention preferably contain the builders mentioned in amounts less than 1 wt. %, preferably less than 0.1% by weight, and / or they contain no consciously added builder.

A preferred object is therefore a rinse aid which has no builder.

The pH of the rinse aid according to the invention can be adjusted by conventional pH regulators. In preferred embodiments, the pH of the agent is selected such that a 1% aqueous solution of the rinse aid at 20 ° C. has a pH in the range from 5.5 to 8.5, preferably from 6.0 to 8.0 , particularly preferably from 6.5 to 7.5.

A preferred object is therefore a rinse aid, the 1% strength aqueous solution of which has a pH value in the range from 5.5 to 8.5 at 20 ° C.

The rinse aid according to the invention preferably contains water. The rinse aid according to the invention preferably contains water in an amount of up to 25% by weight, particularly preferably up to 15% by weight. In particularly preferred embodiments, the rinse aid according to the invention contains from 5 to 25% by weight or from 10 to 20% by weight of water, based on the total amount of rinse aid.

A preferred object is therefore a rinse aid that contains water, preferably in an amount of up to 25% by weight, particularly preferably up to 15% by weight, based on the total amount of rinse aid.

The rinse aid according to the invention can also contain polymers. For example, polyethylene glycols can be contained in the rinse aid according to the invention. Polyethylene glycols of a certain molecular weight range can, for example, be used as solvents in the rinse aid according to the invention. These are preferably polyethylene glycols with an average molecular weight of 150 to 600 g / mol, especially preferably from 190 to 400 g / mol. Particularly suitable polyethylene glycols have, for example, 4 to 8 repeating units and thus have a molar mass of 194 g / mol, 238 g / mol, 282 g / mol, 326 g / mol and 370 g / mol, respectively. In certain embodiments, the rinse aid according to the invention can therefore contain polyethylene glycol, preferably with an average molecular weight of 150 to 600 g / mol, particularly preferably with an average molecular weight of 190 to 400 g / mol.

The rinse aid according to the invention can contain other types of polymers. Automatic dishwashing detergents often have homo- and / or copolymers of maleic acid and / or its salts, acrylic acid and / or its salts, methacrylic acid and / or its salts. These types of polymers can also be contained in the rinse aid according to the invention. However, it is preferred according to the invention that the rinse aid according to the invention does not contain any polymer containing monomers from the group of maleic acid and / or its salts, acrylic acid and / or its salts, methacrylic acid and / or its salts.

A preferred subject is therefore a rinse aid which does not contain any polymer containing monomers from the group of maleic acid and / or its salts, acrylic acid and / or its salts, methacrylic acid and / or its salts.

A preferred subject in the context of the present application is therefore a rinse aid in which the polyol is selected from the group of ethylene glycol, propane-1,2-diol, propane-1,3-diol, dipropylene glycol or mixtures thereof, particularly preferably from propane -1,2-diol and / or propane-1,3-diol, very particularly preferably the at least one polyol is propane-1,2-diol, and / or in which nonionic surfactant and polyol in a weight ratio of 4: 1 to 1: 4, preferably from 3: 1 to 1: 3, particularly preferably from 3: 2 to 2: 3, are present to one another and / or which does not contain any builder and / or no polymer containing monomers from the group of maleic acid and / or its salts , Acrylic acid and / or its salts, methacrylic acid and / or its salts and wherein preferably at least one surfactant according to the formula R ¹ O [C ₂ H ₄ O] _x [C ₄ H ₈ O] _y R ^{2 is} used as the nonionic surfactant, where, in the aforementioned formula, R ^{1 is} a linear or branched aliphatic hydrocarbon remainder with 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 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, stands. A further preferred subject matter in the context of the present application is therefore a rinse aid which has 10 to 60% by weight of polyol, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight and / or which has 10% by weight to 60% by weight of nonionic surfactant, particularly preferably 20 to 55% by weight, very particularly preferably 30 to 50% by weight, based in each case on the total amount of rinse aid, and in which the polyol is selected from the group of Ethylene glycol, propane-1,2-diol, propane-1,3-diol, dipropylene glycol or mixtures thereof, particularly preferably from propane-1,2-diol and / or propane-1,3-diol, at least that is particularly preferred a polyol propane-1,2-diol, and / or which has water, preferably in an amount of up to 25% by weight, particularly preferably up to 15% by weight, based on the total amount of rinse aid, and as nonionic surfactant preferably at least one surfactant according to the formula R ¹ O [C ₂ H ₄ O] _x [C ₄ H ₈ O] _y R ^{2 is} used rd, where, in the aforementioned formula, R ^{1 stands} 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 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, stands.

Yet another preferred subject matter in the context of the present application is a rinse aid in which the polyol is selected from the group of ethylene glycol, propane-1,2-diol, propane-1,3-diol, dipropylene glycol or mixtures thereof, particularly preferred from propane-1,2-diol and / or propane-1,3-diol, very particularly preferably the at least one polyol is propane-1,2-diol, and / or in which nonionic surfactant and polyol in a weight ratio of 4: 1 to 1: 4, preferably from 3: 1 to 1: 3, particularly preferably from 3: 2 to 2: 3, are present to one another and / or which has no builder and / or which has water, preferably in an amount of up to 25% by weight, particularly preferably up to 15% by weight, based on the total amount of rinse aid, and where the nonionic surfactant is preferably at least one surfactant according to the formula R ¹ O [C ₂ H ₄ O] _x [C ₄ H ₈ O] _y R ^{2 is} used, where, in the aforementioned formula, R ^{1 is} a linear or branched aliphatic Ko hydrogen radical with 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 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, for example .

The rinsing agents described herein are preferably pre-packaged into dosage units. These dosing units preferably include the amount of surface-active substances required for a rinse cycle. Preferred dosage units have a weight of 0.25 g to 25 g, preferably 1 g to 7.5 g, particularly preferably 3 g to 6 g. Preferred dosage units contain nonionic surfactant in an amount from 0.1 g to 10 g, preferably from 0.3 g to 5 g and particularly preferably from 0.5 to 3 g.

Prefabricated dosage units of the rinse aid described herein have a water-soluble coating.

A preferred object is therefore a rinse aid which is present as a pre-portioned single portion in a water-soluble envelope.

Another preferred subject is a rinse aid, which is present as a pre-portioned one-time portion in a water-soluble envelope, the one-time portion having an amount of rinse aid from 0.25 g to 25 g, preferably from 1 g to 7.5 g, particularly preferably from 3 g to 6 g.

Another preferred subject is a rinse aid which is present as a pre-portioned one-time portion in a water-soluble envelope, the one-time portion having an amount of nonionic surfactant of 0.1 g to 10 g, preferably 0.3 g to 5 g and particularly preferably 0, 5 to 3 g.

This water-soluble envelope is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The envelope 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.

The water-soluble packaging can have one or more chambers. The agent can be contained in one or more chambers, if present, of the water-soluble envelope. The amount of agent preferably corresponds to the full or half the dose that is required for one wash cycle.

It is preferred that the water-soluble casing contains 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 the water-soluble envelope are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which 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.

Another preferred subject is a rinse aid, which is present as a pre-portioned one-time portion in a water-soluble envelope, the one-time portion having an amount of rinse aid from 0.25 g to 25 g, preferably from 1 g to 7.5 g, particularly preferably from 3 g to 6 g and wherein the water-soluble envelope comprises polyvinyl alcohol.

Another object of the invention is the use of nonionic surfactant and polyol to improve the rinsing performance.

• Dosierung eines Reinigungsmittels für die maschinelle Geschirrreinigung,
• Dosierung eines Klarspülmittels nach einem der Ansprüche 1 bis 10,
• Durchlaufen eines normalen Reinigungszyklus zur Reinigung von Spülgut, insbesondere verschmutztem Geschirr,

wobei das Reinigungsmittel für die maschinelle Geschirrreinigung in fester und/oder flüssiger Form und/oder gelförmig vorliegen kann.The invention also relates to an automatic dishwashing method for cleaning dishes, comprising the steps

• Dosing of a detergent for machine dish washing,
• Dosage of a rinse aid according to one of Claims 1 to 10,
• Run through a normal cleaning cycle for cleaning items to be washed, especially dirty dishes,

wherein the cleaning agent for machine dishwashing can be in solid and / or liquid form and / or in gel form.

Usual cleaning cycles in automatic dishwashing processes can have one or more pre-wash cycles and have one or more cleaning cycles, preferably one cleaning cycle, and one or more final rinse cycles, preferably one final rinse cycle.

Automatic dishwashing processes in which the cleaning cycle is carried out at a temperature in the range from 30 ° C. to 70 ° C., preferably from 35 ° C. to 60 ° C., particularly preferably from 35 ° C. to 50 ° C., particularly preferably from 40 to 45, are preferred ° C takes place and / or the rinse cycle is preferably carried out at a temperature in the range from 45 ° C to 80 ° C, particularly preferably from 50 ° C to 75 ° C.

The embodiments described in the context of the agents according to the invention can easily be transferred to the methods and uses according to the invention, and vice versa.

Embodiment:

The rinse aid tests were carried out in a Bosch SMS 86M12 DE with the Eco 50 ° C program (shortened time) at a water hardness of 21 ° dH in the presence of 100 g of ballast dirt (4 g margarine, 4 g potato starch, 1.6 table salt, 16 g whole egg, 74.4 g of water).

33.6 g of cleaning gel A or B and, if necessary, the composition according to the invention were used per wash cycle.

The items to be washed were evaluated visually by comparing them with a reference scale (5 = no stains; 1 = very strong stains).

The cleaning gel B with Ecosurf Bright 1 was not storage-stable for 4 weeks at room temperature or at 40 ° C. Cleansing gel A Cleansing gel B Booster E. Wt% Wt% Wt% Ecosurf Bright 1 (DOW) - 6.0 40.0 Propane-1,2-diol - - 50.0 water 52.2 46.2 10.0 Acusol 810 4.7 4.7 - Polymer containing sulfonic acid groups 4.5 4.5 - Sorbitol 8.0 8.0 - Sodium citrate 9.5 9.5 - Trilon M Max 18.5 18.5 - citric acid 1.2 1.2 - Cationic acrylate copolymer (Mirapol Surf S 480 PF) 0.5 0.5 - Protease (% by weight of active enzyme) 0.3 0.3 - Amylase (% by weight of active enzyme) 0.1 0.1 - Acticide SR 1500 0.5 0.5 - Glass stainless steel Porcelain (Friesland) Porcelain (fun fact.) plastic Cleaner gel A (without Ecosurf Bright 1) 2.5 3.0 2.5 2.0 2.5 Cleaner gel B (with 2g Ecosurf Bright 1 per wash cycle) 3.0 3.0 3.0 2.5 2.0 Cleaner gel A plus Booster E (with 2g Ecosurf Bright 1 per wash cycle) 4.5 3.5 4.5 4.0 2.5

The use of the cleaning gel A in combination with the booster E surprisingly delivers significantly better rinse aid results on glass and porcelain than the use of the cleaning gel B.

Claims (13)

Rinse aid for machine dishwashing containing at least one nonionic surfactant and at least one polyol. Rinse aid according to claim 1, characterized in that nonionic surfactant and polyol are present in a weight ratio of 4: 1 to 1: 4, preferably 3: 1 to 1: 3, particularly preferably 3: 2 to 2: 3, to one another. Rinse aid according to one of claims 1 or 2, characterized in that the polyol is selected from the group of ethylene glycol, propane-1,2-diol, propane-1,3-diol, dipropylene glycol or mixtures thereof. Rinse aid according to one of the preceding claims, characterized in that the nonionic surfactant is an alkoxylated alcohol, particularly preferably an alkoxylated alcohol 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, 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 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, stands. Rinse aid according to one of the preceding claims, characterized in that the rinse aid has 10 to 60% by weight of nonionic surfactant and / or 10 to 60% by weight of polyol, each based on the total amount of rinse aid. Rinse aid according to one of the preceding claims, characterized in that the rinse aid has no builder. Rinse aid according to one of the preceding claims, characterized in that a 1% strength aqueous solution of the rinse aid has a pH value in the range from 5.5 to 8.5 at 20 ° C. Rinse aid according to one of the preceding claims, characterized in that the rinse aid contains water, preferably in an amount of up to 25% by weight, particularly preferably up to 15% by weight, based on the total amount of rinse aid. Rinse aid according to one of the preceding claims, characterized in that the rinse aid does not contain any polymer containing monomers from the group of maleic acid and / or its salts, acrylic acid and / or its salts, methacrylic acid and / or its salts. Rinse aid according to one of the preceding claims, characterized in that the rinse aid is present as a pre-portioned single portion in a water-soluble envelope. Rinse aid according to claim 10, characterized in that the single portion has an amount of rinse aid of 0.25 g to 25 g, preferably 1 g to 7.5 g, particularly preferably 3 g to 6 g. Use of nonionic surfactant and polyol in automatic dishwashing processes to improve the rinsing performance. Automatic dishwashing process comprising the steps - Dosing of a detergent for machine dishwashing, - Dosage of a rinse aid according to one of claims 1 to 11, - Running through a normal cleaning cycle for cleaning items to be washed, especially dirty dishes, wherein the cleaning agent for machine dishwashing can be in solid and / or liquid form and / or in gel form.