EP2109663B1 - Cleaning compositions for glass surfaces - Google Patents

Abstract

Multi-armed silyl polyalkoxylates of the formula (I), (H-A)n-Z-[A-B—Si(OR1)r(R2)3−r]m (I), where Z is an (m+n)-valent radical having at least three carbon atoms, A is a divalent polyoxyalkylene radical, B is a chemical bond or a divalent organic radical having 1 to 50 carbon atoms, OR1 is a hydrolysable group, R1 and R2 independently of one another are a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer from 1 to 3, and m is an integer ≈1 and n is 0 or an integer ≈1, and m+n has a value from 3 to 100, for reducing glass corrosion and/or for improving the drying performance during mechanical cleaning of a glass surface. Also compositions, in particular for the cleaning of glass surfaces, which compositions contain compounds of the formula (I).

Description

The present invention relates to the technical field of glass surface cleaners, and more particularly to agents which reduce glass corrosion in machine cleaning of glass surfaces.

Damage to the surface of glassware during cleaning and / or rinsing operations has been a well-known problem due to the leakage of minerals from the glass composition, accompanied by hydrolysis of the silicate network, and deposition of silicate material on the glass Glassware takes place.

A special case of this problem is the field of automatic dishwashing, as it is known, for example, to a consumer when rinsing glassware in a domestic dishwasher. Especially with multiple rinsing of glassware in a dishwasher, the above-described phenomena can lead to damage to the glass surfaces, which manifest themselves in opacities, scratches, streaks or the like. Such impairments to the appearance of machine-washed glassware are still one of the most common problems that occur when using mechanical cleaning agents.

In the prior art, among other things, the use of zinc to overcome the aforementioned problems is proposed. For example, the document describes EP 0383482 automatic dishwasher detergents containing insoluble zinc salts, which are distinguished by improved glass corrosion protection. The insoluble zinc salts must have a certain particle size to achieve such an effect.

The WO 00/39259 discloses water-soluble glasses according to DIN ISO 719, which contain at least one glass corrosion inhibiting active ingredient whose weight fraction of the glass is not more than 85 wt .-% and which is released under the conditions of the cleaning and / or rinse cycle from this glass.

However, the means known in the art are not fully satisfactory. In some cases, they have the disadvantage that they can be used only in pre- or Hauptreinigungsgängen, or act only in the rinse cycle when the consumer is a depot product such as the glass body of WO 00/39259 in the dishwasher. Although some of them can be used in the rinse cycle, they are not satisfactory in their effectiveness.

The US 6423661 B1 describes silyl-terminated prepolymers for the preparation of which the OH groups of a polyether polyol, which may have up to eight arms, are reacted with an isocyanate silane. The resulting compounds called prepolymers are for use in adhesives. A use of the prepolymers, for example in cleaning agents or for the corrosion protection of glass is not disclosed.

From the US 2003/0153712 A1 For example, a polyurethane prepolymer having terminal alkoxysilane and hydroxy groups is known. For the preparation, a polyether-diol is first reacted with stoichiometric diisocyanate, and the resulting isocyanate-hydroxy compound is then further treated with an aminosilane to introduce the silyl groups. The described, two-armed polyalkoxylates representing prepolymers are used for the production of sealants and adhesives.

The US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a completely silyl-terminated derivative which can be prepared starting from sorbitol as a central unit. The polyethylene glycol derivatives described in the document are said to be useful for the preparation of biodegradable polymeric hydrogels and for medical pharmaceutical use, for example, for implants.

The object of the present invention is to provide means for reducing the glass corrosion when mechanically cleaning glass surfaces, which have advantages over conventional means, in particular a better efficacy and / or advantages in terms of freedom from formulation of the active substances contained in the agent.

It has now been found that certain multi-arm silyl polyalkoxylates are particularly suitable for providing agents with the desired properties.

It has further been found that the use of these silyl polyalkoxylates in the automated cleaning of glass surfaces causes an improvement in the drying performance of the cleaned surfaces. This is understood in particular to mean a shortening of the drying time and / or a reduction in the formation of limescale and deposits on the cleaned surfaces.

• Z für einen (m+n)-wertigen Rest mit mindestens drei Kohlenstoffatomen steht,
• A einen zweiwertigen Polyoxyalkylenrest bedeutet, wobei die an Z gebundenen m+n Polyoxyalkylenreste voneinander unterschiedlich sein können, und wobei ein Rest A jeweils über ein zu Z gehöriges Sauerstoffatom mit Z und ein zu A gehöriges Sauerstoffatom mit B beziehungsweise Wasserstoff verbunden ist,
• B für eine chemische Bindung oder einen zweiwertigen organischen Rest mit 1 bis 50 Kohlenstoffatomen steht,
• OR¹ eine hydrolysierbare Gruppe bedeutet, R¹ und R² unabhängig voneinander eine lineare oder verzweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen bedeuten und r für eine ganze Zahl von 1 bis 3 steht, und
• m eine ganze Zahl ≥ 1 ist und n für 0 oder eine ganze Zahl ≥ 1 steht, und m+n einen Wert von 3 bis 100 aufweist.

The present invention therefore provides the use of a multi-arm silyl polyalkoxylate of the formula (I) for reducing glass corrosion and / or for improving the drying performance in the mechanical cleaning of a glass surface, where in formula (I)

(HA) _n -Z- [AB-Si (OR ¹ ) _r (R ² ) _3-r ] _m (I),

• Z is an (m + n) -valent radical having at least three carbon atoms,
• A denotes a divalent polyoxyalkylene radical, where the m + n polyoxyalkylene radicals bonded to Z can differ from one another, and where one radical A is in each case linked to Z via an oxygen atom belonging to Z and one to A belongs to oxygen atom with B or hydrogen,
• B is a chemical bond or a bivalent organic radical having 1 to 50 carbon atoms,
• OR ^{1 is} a hydrolyzable group, R ¹ and R ^{2 are} independently a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer of 1 to 3, and
• m is an integer ≥ 1 and n is 0 or an integer ≥ 1, and m + n has a value of 3 to 100.

The use of the silyl polyalkoxylates of the formula (I) in the mechanical cleaning of glass surfaces causes an improvement in the drying performance of the cleaned surfaces. It is particularly advantageous if the silyl polyalkoxylates are used in a rinse cycle downstream of the cleaning cycle.

An improvement in the drying performance has the advantage, for example, in the conventional household dishwashing that the consumer after the expiration of the program can take the cleaned dishes earlier from the machine and reuse. In particular, however, this improvement results in the consumer being able to use lower temperature rinse programs (e.g., 40 ° C) for which the drying result has not been satisfactory.

For the purposes of this invention, multi-armed silyl polyalkoxylates contain polymer arms which are essentially star-shaped or radially bonded to a central unit.

In a preferred embodiment of the invention, a silyl polyalkoxylate of the formula (I) or a mixture of several of these compounds is used, wherein the weight average molecular weight is from 500 to 50,000, preferably from 1,000 to 20,000, and most preferably from 2,000 to 10,000. The silyl polyalkoxylate preferably contains 0.3 to 10 wt .-%, particularly preferably 0.5 to 5 wt .-% silicon, based on the total weight of the silyl polyalkoxylate.

Z preferably represents an at least trihydric, in particular tri-to octahedral, acyclic or cyclic hydrocarbon radical having 3 to 12 carbon atoms, where the radical may be saturated or unsaturated and in particular also aromatic. Z is particularly preferably the trivalent radical of glycerol or the trihydric to hexahydric radical of a sugar, for example, the hexavalent residue of sorbitol or the octahedral residue of sucrose. The x-valent radical of one of the abovementioned polyols is to be understood as meaning that molecule fragment which remains from the polyol after removal of the hydrogen atoms from x alcoholic or phenolic hydroxyl groups. In principle, Z can stand for any central unit which is known from the literature for the preparation of star-shaped (pre) polymers.

Furthermore, it is particularly preferred if in formula (I) n is 0, 1 or 2 and m is a number from 3 to 8.

A is preferably selected from poly-C ₂ -C ₄ -alkylene oxides, more preferably a (co) polymer of ethylene oxide and / or propylene oxide, in particular a copolymer having a propylene oxide content of up to 60% by weight, preferably up to to 30 wt .-% and particularly preferably of up to 20 wt .-%, which may be random and / or block copolymers. Accordingly, another preferred embodiment of the invention is the use of multi-arm silyl polyalkoxylates of the formula (I) in which A is - (CHR ³ -CHR ⁴ -O) _p -, where R ³ and R ⁴ independently of one another are hydrogen, Methyl or ethyl and p is an integer from 2 to 10,000.

B is in particular a chemical bond or a bivalent, low molecular weight organic radical having preferably 1 to 50, in particular 2 to 20 carbon atoms. Examples of divalent low molecular weight organic radicals are short-chain aliphatic and heteroaliphatic radicals such as - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -C (O) -NH- (CH ₂ ) ₃ - and -C (O) -NH-X-NH-C (O) -NH- (CH ₂ ) ₃ -, wherein X is a bivalent aromatic radical such as the phenylene radical or an alkylidene radical. Most preferably, B is a bond or the radical -C (O) -NH- (CH ₂ ) ₃ -.

Preferably, R ¹ and R ² independently of one another are methyl or ethyl, and r is 2 or 3. Examples of radicals -Si (OR ¹ ) _r (R ² ) _3-r are dimethylethoxysilyl, dimethylmethoxysilyl, diisopropylethoxysilyl, methyldimethoxysilyl However, trimethoxysilyl and triethoxysilyl radicals are most preferred.

It is most preferred when R ¹ and R ^{2 are the} same and are methyl or ethyl.

Furthermore, it is particularly preferred if r stands for the number 3.

The sum m + n is preferably 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8, and coincides with the number of arms which is bound in the compound (I) to the central unit Z. The central unit therefore preferably has 3 to 50, in particular 3 to 10 and more preferably 3 to 8 oxygen atoms, which serve as attachment points for the arms.

In a particular embodiment, n is 0. In the case where n> 0, the ratio n / m is between 99/1 and 1/99, preferably 49/1 and 1/49, and especially 9/1 and 1 /. 9

In a further preferred embodiment of the invention, a mixture of at least two, in particular two to four, different multi-armed silyl polyalkoxylates of the formula (I) is used.

It is particularly preferred if the at least two different multi-armed silyl polyalkoxylates differ in the number of their arms. Advantageously, a first silyl polyalkoxylate having 3 to 6 arms is combined with a second silyl polyalkoxylate having 6 to 10 arms.

Particularly preferred is the use of a mixture comprising at least two different multi-armed silyl polyalkoxylates of the formula (I) with n = 0, which are selected from the group of the multi-armed silyl polyalkoxylates of the formula (I) with m = 3, m = 6 and m =. 8

When two different multi-arm silyl polyalkoxylates are used, they are generally present in a quantitative ratio of from 99: 1 to 1:99, preferably from 49: 1 to 1:49, and more preferably from 9: 1 to 1: 9.

In a further particularly preferred embodiment of the invention, the use of the multi-armed silyl polyalkoxylates of the formula (I) is carried out in the presence of at least one hydrolyzable silicic acid derivative.

Hydrolyzable silicic acid derivatives are to be understood as meaning in particular the esters of orthosilicic acid, in particular the tetraalkoxysilanes and very particularly preferably tetraethoxysilane.

In this embodiment, it is particularly advantageous if the quantitative ratio of silyl polyalkoxylate or silyl polyalkoxylate mixture to the at least one hydrolyzable silicic acid derivative 90:10 to 10:90, preferably 50:50 to 10:90, and especially 40:60 to 20:80.

Insofar as the multi-arm silyl polyalkoxylates of the general formula (I) used according to the invention are not known from the literature, their preparation can be carried out by functionalization of suitable polyhydric polyalkoxylate precursors in analogy to known functionalization processes of the prior art.

That in the US 2003/0153712 A1 described two-arm polyurethane prepolymer having terminal alkoxysilane and hydroxy groups is prepared by first reacting a polyether diol with stoichiometric lower diisocyanate, and then treating the resulting isocyanate-hydroxy compound further with an aminosilane to introduce the silyl groups , The synthesis principles used there can be basically transferred to the preparation of multi-armed polyalkoxylates according to the teachings of the present invention.

In the US 6423661 B1 silyl-terminated prepolymers are described, for their preparation, the OH groups of a polyether polyol, which may have up to eight arms, are reacted with an isocyanate silane. The teaching of this document includes prepolymers which fall under the general formula (I) of the present invention.

The US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a fully silyl-terminated derivative which can be prepared starting from sorbitol as a central unit and which falls under the general formula (I) of the present invention.

Suitable polyalkoxylate precursors for the preparation of the silyl polyalkoxylates used according to the invention are in turn polyaromatic polyalkoxylates which already have the above-described multi-arm structure and which each have a hydroxyl group at the ends of the polymer arms which is partially or completely group (n) -B -Si (OR ¹ ) _r (R ² ) _3-r can be converted. The polyalkoxylate precursors of the silyl polyalkoxylates used according to the invention can be represented by the general formula (II)

Z- (A-OH) _{m + n} (II)

represent, wherein Z, A, m and n have the same meaning as previously described for the compounds of formula (I).

For example, suitable polyalkoxylate precursors are known from the literature under the name star-shaped or multi-arm polyether polyols. These polyalkoxylate precursors are prepared by polymerization of the appropriate monomers, especially ethylene oxide and / or propylene oxide, using polyfunctional small molecules such as glycerol or sorbitol as initiator. Examples of polyhydric polyether polyols ethoxylates or propoxylates of glycerol, sucrose and sorbitol, as described in the patent US 6423661 are described. Due to the statistical nature of the polymerization reaction, the above information on the polymer arms of the invention understand used silyl polyalkoxylates, especially in terms of arm length and arm number (m + n) each as a statistical average.

Suitable polyalkoxylate precursors are also commercially available in part. An example of this is Voranol 4053, a polyether polyol (poly (ethylene oxide-co-propylene oxide)) from DOW Chemicals. It is a mixture of two different polyether polyols, consisting of a 3-arm polyether polyol with glycerol as the central unit and an 8-arm polyether polyol with cane sugar as the central unit. The arms represent random copolymers of about 75% EO and about 25% PO, the OH functionality (hydroxy end groups) is an average of 6.9 at a weight average molecular weight of about 12000. This results in a Ratio of about 78% 8-arm polyether polyol and about 22% 3-arm polyether polyol.
Another example is Wanol R420 from WANHUA, China, which is a mixture of a linear poly (propylene / ethylene) diethylene glycol and an 8-arm polyether polyol (poly (propyleneoxy / ethyleneoxi) sucrose) in a ratio of about 15 -25: 85-75 represents. Also commercially available is the polyether polyol Voranol CP 1421 from DOW Chemicals, which is a 3-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of about 75/25 and a weight average (Weight average molecular weight) of about 5000 is.

As starting materials for the conversion of the hydroxy end groups of the polyhydric polyalkoxylate precursor in the groups -B-Si (OR ¹ ) _r (R ² ) _3-r are in principle all functional silanes in question, which have a functional group which is opposite to the hydroxy End groups of the polyalkoxylate precursor is reactive. Examples are tetraalkoxy silanes such as tetramethyl silicate and tetraethyl silicate, (meth) acrylate silanes such as (3-methacryloxypropyl) trimethoxysilane, (methacryloxymethyl) triethoxysilane, (meth-acryloxymethyl) methyldimethoxysilane and (3-acryloxypropyl) trimethoxysilane, isocyanato-silanes such as Isocyanatopropyl) trimethoxysilane, (3-isocyanato-propyl) triethoxysilane, (isocyanatomethyl) methyldimethoxysilane and (isocyanatomethyl) trimethoxysilane, aldehyde-silanes such as triethoxysilylundecanal and triethoxysilylbutyraldehydes, epoxy-silanes such as (3-glycidoxypropyl) -trimethoxysilane, anhydride-silanes such as 3 (Triethoxysilyl) propylsuccinic anhydride, halogenated silanes such as chloromethyltrimethoxysilane and 3-chloropropyl-methyldimethoxysilane, hydroxy-silanes such as hydroxymethyltriethoxysilane, and tetraethylsilicate (TEOS), which are commercially available, for example, from Wacker Chemie GmbH (Burghausen), Gelest, Inc. (US Pat. Morrisville, USA) or ABCR GmbH & Co. KG (Karlsruhe) or herge by known methods can be made. Tetraalkoxysilanes, isocyanato-silanes or anhydride-silanes, but especially tetraalkoxysilanes, are particularly preferably reacted with polyhydric polyalkoxylate precursors of the general formula (II). In a complete reaction of all hydroxy ends with the functional silanes obtained according to the invention used multi-arm silyl polyalkoxylates, which at the Ends of the arms carry only radicals -B-Si (OR ¹ ) _r (R ² ) _3-r , ie where n = 0. The group B is in such a case, for example, exclusively in a bond, or it comprises, when an isocyanatosilane was used as a functional silane, together with the terminal oxygen atom of group A, for example, a urethane group and the atomic group, in the starting isocyanatosilane between the isocyanato group and the silyl group stands. In a complete reaction of all hydroxy ends with anhydride silanes, for example 3- (triethoxysilyl) propylsuccinic, one obtains multi-armed silyl polyalkoxylates, which also carry only radicals -B-Si (OR ¹ ) _r (R ² ) _3-r . Group B in such a case, together with the terminal oxygen atom of group A, comprises an ester group and the atomic group which in the starting anhydride silane is between the anhydride group and the silyl group.

If multi-arm silyl polyalkoxylates of the general formula (I) used according to the invention are used which carry both hydroxy and -B-Si (OR ¹ ) _r (R ² ) _3-r groups at the ends of their arms, preference is given to this proceeded that a polyalkoxylate precursor of the general formula (II) is reacted with a relation to the total of the terminal hydroxy groups substoichiometric amount of a functional silane, ie there are described above, first -B-Si (OR ¹ ) _r (R ² ) Introduced _3-r groups, but not all terminal hydroxyl groups in the polyhydric polyalkoxylate precursor reacted. In this way one obtains multi-armed polyalkoxylates which carry both hydroxy and -Si (OR ¹ ) _r (R ² ) _3-r groups. Thus, for example, in the case of a partial reaction of the hydroxy ends of a polyhydric polyether polyol with isocyanato-silanes, polyaromatic polyalkoxylates which carry both terminal silyl groups and OH groups (R '= OH) are obtained. In a further step, the remaining or a part of the remaining hydroxyl groups can be modified as described to give radicals B-Si (OR ¹ ) _r (R ² ) _3-r .

Another object of the present invention is a method for machine cleaning a glass surface in which the glass surface is brought into contact with a multi-arm silyl polyalkoxylate of the formula (I).

Advantageously, this is done in such a way that the silyl polyalkoxylate is metered in the form of a solution in water and / or a non-aqueous solvent in the course of the cleaning process and brought into contact with the glass surface.

In a particular embodiment, the solution of the silyl polyalkoxylate has an acidic pH, in particular a pH of from 1 to 6, preferably from 2 to 4. To set an acidic pH, the solution preferably contains an acidifying agent.

In a particularly preferred embodiment of the purification process according to the invention, this comprises a purification step and an adjoining final rinse step in which the silyl polyalkoxylate is metered in during the rinse step and brought into contact with the glass surface.

However, it is also possible to dose the silyl polyalkoxylate in the course of the cleaning step of a cleaning process according to the invention. In this case, the silyl polyalkoxylate, for example, in addition to a cleaning agent usually used in such a method can be dosed simultaneously or sequentially, or it can also be dosed as part of a cleaning agent. In the latter case, the silyl polyalkoxylate forms a part of the cleaning agent. The silyl polyalkoxylate can be incorporated in a conventional manner in a cleaning agent. The cleaning agent is preferably a water-soluble portion pack, in particular in the form of a tablet or a deep-drawn or injection-molded portion pack made of a water-soluble film. Advantageously, the silyl polyalkoxylate is integrated in such a cleaning agent in basically the same way as is usually the case with the cleaning agents responsible for rinsing.

In a purification process according to the invention, it is advantageous to use agents which, in addition to the silyl polyalkoxylates, also contain at least one nonionic surfactant.

1. a) 0,05 bis 10, vorzugsweise 0,1 bis 7, besonders bevorzugt 0,2 bis 5 und insbesondere 0,3 bis 3 Gew.-% mindestens eines mehrarmigen Silyl-Polyalkoxylats der Formel (I)
   
           (H-A)_n-Z-[A-B-Si(OR¹)_r(R²)_3-r]_m     (I)
   
   worin
   • Z für einen (m+n)-wertigen Rest mit mindestens drei Kohlenstoffatomen steht,
   • A einen zweiwertigen Polyoxyalkylenrest bedeutet, wobei die an Z gebundenen m+n Polyoxyalkylenreste voneinander unterschiedlich sein können, und wobei ein Rest A jeweils über ein zu Z gehöriges Sauerstoffatom mit Z und ein zu A gehöriges Sauerstoffatom mit B beziehungsweise Wasserstoff verbunden ist,
   • B für eine chemische Bindung oder einen zweiwertigen organischen Rest mit 1 bis 50 Kohlenstoffatomen steht,
   • OR¹ eine hydrolysierbare Gruppe bedeutet, R¹ und R² unabhängig voneinander eine lineare oder verzweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen bedeuten und r für eine ganze Zahl von 1 bis 3 steht, und
   • m eine ganze Zahl ≥ 1 ist und n für 0 oder eine ganze Zahl ≥ 1 steht, und m+n einen Wert von 3 bis 100 aufweist,
2. b) 0,1 bis 40 Gew.-% nichtionische(s) Tensid(e), und
3. c) gewünschtenfalls Wasser und/oder einen oder mehrere Stoffe ausgewählt aus korrosionsschützenden Agenzien, Acidifizierungsmitteln, nichtwässrigen Lösungsmitteln und Lösungsvermittlern.

The subject of the present invention is therefore also an agent, in particular cleaning agent, preferably for cleaning a glass surface containing

1. a) 0.05 to 10, preferably 0.1 to 7, particularly preferably 0.2 to 5 and in particular 0.3 to 3 wt .-% of at least one multi-armed silyl polyalkoxylate of the formula (I)
   
   (HA) _n -Z- [AB-Si (OR ¹ ) _r (R ² ) _3-r ] _m (I)
   
   wherein
   • Z is an (m + n) -valent radical having at least three carbon atoms,
   • A denotes a divalent polyoxyalkylene radical, where the m + n polyoxyalkylene radicals bonded to Z can differ from one another, and where one radical A is in each case linked to Z via an oxygen atom belonging to Z and one to A belongs to oxygen atom with B or hydrogen,
   • B is a chemical bond or a bivalent organic radical having 1 to 50 carbon atoms,
   • OR ^{1 is} a hydrolyzable group, R ¹ and R ^{2 are} independently a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer of 1 to 3, and
   • m is an integer ≥ 1 and n is 0 or an integer ≥ 1, and m + n has a value of 3 to 100,
2. b) 0.1 to 40% by weight of nonionic surfactant (s), and
3. c) if desired, water and / or one or more substances selected from anti-corrosive agents, Acidifizierungsmitteln, non-aqueous solvents and solubilizers.

Further preferred embodiments of the agents according to the invention contain at least one multi-armed silyl polyalkoxylate in those preferred embodiments which have already been described in the preceding text as preferred embodiments of the silyl polyalkoxylates of the formula (I).

In addition, the agent may optionally contain further components, which are described in more detail below. Of course, the optional components according to their nature and the amount used are to be selected so that there are no undesirable reactions with the silyl polyalkoxylates, which could affect the stability of the composition.

In a preferred embodiment, in addition to the at least one multi-arm silyl polyalkoxylate of the formula (I) and a nonionic surfactant, the agent also contains water and / or a nonaqueous solvent and optionally also an acidifier. It may be particularly preferred if the agent also contains no other ingredients.

It has been found that it is particularly advantageous when the glass corrosion inhibiting silyl polyalkoxylates in the last rinse, i. in the rinse cycle, are present. In this way, the beneficial effect is not mitigated by subsequent rinses.

The automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses. The temperature of the main wash cycle varies between 30 and 75 ° C, depending on the machine type and program level selection. In the rinse cycle, rinse aids are added from a dosing tank in the machine, which are usually present in liquid form.

A further embodiment of the invention is therefore an agent as described above which constitutes a means for mechanically cleaning a glass surface, in particular a rinse aid for automatic dishwashing, and in particular contains components as further optional constituents, such as are customary constituents of a rinse aid from the state known in the art.

The agents according to the invention contain at least one nonionic surfactant. As nonionic surfactants are preferably polyalkylene oxides, in particular alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may linear or preferably methyl branched in the 2-position or linear and methyl-branched radicals in a mixture may contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylaminoxid, and the fatty acid alkanolamides may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the following formula

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the following formula

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here, rinse aids according to the invention are preferred which contain surfactants of the general formula (III) as nichionic surfactant (s)

R ^{1 is} -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CHR ² -O) _x - (CH ₂ -CH _r -O) _y - (CH ₂ -CHR ³ -O) _z -H (III)

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 are integers from 1 to 6.

The preferred nonionic surfactants of the formula (III) can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula (III) may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals. Regardless of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, agents according to the invention are preferred in which R ¹ in formula (III) is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preferred agents are characterized in that R ² and R ³ are each a residue -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

In summary, nonionic surfactants 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 are particularly preferred for use in the agents according to the invention.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the agents according to the invention contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, particularly preferably up to 20 wt .-% and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants are included.

Further particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25 Wt .-% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred agent according to the invention contains nonionic 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 having 4 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 for values between 0.5 and 1.5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-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 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may 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, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , 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. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when 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 may be joined 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 selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula zu

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 is 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 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

In summary, agents according to the invention are preferred, the end-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 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Anionic, cationic and / or amphoteric surfactants may also be used in conjunction with the surfactants mentioned, these having only minor importance owing to their foaming behavior in automatic dishwashing, and in most cases only in amounts below 10% by weight, in most cases even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent used, provided that the agent is a machine dishwashing detergent. The agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.

In the context of the present invention, surfactant-capped surfactants and nonionic surfactants with butoxy groups are preferably also usable as nonionic surfactants. The first group includes in particular representatives of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x R ² ,

in the R ¹ for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms, R ^{2 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 C atoms, which is optionally substituted by 1, 2, 3, 4 or 5 hydroxy groups and optionally by further ether groups, R ^{3 is} -H or methyl, ethyl, n- propyl, iso -propyl, n- butyl, iso -butyl or tert -butyl and x can take values between 1 and 40. R ² may optionally be alkoxylated, wherein the alkoxy group is preferably selected from ethoxy, propoxy, butoxy groups and mixtures thereof.

In this case, preference is given to surfactants of the abovementioned formula in which R ^{1 is} a C _9-11 or C _11-15 -alkyl radical, R ³ = H and x assumes a value of 8 to 15, while R ² preferably represents a straight-chain or branched saturated Alkrest stands. Particularly preferred surfactants can be defined by the formulas C _9-11 (EO) ₈ -C (CH ₃ ) ₂ CH ₂ CH ₃ , C _11-15 (EO) ₁₅ (PO) ₆ -C _12-14 , C _9-11 (EO) ₈ (CH ₂ ) ₄ CH ₃ .

Also suitable are mixed-alkoxylated surfactants, preference being given to those having butoxy groups. Such surfactants can be defined by the formula

R ¹ (EO) _a (PO) _b (BO) _c

in which R ^{1 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c is between 1 and 30, preferably between 1 and 20.

Alternatively, the EO and PO groups in the above formula may also be reversed so that surfactants of the general formula

R ¹ (PO) _b (EO) _a (BO) _c ,

in the R ¹ for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c for values between 1 and 30, preferably between 1 and 20, is also usable with preference.

Particularly preferred representatives of this group of surfactants can be distinguished by the formulas C _9-11 (PO) ₃ (EO) ₁₃ (BO) ₁₅ , C _9-11 (PO) ₃ (EO) ₁₃ (BO) ₆ , C _{9- 11} (PO) ₃ (EO) ₁₃ (BO) ₃ , C _9-11 (EO) ₁₃ (BO) ₆ , C _9-11 (EO) ₁₃ (BO) ₃ , C _9-11 (PO) (EO) ₁₃ (BO) ₃ , C _9-11 (EO) ₈ (BO) ₃ , C _9-11 (EO) ₈ (BO) ₂ , C _12-15 (EO) ₇ (BO) ₂ , C _9-11 ( EO) ₈ (BO) ₂ , C _9-11 (EO) ₈ (BO). A particularly preferred surfactant of formula C _13-15 (EO) _9-10 (BO) _1-2 is commercially available under the name Plurafac LF ^® 221st It is also possible to use a surfactant of the formula C _12-13 (EO) ₁₀ (BO) ₂ .

In the context of the present invention, agents, in particular rinse aids, are preferred which contain the at least one nonionic surfactant in amounts of from 1 to 30% by weight, preferably from 2.5 to 25% by weight, particularly preferably from 3.5 to 20 Wt .-%, and in particular from 5 to 15 wt .-%, each based on the agent included.

In the compositions according to the invention, the glass corrosion-inhibiting multi-arm silyl polyalkoxylates can also be used in combination with other glass corrosion protection agents known from the prior art.

In a further embodiment of the invention, therefore, the compositions according to the invention additionally contain, in addition to the glass corrosion-inhibiting multi-arm silyl polyalkoxylate, at least one corrosion-protecting agent which is suitable for reducing glass corrosion when mechanically cleaning a glass surface.

This at least one optionally additionally present corrosion-protective agent is in particular selected from the group of the magnesium and / or zinc salts of at least one monomeric and / or polymeric organic acid, wherein the at least one acid is selected is from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms, the resin acids, the aromatic mono , Di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids.

Suitable additional agents which are capable of providing corrosion protection for glassware in cleaning and / or rinsing operations, particularly in a dishwashing machine, are compounds containing zinc in oxidized form, i. Zinc compounds in which zinc is cationic. Similarly, magnesium salts are also preferred. Both soluble and poorly soluble or insoluble zinc or magnesium compounds can be present in the compositions according to the invention, with poorly soluble or non-soluble compounds having to be stabilized against settling in a suitable manner (for example via the parameters particle size of the particles and viscosity of the composition). In one embodiment, agents according to the invention contain at least one magnesium and / or zinc salt of at least one monomeric and / or polymeric organic acid.

The acids concerned preferably originate from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms and / or resin acids.

• Aus der Gruppe der unverzweigten gesättigten oder ungesättigten Monocarbonsäuren: Methansäure (Ameisensäure), Ethansäure (Essigsäure), Propansäure (Propionsäure), Pentansäure (Valeriansäure), Hexansäure (Capronsäure), Heptansäure (Önanthsäure), Octansäure (Caprylsäure), Nonansäure (Pelargonsäure), Decansäure (Caprinsäure), Undecansäure, Dodecansäure (Laurinsäure), Tridecansäure, Tetradecansäure (Myristinsäure), Pentadecansäure, Hexadecansäure (Palmitinsäure), Heptadecansäure (Margarinsäure), Octadecansäure (Stearinsäure), Eicosansäure (Arachinsäure), Docosansäure (Behensäure), Tetracosansäure (Lignocerinsäure), Hexacosansäure (Cerotinsäure), Triacotansäure (Melissinsäure), 9c-Hexadecensäure (Palmitoleinsäure), 6c-Octadecensäure (Petroselinsäure), 6t-Octadecensäure (Petroselaidinsäure), 9c-Octadecensäure (Ölsäure), 9t-Octadecensäure (Elaidinsäure), 9c,12c-Octadecadiensäure (Linolsäure), 9t,12t-Octadecadiensäure (Linolaidinsäure) und 9c,12c,15c-Octadecatreinsäure (Linolensäure).

Although according to the invention all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be included in the compositions according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the Groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred. Within these groups, the acids mentioned below are again preferred in the context of the present invention:

• From the group of unbranched saturated or unsaturated monocarboxylic acids: methanoic acid (formic acid), ethanoic acid (acetic acid), propionic acid (propionic acid), pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), Octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid) , Docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid), 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t Octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid), and 9c, 12c, 15c-octadecatenic acid (linolenic acid).

From the group of branched saturated or unsaturated monocarboxylic acids: 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid, 2-decyltetradecanoic acid, 2-undecylpentadecanoic acid, 2-dodecylhexadecanoic acid, 2-tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, and 2-heptadecylheneicosanoic acid.

From the group of unbranched saturated or unsaturated di- or tricarboxylic acids: propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid ( Sebacic acid), 2c-butenedioic acid (maleic acid), 2t-butenedioic acid (fumaric acid) and 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

From the group of aromatic mono-, di- and tricarboxylic acids: benzoic acid, 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid) and 3,5-dicarboxybenzoic acid (Trimesionsäure).

From the group of sugar acids: galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid and alginic acid.

From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-dihydroxybutanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2 Hydroxybenzoic acid (salicylic acid) and 3,4,5-trihydroxybenzoic acid (gallic acid).

From the group of oxo acids: 2-oxopropionic acid (pyruvic acid) and 4-oxopentanoic acid (levulinic acid).

From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine and histidine.

From the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methylmethacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers and vinylpyrrolidone / vinyl acrylate copolymers.

The spectrum of the preferred zinc salts of organic acids, preferably organic carboxylic acids, ranges from salts which are sparingly soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, to those salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature). The first group of zinc salts include, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate, zinc tosylate (p-toluenesulfonic acid Zn salt) and zinc gluconate:

In a further embodiment of the present invention, the agents according to the invention comprise at least one zinc salt but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate, Zinc lactate and / or zinc citrate. Furthermore, zinc ricinoleate, zinc abietate and zinc oxalate are also preferably used.

The at least one anticorrosive agent optionally additionally present in the composition according to the invention, in addition to the glass corrosion-inhibiting multi-arm silyl polyalkoxylate, is particularly preferred in the composition in amounts of from 0.2 to 15% by weight, preferably from 0.5 to 10% by weight preferably from 1.0 to 7.5 wt .-% and in particular from 2 to 5 wt .-%, each based on the agent.

In addition to the at least one multi-arm silyl polyalkoxylate and the at least one nonionic surfactant, the agents according to the invention may contain water and / or other active ingredients and / or auxiliaries ad 100%. The most important ingredients that may be included in the compositions of this invention besides multi-arm silyl polyalkoxylates and nonionic surfactants are described below.

Acidifying agents can be added to the compositions according to the invention, in particular to set a desired pH. Both inorganic acids such as, for example, hydrochloric or sulfuric acid and organic acids such as, for example, acetic acid, lactic acid or citric acid are suitable here, provided they are compatible with the other ingredients. For example, in the event that the agent according to the invention is a rinse aid, it is generally desirable to lower the pH of the liquor in the rinse cycle and to adjust the rinse aid to a pH of less than 7. For reasons of consumer protection and handling safety, the use of solid mono-, oligo- and polycarboxylic acids is particularly advantageous. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).

The acidifying agents, in particular mono-, oligo- and polycarboxylic acids, particularly preferably tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid and especially citric acid, can be used in the compositions according to the invention, for example in amounts of from 0.5 to 15% by weight. %, preferably from 1 to 7.5 wt .-%, particularly preferably from 2 to 5 wt .-% and in particular from 2.5 to 4 wt .-%, each based on the agent, be contained.

Of course, the agents according to the invention may also contain, as buffer substances, salts of the abovementioned acids, i. the acidifying agents described above may be partially neutralized in the composition of the invention. Preferred here are the alkali metal salts, and among these, the sodium salts are particularly preferred. Especially preferred according to the invention is the use of trisodium citrate.

In a preferred embodiment of the invention, the agents according to the invention have an acidic to slightly alkaline pH, in particular a pH of up to 9. Preference is given to pH values from 1 to 6, with pH values from 2 to 4 being very particular are preferred.

Non-aqueous solvents which can be used in the compositions according to the invention originate, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents, so that preferred agents are characterized in that they contain at least one non-aqueous solvent, preferably ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, glycol, propanediol, butanediol, glycerol, diglycol, propyldiglycol , Butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol. 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether or mixtures of these solvents. Ethanol is very particularly preferred as the non-aqueous solvent.

The compositions according to the present invention may further contain hydrotropes, also called solubilizers. The addition of such substances causes a poorly soluble substance in the presence of the hydrotrope, which is itself no solvent, becomes water-soluble. Substances which cause such solubility improvement are termed hydrotropes or hydrotropes. Typical hydrotropes, e.g. in the manufacture of liquid detergents or cleaners, xylene and cumene sulfonate. Other substances, e.g. Urea or N-methylacetamide increase the solubility by a structure-breaking effect, in which the water structure in the vicinity of the hydrophobic group of a poorly soluble substance is degraded.

in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise von 1 bis 7,5 Gew.-%, besonders bevorzugt von 2 bis 5 Gew.-% und insbesondere von 2,5 bis 4 Gew.-%, jeweils bezogen auf das Mittel, wobei jeder der Reste R₁, R₂, R₃, R₄, R₅ unabhängig voneinander ausgewählt ist aus H oder einem C_1-5-Alkyl- oder -Alkenylrest und X für ein Kation steht.Agents preferred in the context of the present invention comprise solubilizers, preferably aromatic sulfonates of the formula

in amounts of 0.5 to 10 wt .-%, preferably from 1 to 7.5 wt .-%, particularly preferably from 2 to 5 wt .-% and in particular from 2.5 to 4 wt .-%, in each case based to the agent wherein each of R ₁ , R ₂ , R ₃ , R ₄ , R _{5 is} independently selected from H or a C _1-5 alkyl or alkenyl group and X is a cation.

Preferred substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are independently selected from H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl or neo-pentyl. In general, at least three of said radicals R ¹ to R ^{5 are} hydrogen atoms, with aromatic sulfonates being preferred in which three or four substituents on the aromatic ring are hydrogen atoms. The remaining or the remaining two radicals can take any position to the sulfonate group and each other. For monosubstituted compounds of the formula I, it is preferred that the radical R _{3 is} an alkyl radical, while R ₁ , R ₂ , R ₄ , and R _{5 are} H (para-substitution).

Particularly preferred aromatic sulfonates in the context of the present invention are toluene, cumene or xylene sulfonate.

Of the two commercially available toluenesulfonates (ortho- and para-toluenesulfonate), the para-isomer is preferred in the context of the present invention. The para-isopropylbenzenesulfonate is also the preferred compound in the case of the cumene sulfonates. Since xylene is usually used industrially as a mixture of isomers, the industrially available xylenesulfonate is also a mixture of several compounds resulting from the sulfonation of ortho, meta and para xylene result. In these mixtures of isomers, the compounds dominate, in each of which the following radicals in the general formula I are methyl groups (all other radicals are H): R ₁ and R ₂ , R ₁ and R ₄ , R ₁ and R ₃ and R ₁ and R ₅ . Thus, in the xylenesulfonates, at least one methyl group is preferably ortho to the sulfonate group.

X in the general formula given above represents a cation, for example an alkali metal cation such as sodium or potassium. However, X may also represent the equivalent charge portion of a more cost cation, such as Mg ²⁺ / 2 or Al ³⁺ / 3, wherein the said cations, sodium is preferred.

1. a) 0,05 bis 10, vorzugsweise 0,1 bis 7, besonders bevorzugt 0,2 bis 5 und insbesondere 0,3 bis 3 Gew.-% mindestens eines mehrarmigen Silyl-Polyalkoxylats der Formel (I)
2. b) 0,1 bis 40, vorzugsweise 1 bis 20, besonders bevorzugt 5 bis 20 Gew.-% mindestens eines nichtionischen Tensids, insbesondere ein Gemisch aus mindestens einem Polyalkoxylat und mindestens einem endgruppenverschlossenen poly(oxyalkylierten) Niotensid
3. c) 0 bis 15, vorzugsweise 1 bis 10, besonders bevorzugt 2 bis 7 Gew.-% mindestens eines Acidifizierungsmittels
4. d) 1 bis 20, vorzugsweise 2 bis 15, besonders bevorzugt 3 bis 10 Gew.-% mindestens eines nichtwässrigen Lösungsmittels und/oder Lösungsvermittlers
5. e) Wasser.

Further preferred embodiments of the present invention are means for machine cleaning a glass surface, in particular dishwashing rinse aid containing

1. a) 0.05 to 10, preferably 0.1 to 7, particularly preferably 0.2 to 5 and in particular 0.3 to 3 wt .-% of at least one multi-armed silyl polyalkoxylate of the formula (I)
2. b) 0.1 to 40, preferably 1 to 20, particularly preferably 5 to 20 wt .-% of at least one nonionic surfactant, in particular a mixture of at least one polyalkoxylate and at least one endgruppenverschlossenen poly (oxyalkylated) nonionic surfactant
3. c) 0 to 15, preferably 1 to 10, particularly preferably 2 to 7 wt .-% of at least one Acidifizierungsmittels
4. d) 1 to 20, preferably 2 to 15, particularly preferably 3 to 10 wt .-% of at least one nonaqueous solvent and / or solubilizer
5. e) water.

If the composition is a concentrate which is to be diluted before use, then the content of nonionic surfactants is in the upper range of the stated range, while for a ready-to-use agent it is in the lower range of the indicated range, and preferably up to about 15% by weight. -% is.

In another embodiment of the invention, the agents according to the invention may additionally contain one or more substances from the groups of soil release polymers, dyes and fragrances.

Substances which prevent the re-soiling of surfaces and / or facilitate the removal of soil after a single use are so-called "soil release compounds". The soil release compounds which can be used according to the invention include all known compounds known in the prior art. Particularly suitable are cationic polymers, in particular polymers with imino groups, cationic cellulose derivatives or cationic homo- and / or copolymers with quaternized ammonium alkyl methacrylate groups as monomer units.

The cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides with quaternary side groups as soil release compounds.

Natural polyuronic acids and related substances, as well as polyampholytes and hydrophobized polyampholytes, or mixtures of these substances, are particularly preferred within the scope of the invention.

In order to improve the aesthetic impression of the agents according to the invention, they can be dyed with suitable dyes. Dyes which are preferred in the context of the present invention and whose selection is not difficult for the skilled person, possess a high storage stability and insensitivity to the other ingredients of the compositions and to light, and in particular no pronounced substantivity towards dishes in order not to stain them.

Preferred for use in the compositions according to the invention are all colorants which can be oxidatively destroyed and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a commercial product ^® for example as Basacid Green 970 from BASF, Ludwigshafen, is, as well as mixtures thereof with suitable. blue dyes. Further suitable colorants Pigmosol ^® come ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl Red 545 FL (CI 45170), Sandolan® ^® rhodamine EB400 (CI 45100), Basacid® ^® Yellow 094 (CI 47005) Sicovit ^® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), pigment Blue 15 (CI 74160), Supranol Blue ^® GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan Yellow ^® N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.

When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the surfaces to be treated and, in particular, for plastics possibly present at the same time. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the compositions according to the invention varies. For highly soluble colorants, such as the Basacid Green ^® above or also above Sandolan Blue ^®, dye concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-% are typically chosen. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant, however, is typically a few 10 ^-3 to 10 ^-4 wt .-%.

The compositions according to the invention may furthermore comprise at least one perfume, in particular a perfume. In the event that the agent of the invention is a dishwasher detergent or a rinse aid, can be eliminated by late release of the perfume in the rinse cycle often occurring in dishwashers "alkali odor" when opening the machine. Fragrances may also be added to the compositions within the scope of the present invention to enhance the aesthetics of the products and to provide the user with a visually and sensory "typical and distinctive" product in addition to the performance of the product.

In the context of the present invention, all substances and mixtures of substances which are customary for the perfuming of cleaning agents and which are compatible with the other constituents of the agents according to the invention may in principle be used as perfume oils or fragrances.

Another object of the present invention is the use of an agent as described above to reduce glass corrosion and / or to improve the drying performance of cleaning a glass surface mechanically, especially in automatic dishwashing.

Examples: 1. Preparation of a six-armed triethoxysilyl-terminated polyalkoxylate

The starting material used was a polyether polyol which is a 6-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of 80/20 and a molecular weight of 12,000 g / mol, obtained by anionic ring-opening polymerization of ethylene oxide and propylene oxide using sorbitol as initiator. Before further reaction, the polyether polyol was heated in vacuo with stirring for 1 h at 80 ° C. A solution of polyether polyol (3 g, 0.25 mmol), triethylenediamine (9 mg, 0.081 mmol) and dibutyltin dilaureate (9 mg, 0.014 mmol) in 25 mL of anhydrous toluene was added, to which was added a solution of (3-isocyanatopropyl ) triethoxysilane (0.6 ml, 2.30 mmol) in 10 ml of anhydrous toluene was added dropwise. The solution was further stirred at 50 ° C overnight. After removing the toluene under vacuum, the crude product was repeatedly washed with anhydrous ether. After vacuum drying, the product, each having a triethoxylsilyl group at the free ends of the polymer arms of the star-shaped prepolymer, was obtained as a colorless viscous liquid. IR (film, cm ^-1 ): 3349 (m, -CO-NH-), 2868 (s, -CH ₂ -, -CH ₃ ), 1719 (s, -C = O), 1456 (m, -CH ₂ -, -CH ₃ ), 1107 (s, -COC-), 954 (m, -Si-O-). ¹ H-NMR (benzene-d ₆ , ppm): 1.13 (d, -CH ₃ of polymer arms), 1.21 (t, -CH ₃ of silane end groups), 3.47 (s, -CH ₂ of polymer arms), 3.74 (q, -CH ₂ of silane end groups). The triethoxysilyl-terminated polyalkoxylate obtained has a molecular weight of 13,500.

2. Preparation of a three-armed triethoxysilyl-terminated polyalkoxylate

Voranol CP 1421 from DOW Chemicals was dried in vacuo with stirring for 1 h at 80 ° C. To 2.04 g (0.41 mmol) of the dried polyether polyol was slowly added 317 mg (1.0 equivalents) of 3-isocyanato-propyltriethoxysilane. The reaction mixture was further stirred under inert gas at 100 ° C for 2 days until the vibration band of the NCO group disappeared upon IR measurement. The product, each having a triethoxylsilyl group at the free ends of the polymer arms of the polyether polyol, was obtained as a colorless viscous liquid.

3. Preparation of a mixture containing a three-armed and an eight-armed triethoxysilyl-terminated polyalkoxylate

Voranol 4053 from DOW Chemicals was dried in vacuo with stirring for 1 h at 80 ° C. To 209 g (16.9 mmol) of the dried polyether polyol was added 20.9 mg (0.01%). Dibutyltin dilaureate and 30.3 g (1.0 equivalent) of 3-isocyanato-propyltriethoxysilane were added slowly. The reaction mixture was further stirred under inert gas at room temperature for 2 days until the NCO band disappeared on IR measurement. The product was obtained, which in each case has a triethoxylsilyl group at the free ends of the polymer arms of the polyether polyol and represents a mixture of a 3-armed and an 8-armed polyalkoxylate in a ratio of about 20/80, as a colorless viscous liquid.

4. Glass corrosion test according to the prior art (comparative experiment A):

In a Miele G 6xx continuous domestic dishwashing machine, various commercially available drinking glasses and plates were rinsed at a water hardness of 0-1 ° dH with a commercially available machine dishwashing detergent available as a tablet. After 50 rinsing cycles, the glass corrosion observed on the items to be washed was evaluated with regard to the parameters haze and line corrosion. The following table shows the results. Glass Type cloudiness line corrosion Highlight (Bohemia Crystal) Kalikristall 2.5 0 Tina (Steklarna Hrastnik) soda lime 2.5 3 Balloon (ARC) soda lime 2 3 Chardonnay (Stöltzle Oberglas) Kalikristall 2 1 Riserva (Bormioli Rocco) Kalikristall 1 2.5 Michelangelo (Luigi Bormioli) Kalikristall 2 3 Panal Tumbler (Libbey) soda lime 2 0 Vina (Libbey) soda lime 3 3 Rating scale: 0 to 5, where 0 stands for undamaged glasses and 5 for a very strong corrosion damage.

The following table shows the results for decor fading after 50 rinse cycles: Type fading Drinking glass Flower green (Montana) 2 Drinking glass flower blue (Montana) 1.5 Plate Piano (Bormioli Rocco) 1 Rating scale: 0 to 5, where 0 is an imperceptible fade and 5 is a very severe fade.

Differences of 1 grade are considered significant.

5. Glass corrosion test according to the prior art (comparative experiment B):

The procedure was as described under 4. (glass corrosion test according to the prior art, comparative experiment A), but at the beginning of the rinse cycle 3 ml of a commercial rinse aid were automatically metered directly into the machine. This rinse aid contained 2.5% by weight of zinc acetate as a glass corrosion protection component. After 50 rinsing cycles, the glass corrosion observed on the items to be washed was evaluated with regard to the parameters haze and line corrosion. The following table shows the results. Glass Type cloudiness line corrosion Highlight (Bohemia Crystal) Kalikristall 1.5 0 Tina (Steklarna Hrastnik) soda lime 0.5 0 Balloon (ARC) soda lime 0.5 0 Chardonnay (Stöltzle Oberglas) Kalikristall 0 0 Riserva (Bormioli Rocco) Kalikristall 1.5 0 Panal Tumbler (Libbey) soda lime 1.5 0 Vina (Libbey) soda lime 0.5 0

The following table shows the results for decor fading after 50 rinse cycles:. Type fading Drinking glass Flower green (Montana) 1 Drinking glass flower blue (Montana) 0.5 Plate Piano (Bormioli Rocco) 0.5

6. Glass corrosion test according to the present invention:

• 1,0 Gew.-% des Triethoxysilyl-terminierten Polyalkoxylats aus Beispiel 1
• 20,0 Gew.-% Ethanol
• 79,0 Gew.-% Wasser.

First, a formulation F was prepared with the following composition:

• 1.0% by weight of the triethoxysilyl-terminated polyalkoxylate from Example 1
• 20.0% by weight of ethanol
• 79.0% by weight of water.

In a continuous domestic dishwashing machine type Miele G 6xx various commercially available drinking glasses and plates were rinsed at a water hardness of 0-1 ° dH with a commercial, available as Tab machine dishwashing detergent. At the beginning of the rinse cycle, 1 ml of Formulation F was automatically metered directly into the machine.
The following table shows the results for glass corrosion (haze and line corrosion) after 50 rinse cycles: Glass Type cloudiness line corrosion Highlight (Bohemia Crystal) Kalikristall 1 0 Tina (Steklarna Hrastnik) soda lime 0.5 0 Balloon (ARC) soda lime 0.5 0 Chardonnay (Stöltzle Oberglas) Kalikristall 0 0 Riserva (Bormioli Rocco) Kalikristall 0 0 Michelangelo (Luigi Bormioli) Kalikristall 0 0 Panal Tumbler (Libbey) soda lime 0.5 0 Vina (Libbey) soda lime 0 0

The following table shows the results for decor fading after 50 rinse cycles: Type fading Drinking glass Flower green (Montana) 1 Drinking glass flower blue (Montana) 1 Plate Piano (Bormioli Rocco) 0.5

7. Evaluation of Experiments 4 to 6

The comparison of the flushing tests of Examples 4 and 6 shows that the use of 10 mg of the silyl polyalkoxylate caused a significantly reduced glass corrosion. This was reflected both in the dimensions turbidity and line corrosion. Furthermore, the durability of decorated glassware is improved, as evidenced by reduced fading of the decorations.
Comparison of the rinsing tests from Examples 5 and 6 shows that comparably good or even better effects were achieved with the silyl polyalkoxylate according to the invention even at a use concentration which is 7.5 times lower than with zinc acetate, which is a conventional active glass protection agent represents the technology.

Similarly good results were obtained when one of the triethoxysilyl-terminated polyalkoxylates from Examples 2 and 3 was used in the flushing tests instead of the triethoxysilyl-terminated polyalkoxylate of Example 1.

8. Test results for further effects

It has also been found that the use of multi-arm silyl polyalkoxylates in the automated cleaning of glass surfaces causes an improvement in the drying performance of the cleaned surfaces. This is understood in particular to mean a shortening of the drying time and / or a reduction in the formation of limescale and deposits on the cleaned surfaces.
This was demonstrated by rinsing tests in a household dishwasher type Miele G 1730 (automatic program, temperature in the cleaning cycle 45-65 ° C). The dishes used were wine glasses and black glass plates, which had been pre-cleaned with a commercially available dishwashing detergent. The silyl polyalkoxylate was metered in each case in the form of 5 ml of a formulation G in the cleaning cycle into the interior of the dishwasher. After completion of the program, the time to surface drying was measured, and the extent of limescale was visually determined and evaluated in relation to the reference values, respectively. The reference value was washed dishes cleaned in the same way, but the formulation G contained instead of the silyl compound (s) a weight-equivalent amount of water.
The following scale was used for the evaluation: +++ ' very much better ¹⁾ as a reference, ++ much better than reference, + a little better than reference, - no difference to the reference, ¹⁾ "better" means in the case of
a) Drying time: faster drying
b) staining: less water residue, less stain

08.01:

As the silyl polyalkoxylate, the six-armed triethoxysilyl-terminated polyalkoxylate of Synthesis Example 1 was used.
Formulation G consisted of: xg Silyl polyalkoxylate (values of x see table) yg Tetraethoxysilane (values of y see table). 2.5 g water 2.5 g acetic acid ad 100 g Ethanol.

Results:

x y drying time spotting 5.0 0 - - 15 0 + + 5.0 10 +++ +++ Similar results were obtained when, instead of the silyl polyalkoxylate from Synthesis Example 1, the silyl polyalkoxylate from Synthesis Example 3 was used.
Equally identical results were obtained in each case with the two silyl polyalkoxylates if the formulation G was not dosed in each case in the cleaning cycle, but in the rinse cycle into the interior of the dishwasher.

08.02:

The silyl polyalkoxylate used was the mixture comprising a three-armed and an eight-armed triethoxysilyl-terminated polyalkoxylate from Synthesis Example 3.
Formulation G consisted of: xg Silyl polyalkoxylate (values of x see table) ad 100 g Water.

Results:

x drying time spotting 2.5 - - 5.0 ++ ++ 10 +++ +++ The same results were obtained when the formulation G was not dosed in the cleaning cycle, but in the final rinse cycle in the interior of the dishwasher.

Similar results were obtained in the experimental arrangements 8.1 and 8.2, when the silyl polyalkoxylate from Synthesis Example 2 was used as the silyl polyalkoxylate.

Claims (15)

1. The use of a multi-arm silyl-polyalkoxylate of formula (I)
   
           (H-A)_n-Z-[A-B-Si(OR¹)_r(R²)_3-r]_m     (I),
   
   

   wherein Z represents a (m+n)-valent radical with at least three carbon atoms,

   A designates a bivalent polyoxyalkylene radical, wherein the m+n polyoxyalkylene radicals bound to Z may be different from each other, and wherein a radical A is respectively bound to Z via an oxygen atom belonging to Z and bound to B or hydrogen via an oxygen atom belonging to A,

   B represents a chemical bond or a bivalent organic radical with 1 to 50 carbon atoms,

   OR¹ designates a hydrolyzable group, R¹ and R² designate independently of each other a linear or branched alkyl group with 1 to 6 carbon atoms and r represents an integer from 1 to 3, and

   m is an integer ≥ 1 and n represents 0 or an integer ≥ 1, and m+n has a value from 3 to 100,

   for reducing glass corrosion and/or for improving the drying performance for machine-cleaning of a glass surface.
2. The use according to claim 1, characterized in that the silyl-polyalkoxylate of formula (I) has a mass average (weight average of the molecular weight) from 500 to 50,000.
3. The use according to claim 1 or 2, characterized in that, in formula (I), Z represents an at least trivalent, in particular trivalent to octavalent, acyclic or cyclic hydrocarbon radical with 3 to 12 carbon atoms.
4. The use according to any of claims 1 to 3, characterized in that in formula (I), n represents 0, 1 or 2, and m designates a number from 3 to 8.
5. The use according to any of claims 1 to 4, characterized in that, in formula (I), A represents -(CHR³-CHR⁴-O)_p-, wherein R³ and R⁴ designate independently of each other hydrogen, methyl or ethyl, and p designates an integer from 2 to 10,000.
6. The use according to any of claims 1 to 5, characterized in that in formula (I), B represents a bond or the radical -C(O)-NH-(CH₂)₃-.
7. The use according to any of claims 1 to 6, characterized in that in formula (I), R¹ and R² represent independently of each other a methyl or ethyl.
8. The use according to any of claims 1 to 7, characterized in that in formula (I), r is equal to 3.
9. The use according to any of claims 1 to 8, characterized in that a mixture of at least two different multi-arm silyl-polyalkoxylates of formula (I) is applied.
10. The use according to claim 9, characterized in that said at least two different multi-arm silyl-polyalkoxylates differ in the number of their arms.
11. The use according to any of claims 1 to 10, characterized in that it takes place in the presence of at least one hydrolyzable silicic acid derivative, preferably at least one ester of orthosilicic acid, in particular at least one tetraalkoxysilane and more preferably tetraethoxysilane.
12. A method for machine-cleaning a glass surface, in which the glass surface is brought into contact with a multi-arm silyl-polyalkoxylate of formula (I) according to claim 1.
13. An agent for cleaning a glass surface, in particular for machine-rinsing a glass surface, containing

    a) 0.05 to 10% by weight of at least one multi-arm silylpolyalkoxylate of formula (I)
    
            (H-A)_n-Z-[A-B-Si(OR¹)_r(R²)_3-r]_m     (I),
    
    wherein

    Z represents a (m+n)-valent radical with at least three carbon atoms, A designates a bivalent polyoxyalkylene radical, wherein the m+n polyoxyalkylene radicals bound to Z may be different from each other, and wherein a radical A is respectively bound to Z via an oxygen atom belonging to Z and bound to B or hydrogen via an oxygen atom belonging to A,

    B represents a chemical bond or a bivalent organic radical with 1 to 50 carbon atoms,

    OR¹ designates a hydrolyzable group, R¹ and R² designate independently of each other a linear or branched alkyl group with 1 to 6 carbon atoms and r represents an integer from 1 to 3, and

    m is an integer ≥ 1 and n represents 0 or an integer ≥ 1, and m+n has a value from 3 to 100,

    b) 0.1 to 40% by weight of at least one non-ionic surfactant,

    c) if desired, water and/or one of several substances selected from corrosion inhibiting agents, acidification agents, non-aqueous solvents and solubilizers.
14. The agent according to claim 13, characterized in that it contains said at least one non-ionic surfactant in amounts from 1 to 30% by weight, preferably from 2.5 to 25% by weight, more preferably from 3.5 to 20% by weight, and in particular from 5 to 15% by weight, respectively based on the agent.
15. The use of an agent according to any of claims 13 or 14 for reducing glass corrosion and/or for improving the drying performance in machine-cleaning of a glass surface, in particular in machine dishwashing.