Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0073—Anticorrosion compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3776—Heterocyclic compounds, e.g. lactam
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/18—Glass; Plastics

Definitions

• the present invention relates to a method for cleaning glass surfaces of buildings or of automobiles, characterized in that at least one aqueous formulation containing
• (C) a total of from 0.5 to 50% by weight of at least one high foaming surfactant
• the present invention relates to formulations and a process for their preparation. Furthermore, the present invention relates to the use of formulations according to the invention. Glass surfaces of buildings, in particular windows, are repeatedly cleaned during their "service life", for example at least once a year.Windows of automobiles are cleaned much more frequently. Typically, surfactant-containing formulations are used for cleaning.After the actual cleaning, the rest of the liquid with a squeegee or similar tool, and only a thin film of liquid remains on the glass surface and dries.
• glass surfaces of buildings are to be understood as meaning large-area surfaces, curved or preferably planar, of glass, for example window glass.
• Glass surfaces of buildings may preferably be glass facades or windows or glass doors of buildings. Examples of glass surfaces of automobiles are the windshield and the side windows.
• aqueous formulation is understood to mean a formulation which is liquid or foamy under the conditions of the inventive cleaning process and which contains at least 30% by weight, preferably from 50 to 99% by weight, of water. Contain in the cleaning process according to the invention used aqueous formulations
• (A) in total in the range from 1 to 50% by weight of at least one compound selected from methylglycine diacetate (MGDA) and glutamic acid diacetate and their salts and derivatives, in short also called compound (A),
• Co cationic polymer
• B cationic polymer
• B preferably at least one homopolymer or copolymer of ethyleneimine, in short also called polyethyleneimine (B)
• surfactant (C) a total of from 0.5 to 50% by weight of at least one high-foaming surfactant, also referred to as surfactant (C) for short,
• Compound (A) is selected from aminocarboxylates and polyaminocarboxylates, in the context of the present invention also briefly aminocarboxylate (A) or polyaminocarboxylate (A) or compound (A) called, as well as their derivatives and preferably salts.
• Compound (A) may be in the form of a free acid or preferably in partially or completely neutralized form, ie as a salt.
• Suitable counterions are, for example, inorganic cations, for example ammonium, alkali or alkaline earth metal, preferably Mg 2+ , Ca 2+ , Na + , K + , or organic cations, preferably ammonium substituted with one or more organic radicals, in particular triethanolammonium, N, N-diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N, N-butyldiethanolammonium or N, N di-Ci-C4-alkylethanolammonium.
• Preference is given to the alkali metal salts and particularly preferably sodium salts.
• compound (A) is selected from derivatives of aminocarboxylates and polyaminocarboxylates, for example from methyl or ethyl esters.
• aminocarboxylates (A) are understood to mean nitrilotriacetic acid and those organic compounds which have a tertiary amino group which has one or two Ch-COOH groups which, as mentioned above, can be partially or completely neutralized or . can.
• polyaminocarboxylates (A) are understood as meaning those organic compounds which have at least two tertiary amino groups which independently of one another have one or two Ch-COOH groups which, as mentioned above, can be partially or completely neutralized or . can.
• aminocarboxylates (A) are selected from those organic compounds having a secondary amino group having one or two CH (COOH) CH 2 -COOH group (s) partially or partially substituted as mentioned above can be completely neutralized or can.
• polyaminocarboxylates (A) are selected from those organic compounds which have at least two secondary amino groups, each containing a CH (COOH) CH 2 COOH group, which, as mentioned above, partially or completely can be neutralized.
• Preferred polyaminocarboxylates (A) are selected from 1,2-diaminoethanetetraacetic acid (EDTA), diethylenetriamine pentaacetate (DTPA), hydroxyethylenediaminetriacetate (HEDTA), and their respective salts, more preferably alkali metal salts, in particular the sodium salts.
• EDTA 1,2-diaminoethanetetraacetic acid
• DTPA diethylenetriamine pentaacetate
• HEDTA hydroxyethylenediaminetriacetate
• alkali metal salts in particular the sodium salts.
• compound (A) is selected from methylglycine diacetate (MGDA), nitrilotriacetic acid (NTA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and derivatives thereof and preferably their salts, in particular the Sodium salts of MGDA, IDS and GLDA. Very particular preference is Methylglycindi- acetate and the trisodium salt of MGDA.
• the aqueous formulation used in the cleaning process according to the invention further contains
• (B) at least one cationic (co) polymer, also called cationic (co) polymer (B).
• Preferred (co) polymers (B) are selected from polyvinylamine and linear and branched homopolymers of alkyleneimine.
• Particularly preferred (co) polymers (B) are selected from homopolymers and copolymers of ethyleneimine, also referred to in short as polyethyleneimine (B), and homopolymers and copolymers of propyleneimine, in short also called polypropyleneimine (B).
• Cationic (co) polymers (B) in the context of the present invention are understood to mean those (co) polymers which have at least one of the following structural features:
• Examples are -NH2 groups, - NH (Ci-Cio-alkyl) groups, -N (Ci-Cio-alkyl) 2 groups, -NH (C 2 -Cio alkylene) groups, - (CH 2) 2-N (CH 3 ) 2 groups, NH-CH 2 CH (C 1 -C 10 -alkyl) groups and - (C 2 -C 10 -alkylene) N (C 2 -C 10 -alkylene) groups, in particular CH 2 -CH 2 -NH-CH 2 -CH 2 -NH- groups and CH 2 -CH 2 -
• Cationic (co) polymer (B) may comprise, per molecule, at least two structural features (i), which may be the same or different, or at least two structural features (ii), which may be the same or different, or at least one structural feature (i ) and at least one structural feature (ii).
• cationic (co) polymer per molecule (B) has at least five structural features (i), which may be the same or different, or at least five structural features (ii), which may be the same or different.
• Cationic (co) polymer (B) can have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic.
• High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol, low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol.
• low molecular weight organic counterions are acetate, propionate and benzoate.
• low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate.
• cationic (co) polymers (B) have a cationic charge density of at least 5 milliequivalents / gram, with the term in g referring to cationic (co) polymer (B) without consideration of the counterions.
• a charge density in the range of 5 to 22 milliequivalents / g is preferred.
• the charge density can be determined, for example, by titration, in particular by titration with potassium polyvinyl sulfate against toluidine blue.
• Cationic (co) polymers (B) may also contain one or more anionic comonomers copolymerized, for example (meth) acrylic acid.
• cationic (co) polymer (B) contains no anionic comonomers in copolymerized form.
• cationic (co) polymers (B) are polyvinylamine-co-vinylformamide, which can be prepared, for example, by partial hydrolysis of polyvinylformamide, furthermore polyvinylpyrrolidone, PolyDADMAC (DADMAC: diallyldimethylammonium chloride), polyvinylpyrrolidone-co-vinyl-3-methylimidazolium, graft copolymers of 3-methyl -N-vinylimidazolium on polyethers such as polyethylene glycol or polypropylene glycol, graft copolymers of 3-methyl-N-vinylimidazolium and N-vinylpyrrolidone on polyethers such as polyethylene glycol or polypropylene glycol.
• cationic (co) polymers (B) are copolymers of (meth) acrylates with N, N-dimethylaminoethyl (meth) acrylate and copolymers of (meth) acrylates with ⁇ , ⁇ , ⁇ -trimethylammoniumethyl (meth) acrylate.
• Another example is cationically modified starch.
• cationic (co) polymer (B) has an average molecular weight M n of from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 50,000 g / mol.
• cationic (co) polymer (B) has an average molecular weight M w in the range of 500 to 1,000,000 g / mol, preferably in the range of 600 to 75,000 g / mol, particularly preferably in the range of 800 to 25,000 g / mol, determinable for example by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• Preferred (co) polymers (B) are selected from polyvinylamines, also referred to as polyvinylamines (B) for short, and from linear and branched homopolymers of alkyleneimines, in short polyalkylenimine (B), and in particular from linear and branched homopolymers of ethyleneimine and / or propylene imine, polyethylenimine (B) or polypropylenimine (B) for short.
• polyvinylamines (B) are not only fully saponified polyvinylamides, for example fully saponified poly-N-vinylformamide, but also so-called hydrophobically modified polyvinylamines, for example by reaction with - one or more linear carboxylic acids with 10 to 22 carbon atoms / molecule, preferably with 14 to 18 carbon atoms / molecule, for example capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margarinic acid, stearic acid, arachidic acid, nonadaptanic acid, linoleic acid, oleic acid, palmitoleic acid, arachidonic acid, behenic acid, stearic acid, oleic acid and Palmitic acid or its esters, in particular ethyl or methyl esters, their acid chlorides or their anhydrides,
• alkyl epoxides having 10 to 22 carbon atoms / molecule, for example 1, 2-hexadecenyl oxide and 1, 2-octadecenyloxide,
• Alkyl ketene dimers having 9 to 21 carbon atoms in the respective alkyl radical, preferably up to 18 carbon atoms, for example dimeric lauryl ketene, dimeric palmityl ketene, lower stearyl ketene and dimeric oleyl ketene, or mixtures thereof,
• Cyclic dicarboxylic anhydrides in particular alkyl-substituted succinic anhydrides having 10 to 22 carbon atoms in the alkyl radical, preferably having 14 to 18 carbon atoms in the alkyl radical, for example dodecenylsuccinic anhydride, tetradecylsuccinic anhydride, Hexadecenylbernsteniklareanhydrid, and with their mixtures, chloroformates of fatty alcohols having 10 to 22 carbon atoms in the alkyl radical , preferably having 14 to 18 carbon atoms in the alkyl radical,
• Alkylene diisocyanates having 10 to 22 carbon atoms in the alkylene radical, preferably having 14 to 18 carbon atoms in the alkyl radical, for example OCN- (CH 2 ) i4-NCO, OCN- (CH 2 ) i6-NCO or OCN- (CH 2 ) i8-NCO or mixtures of at least two of the aforementioned compounds.
• Polyalkyleneimines (B) in the context of the present invention can be prepared not only by polymerization of alkyleneimine, but also, for example, by polycondensation of ⁇ , ⁇ -hydroxy-C 2 -C 10 -alkyleneamines, by polycondensation of ⁇ , (C 2 -C 10 -alkylenediamines with a, (jo-hydroxy-C 2 -C 10 -alkylenediols or by polycondensation of ⁇ , oo-C 2 -C 10 -alkylenediamines
• An example of the polycondensation of ⁇ 1 -C -hydroxy-C 2 -C 10 -alkyleneamines is the polycondensation of triethanolamine (B)
• B triethanolamine
• polyethyleneimine (B) has an average molecular weight M w in the range from 600 to 75,000 g / mol, preferably in the range from 800 to 25,000 g / mol.
• polyethyleneimines (B) are selected from highly branched polyethyleneimines. Highly branched polyethylenimines (B) are characterized by their high degree of branching (DB). The degree of branching can be determined, for example, by 13 C-NMR spectroscopy, preferably in D 2 O, and is defined as follows:
• DB D + T / D + T + L with D (dendritic) corresponding to the proportion of tertiary amino groups, L (linear) corresponding to the fraction of secondary amino groups and T (terminal) corresponding to the proportion of primary amino groups.
• highly branched polyethyleneimines (B) are polyethyleneimines (B) with DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, more preferably in the range from 0.30 to 0, 80 and most preferably at least 0.5.
• polyethylene dendrimers (B) are polyethyleneimines (B) having a structurally and molecularly uniform structure.
• polyethylenimine (B) is a polyethylenimine modified with carboxylate groups or alkoxylate groups, in particular a polyethylenimine modified with ethoxylate, propoxylate or acetate by Michael addition of acrylic acid.
• polyethylenimine (B) has a cationic charge density of at least 5 milliequivalents / gram, with the term in g referring to cationic (co) polymer (B) without consideration of counterions.
• a charge density in the range of 5 to 22 milliequivalents / g is preferred.
• the charge density can be determined, for example, by titration, in particular by titration with potassium polyvinyl sulfate against toluidine blue.
• the aqueous formulation used in the cleaning process according to the invention also contains at least one surfactant (C).
• surfactants (C) are in particular anionic surfactants.
• suitable anionic surfactants (C) are alkali metal and ammonium salts of C 1 -C 2 -alkyl sulfates, of C 12 -C 18 -fatty alcohol polyether sulfates, of sulfuric monoesters of ethoxylated C 4 -C 12 -alkylphenols (ethoxylation: from 3 to 50 mol of ethylene oxide / mol), of C 12- C 18 -alkyl sulfonic acids (alkyl radical) and of C 12 -C 18 -alkylarylsulfonic acids.
• Preferred are
• surfactants (C) are selected from fatty alcohol polyether sulfates, which are in the context of the present invention in particular
• the aqueous formulation used in the process according to the invention also contains at least one solvent (D), ie at least one organic solvent that is miscible with water.
• solvent (D) can be mixed at room temperature with water in any ratio without a phase boundary being formed.
• solvent (D) is selected from ethanol, isopropanol, ethylene glycol, propylene glycol and diethylene glycol.
• suitable solvents (D) are ethylene glycol mono-C 1 -C 4 -alkyl ethers and propylene glycol mono-C 1 -C 4 -alkyl ethers, in particular ethylene glycol monoethyl ether, propylene glycol monoethyl ether and propylene glycol mono-n-butyl ether.
• formulations used in the process of the invention are phosphate-free.
• phosphate is to be understood as meaning inorganic phosphates, with polyphosphates and hydrogen phosphates being subsumed, for example, free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate.
• phosphate-free is to be understood as meaning that the total amount of phosphate is in the range from 10 ppm to 0.2% by weight, determined by gravimetry and based on the solids content in the novel process. drive used aqueous formulation.
• the aqueous formulation used in the process according to the invention is free from heavy metal compounds, in particular from compounds of iron and bismuth.
• "free from” is to be understood in connection with heavy metal compounds in that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, determined by the Leach method and
• the aqueous formulation used in the process according to the invention preferably has a heavy metal content below 0.05 ppm.
• heavy metals are all metals having a specific density of at least 6 g / cm 3.
• heavy metals include noble metals and zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium formulation according to the invention no measurable levels of zinc and bismuth compounds, that is, for example, less than 1 ppm.
• the aqueous formulation used in the process of the invention is free of bleaches.
• Bleaching agents are to be understood as meaning inorganic peroxide compounds, for example sodium perborate, sodium percarbonate, sodium persulfate and sodium peroxodisulfate.
• bleaching agents free from is to be understood as meaning that the proportion of peroxides is at most 0.5% by weight, particularly preferably at most 0.1% by weight In one embodiment, no peroxides can be measured in aqueous formulations. which are used in the process according to the invention.
• the aqueous formulation used in the process according to the invention may contain one or more additives (E), for example one or more dyes or one or more fragrances or one or more biocides, one or more nonionic surfactants or one or more polyacrylates.
• E additives
• nonionic surfactants are, in particular, C 1 -C 10 -alkylpolyglucosides, for example containing on average 1.2 to 4 glucose units per molecule, C 1 -C 10 -alkyl preferably being branched, for example 2-ethylhexyl or 2-propylheptyl.
• nonionic surfactants are alkoxylated fatty alcohols, in particular 3 to 60-fold ethoxylated C 12 -202-fatty alcohols, furthermore di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide and so-called amine oxides.
• alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)
• R 2 selected from Cs-C22-alkyl, for example n-CsH-i, n-doF i, n-Ci2H25, nC-uF s), n-Ci6H33
• R 3 is selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
• neo-pentyl 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or iso-decyl
• m and n are in the range of zero to 300, where the sum of n and m is at least one.
• m is in the range of 1 to 100 and n is in the range of 0 to 30.
• Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
• alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II) where the variables are defined as follows:
• R 1 is identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,
• R 4 selected from C 6 -C 20 -alkyl, in particular n-CsH-i, n-doF i, n-Ci 2 H 25, nC-uF s), n-Ci6H33, n
• a is a number in the range of 1 to 6
• b is a number in the range of 4 to 20
• d is a number in the range of 4 to 25.
• these may be block copolymers or random copolymers, preference being given to block copolymers.
• suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide.
• suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters.
• amine oxides or alkyl glycosides are also suitable.
• An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187. Mixtures of several different nonionic surfactants may also be present.
• polyacrylates is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol.
• copolymeric poly carboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
• copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C3-Cio-mono- or C4-Cio-dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least one hydrophilic or hydrophobically modified monomers as enumerated below.
• Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22- ⁇ -olefin, a mixture of C2o-C24- ⁇ -olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule.
• Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate.
• Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
• Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2- hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-
• Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.
• biocides examples include 1,2-benzisothiazolin-3-one ("BIT”) (commercially available as Proxel® brand from Avecia Lim.) Or its alkali metal salts, other suitable biocides are 2-methyl-2H-isothiazole-3 -on (“MIT”) and 5-chloro-2-methyl-2H-isothiazol-3-one (“CIT”), furthermore 2-bromo-2-nitropropane-1,3-diol, benzalkonium chlorides and 4,4 ' dichloro-2-hydroxy.
• BIT 1,2-benzisothiazolin-3-one
• MIT 2-methyl-2H-isothiazole-3 -on
• CIT 5-chloro-2-methyl-2H-isothiazol-3-one
• 2-bromo-2-nitropropane-1,3-diol benzalkonium chlorides and 4,4 ' dichloro-2-hydroxy.
• aqueous formulation used in the process according to the invention
• the aqueous formulation used in the process according to the invention has a solids content in the range from 2.0 to 50% by weight, preferably up to 35% by weight.
• aqueous formulation described above in one or more portions to the glass surface to be treated, for example as a liquid or as a foam, for example by spraying or spraying.
• a larger part of the aqueous formulation used in the process according to the invention is removed, for example by drying with a blower or for example by means of a scraper, in particular by stripping off.
• a proportion in the range of 65% by volume to 99.5% by volume of the applied formulation should be considered.
• a thin film for example, a film in the thickness of 50 nm to 1 ⁇ m of aqueous formulation used in the process of the invention, remains on the cleaned glass surface and dries over time.
• aqueous formulations comprising (A) a total of 1 to 50 wt .-%, preferably 2 to 15 wt .-% of at least one compound selected from methylglycine diacetate (MGDA) and glutamic acid diacetate and their salts and derivatives,
• (B) a total of 0.001 to 2 wt .-%, preferably 0.1 to 1 wt .-% of at least one homo- or copolymer of ethyleneimine,
• (E) optionally a total of zero to 25 wt .-%, preferably 1 to 15 wt .-% one or more additives.
• Aqueous formulations according to the invention are particularly suitable for carrying out the cleaning process according to the invention.
• the aqueous formulation according to the invention is free of heavy metal compounds.
• the aqueous formulation according to the invention preferably has a heavy metal content below 0.05 ppm, based on the solids content of the aqueous formulation according to the invention.
• the aqueous formulation used in the process of the invention is free of bleaches. In one embodiment of the present invention contains aqueous formulation according to the invention
• the aqueous formulation according to the invention has a pH in the range from 6 to 12, preferably 7 to 10.5.
• Another object of the present invention is the use of inventive aqueous formulations for cleaning glass surfaces.
• inventive aqueous formulations for cleaning glass surfaces.
• (A) at least one compound selected from methylglycine diacetate (MGDA) and glutamic acid diacetate and their salts and
• the respective glass plates were stored in a climatic chamber at 45 ° C and 98% relative humidity, over a period of 35 days. By this storage, the glass corrosion was simulated. Thereafter, the transmission is determined with a Perkin Elmer UV / VIS spectrometer (measurements in the range of 380 to 780 nm with A ma x about 575 nm). The glass plates generally had a very good cleanliness.
• Table 2 Composition of formulations according to the invention, comparison formulations and the results of the purification experiments

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