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EP1838831B1 - Utilisation de polymeres pour la modification de surfaces dans des produits nettoyants - Google Patents

Utilisation de polymeres pour la modification de surfaces dans des produits nettoyants Download PDF

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Publication number
EP1838831B1
EP1838831B1 EP05790952A EP05790952A EP1838831B1 EP 1838831 B1 EP1838831 B1 EP 1838831B1 EP 05790952 A EP05790952 A EP 05790952A EP 05790952 A EP05790952 A EP 05790952A EP 1838831 B1 EP1838831 B1 EP 1838831B1
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EP
European Patent Office
Prior art keywords
weight
component
water
particularly preferably
acid
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EP05790952A
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German (de)
English (en)
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EP1838831A1 (fr
Inventor
Heike Becker
Kai-Uwe Baldenius
Markus Hartmann
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BASF SE
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BASF SE
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • 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
    • C11D3/3719—Polyamides or polyimides
    • 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

Definitions

  • the present invention relates to the use of formulations containing at least one hard surface treatment polymer as an agent for improving the drainage of water from the treated hard surfaces and for reducing soil and salt deposition on the treated hard surfaces, as well as hard surface treatment formulations containing at least one polymer, at least one surfactant and at least one carboxylic acid and / or sulfonic acid and / or inorganic acid, as well as the use of these formulations for the treatment of hard surfaces.
  • Glass cleaners are known which avoid a troublesome amount of filming and / or streaking and so impart a desirable appearance to the glass surface. This desirable look will be over one maintained for a longer period of time, which is achieved by the glass cleaner containing a material that gives the glass a higher hydrophilicity.
  • This material is preferably polycarboxylates, for example poly (vinylpyrrolidone / acrylic acid), polyacrylic acid or sulfonated polystyrene polymers.
  • DE-A 198 59 777 relates to aqueous liquid surfactant-containing hard surface cleaners, especially glass, containing lignin sulfonate.
  • the lignosulfonate in the detergents simultaneously achieves a so-called anti-rain effect (avoidance of dried-in traces of water) and an anti-fogging effect (prevention of the condensation of water on the hard surfaces).
  • formulations which contain the stated polymers (component A) have excellent properties with respect to the run-off behavior of water of surfaces treated with the formulations and in terms of soil and salt deposition on the treated surfaces. This achieves rapid and streak-free drying, the avoidance or reduction of the condensation of water and / or the formation of dried-on traces of water and easier soil removal.
  • Hard surfaces are to be understood as meaning all known hard surfaces. These are in particular smooth surfaces, for example surfaces of glass, ceramic, metal, e.g. Stainless steel, enamel, painted surfaces and plastic.
  • the formulations according to the present application are preferably used for the treatment of glass or ceramics.
  • Treatment means both pre- or post-treatment of hard surfaces before or after cleaning, and treatment during cleaning. Furthermore, the treatment of hard surfaces can be done independently of a cleaning process.
  • treatment of hard surfaces is to be understood as meaning the “contacting” of the hard surface formulations used according to the invention.
  • the "contacting” can be done by rinsing, spraying, wiping or dipping or other methods known in the art.
  • the polymers used in the formulations according to the invention are distinguished by ecologically favorable properties. In natural environments, for example in sewage treatment plants, the polymers precipitate quantitatively or are surface-absorbed. This behavior is also referred to as bioelimination and assessed by the expert ecologically favorable.
  • component A The polymers used in the formulations according to the invention can be used alone, as the only component in aqueous solution, in the formulations for the treatment of hard surfaces.
  • Component A is contained in the formulations used according to the invention generally in an amount of 0.01 to 40 wt .-%, preferably 0.05 to 20 wt .-%, particularly preferably 0.1 to 5 wt .-%.
  • the pH of the formulations used according to the invention depends on the components used in the formulations and their amounts. In general, the pH in the formulations is 1 to 14, preferably 1 to 8, particularly preferably 1 to 6. In order to set an acidic pH (pH ⁇ 7), the formulations used according to the invention can be used in addition to the component A and water at least one carboxylic acid and / or sulfonic acid and / or inorganic acid.
  • Suitable carboxylic acids are carboxylic acids containing from 1 to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids.
  • suitable carboxylic acids are formic acid, acetic acid, glycolic acid, lactic acid, citric acid, succinic acid and adipic acid, preferably acetic acid, citric acid and lactic acid, most preferably acetic acid or citric acid.
  • suitable sulfonic acids are amidosulfonic acid and methanesulfonic acid, preferably amidosulfonic acid.
  • suitable inorganic acids are, for example, hydrochloric acid and phosphoric acid.
  • carboxylic acid and / or sulfonic acid and / or inorganic acid are present in the formulations used according to the invention, their proportion is more preferably 0.01 to 5% by weight, more preferably 0.02 to 3% by weight, very particularly preferably 0.05 to 1 wt .-%.
  • the formulation in addition to the at least one polymer containing at least one structural unit of the formula I (component A), the formulation comprises at least one surfactant as component B.
  • the composition may contain further components C to G, which are commonly used in hard surface cleaners.
  • the components B to G listed below are generally contained in the composition according to the invention in amounts known to those skilled in the art.
  • formulations as defined above which contain no metal oxides and / or metal salts.
  • Ready-to-use formulations are to be understood as meaning aqueous solutions which are in a manner typical for the surface, for example by wiping, spraying, dipping or rinsing, or similar methods as are usually used for the treatment of objects with hard surfaces find use to be applied to the surface.
  • the present invention also relates to the use of concentrates, ie formulations containing the aforementioned components A to G, but no water or less water than stated above, which means that the components A to G are present in higher concentrations.
  • concentrations of the components A to G in the presence of no or less water than stated above are easy to determine for the expert on the basis of the above amounts.
  • the present application further relates to the use of formulations containing the components A to G, which are in powder, granular, paste or gel form.
  • formulations containing the components A to G which are in powder, granular, paste or gel form.
  • Corresponding auxiliaries and additives as well as processes for the preparation of the formulations according to the invention in the various forms are known to the person skilled in the art.
  • the formulations used according to the invention due to the improved drainage behavior of water and the reduced soil and salt deposition effects of rapid and streak-free drying, avoiding or reducing the condensation of water and / or the formation of dried traces of water on the hard surfaces and / or facilitated Soil separation generally lasts for a longer period of time and more than one rewet cycle. This facilitates the cleaning, for example the removal of soil, in cleaning cycles after treatment with the composition according to the invention. This is achieved by modifying (hydrophilizing) the surface of the hard surfaces for a longer period of time. This results in an improved drainage of water as a thin film and at the same time less dirt and salt deposition on the hard surfaces.
  • the at least one polymer used as component A is in WO 2004/001099 disclosed.
  • WO 2004/001099 relates to complexing agents for the treatment of metal and
  • Plastic surfaces Under a treatment of metal and plastic surfaces is within the meaning of WO 2004/001099 to understand the passivation, in particular phosphating of metal surfaces, the pickling of metal surfaces, the sealing of metal surfaces and the metal deposition on metal surfaces, for example by nickel plating, galvanizing, tinning, copper plating or alloy deposits. Furthermore, the according to WO 2004/001099 disclosed compositions containing a polymer according to component A of the present invention for the preparation of paints or rust converters. Furthermore, the compositions according to WO 2004/001099 used for the deposition of metals on plastic surfaces, for example in the manufacture of printed circuit boards. The compositions according to WO 2004/001099 can also be used as cleaning, pickling and polishing formulations.
  • the polymers used as component A according to the present invention are described in US Pat WO 2004/001099 used in a completely different technical field than in the present application. As from the examples of WO 2004/001099 As can be seen, the polymers according to component A of the present invention are used for chemical or electrochemical metal deposition or for the electrolytic cleaning of metal surfaces.
  • WO 2004/001099 does not disclose that formulations containing a polymer containing at least one structural unit of the formula (I) (component A) of the present invention as an agent for improving the drainage of water of hard surfaces treated with said formulations and for reducing soil and salt deposition serve on hard surfaces treated with said formulations.
  • polymer backbone is to be understood as the longest chain forming the polymer.
  • This chain is composed of covalent bonds of catenated carbon atoms, but this carbon chain may be interrupted by heteroatoms, in particular nitrogen, silicon or oxygen.
  • this chain can have branches, which are also composed of carbon atoms and optionally nitrogen and oxygen atoms.
  • An anchor group is to be understood as meaning a group which links the structural unit of the formula (I) to the polymer main chain.
  • Such anchor groups may be alkylene groups having 1 to 14 carbon atoms which may be interrupted by heteroatoms, especially nitrogen or oxygen. These anchor groups may be attached to carbon atoms or to heteroatoms in the polymer backbone.
  • M in the structural unit of the formula (I) is hydrogen or an alkali metal cation, preferably a sodium or potassium ion.
  • M is a divalent or polyvalent cation, preferably an alkaline earth metal cation or Zn, Mn or Cr (III).
  • the weight-average molecular weight of the polymers used as component A is generally from 200 to 10,000,000 g / mol, preferably from 1,000 to 3,000,000 g / mol, more preferably from 2,000 to 1,300,000 g / mol.
  • the weight average was determined by means of light scattering.
  • the polymers used in the formulations used according to the invention are generally water-soluble.
  • component A is water-soluble, carboxalkylated, amino-containing polymers. These can be obtained by using water-soluble, amino-containing polymers with at least an aldehyde and an alkali metal cyanide or a cyanohydrin from an aldehyde and an alkali metal cyanide in aqueous solution.
  • Suitable water-soluble, amino-containing polymers are all water-soluble compounds containing a basic NH group.
  • Compounds of this type according to the invention are polyalkylenepolyamides. Examples of these are polyalkylenepolyamines which have at least four basic nitrogen atoms, such as tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and polyethylenediamines.
  • polyethyleneimines preference is given to polyethyleneimines. These more preferably have molecular weights of 200 to 10,000,000, most preferably 1,000 to 3,000,000 (weight average molecular weight). Particular preference is given to using polyethyleneimines having molar masses of from 2,000 to 1,300,000.
  • modified polyethyleneimines can also be subjected to carboxyalkylation.
  • modified polyethyleneimines are, for example, alkylated polyethyleneimines. They are known and are prepared for example by reaction of polyethyleneimines with alkylating agents such as alkyl halides (see US 3,251,778 and EP-B 0 379 161 ). Another alkylating agent is, for example, dimethyl sulfate.
  • alkylating agent is, for example, dimethyl sulfate.
  • the degree of alkylation of the polyethyleneimines is generally 1 to 50%, preferably 1 to 10%. The degree of alkylation is understood as meaning the percentage of alkylated monomer units in the polymer, based on the total number of monomer units in the polyethyleneimine.
  • Suitable alkyl halides are, for example, C 1-30 -alkyl halides.
  • Suitable modified polyethyleneimines are reaction products of polyethyleneimines with C 2-22 epoxides. These reaction products are usually prepared by alkoxylation of polyethylenimines in the presence of bases as a catalyst.
  • polyethyleneimines are suitable. They can be prepared from the polyethyleneimines by sulfonation or phosphonomethylation.
  • polyalkyleneamines used to prepare component A are prepared before carboxylalkylation with at least bifunctional crosslinkers which have as functional groups a halohydrin, glycidyl, aziridine or isocyanate unit or a halogen atom, partially networked.
  • partially crosslinked is meant that after crosslinking, free amino groups that are suitable for carboxalkylation are present in the polymers.
  • polyalkylenepolyamides preferably polyalkylenepolyamines are used which are at least bifunctional crosslinkers containing as functional groups a halohydrin, glycidyl, aziridine or iso-cyanate unit or a halogen atom have partially crosslinked.
  • Suitable crosslinkers are, for example, epihalohydrins, preferably epichlorohydrin, and also ⁇ , ⁇ -bis (chlorohydrin) polyalkylene glycol ethers and the ⁇ , ⁇ -bis (epoxides) of polyalkylene glycol ethers obtainable therefrom by treatment with bases.
  • the chlorohydrin ethers are prepared, for example, by reacting polyalkylene glycols in the molar ratio 1 to at least 2 to 5 with epichlorohydrin.
  • Suitable polyalkylene glycols are, for example, polyethylene glycol, polypropylene glycol and polybutylene glycols and also block copolymers of C 2 -C 4 -alkylene oxides.
  • the average molecular weights (M w ) of the polyalkylene glycols are generally from 100 to 6000, preferably from 300 to 2000, g / mol. ⁇ , ⁇ -bis (chlorohydrin) polyalkylene glycol ethers are used, for example, in US 4,144,123 described. As also disclosed therein, the corresponding bisglycidyl ethers of the polyalkylene glycols are formed from the dichlorohydrin ethers by treatment with bases.
  • crosslinkers are ⁇ , ⁇ -dichloropolyalkylene glycols, as described, for example, in US Pat EP-A 0 025 515 are disclosed.
  • These ⁇ , ⁇ -dichloropolyalkylene glycols are obtainable by reacting dihydric to tetrahydric alcohols, preferably alkoxylated dihydric to tetrahydric alcohols, either with thionyl chloride with elimination of HCl and subsequent catalytic decomposition of the chlorosulfonated compounds with elimination of sulfur dioxide, or with phosgene with HCl elimination converted into the corresponding Bischcorkohlenklaer and then obtained by catalytic decomposition with carbon dioxide cleavage ⁇ , ⁇ -dichloro.
  • the dihydric to tetrahydric alcohols are preferably ethoxylated and / or propoxylated glycols which are reacted with from 1 to 100, in particular from 4 to 40, mol of ethylene oxide per mole of glycol.
  • crosslinkers are ⁇ , ⁇ or vicinal dichloroalkanes, for example 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,4-dichlorobutane and 1,6-dichlorohexane.
  • Further suitable crosslinkers are the reaction products of at least trihydric alcohols with epichlorohydrin to give reaction products which have at least two chlorohydrin units.
  • Crosslinkers of this kind are for example made DE-A 29 16 356 known. Further suitable are crosslinkers containing blocked isocyanate groups, for example trimethylhexamethylene diisocyanate blocked with 2,2,3,6-tetramethylpiperidinone-4. These crosslinkers are off, for example DE-A 40 28 285 known.
  • crosslinkers can be used individually or as mixtures of two or more crosslinkers.
  • Epihalohydrins preferably epichlorohydrin, ⁇ , ⁇ -bis (chlorohydrin) polyalkylene glycol ethers, ⁇ , ⁇ -bis (epoxides) of the polyalkylene glycol ethers and / or bisglycidyl ethers of the polyalkylene glycols are particularly preferably used as crosslinkers.
  • the crosslinking of the polymers, preferably the polyalkyleneamines, particularly preferably polyethyleneimines, with the crosslinkers mentioned is carried out by methods known to the person skilled in the art.
  • the crosslinking takes place at a temperature of 10 to 200 ° C, preferably 30 to 100 ° C.
  • the reaction is usually carried out at atmospheric pressure.
  • the reaction times depend on the polyalkyleneamines and crosslinkers used. In general, the reaction time is 0.5 to 20 hours, preferably 1 to 10 hours.
  • the crosslinker is generally added in aqueous solution, so that the reaction is usually carried out in aqueous solution.
  • the product obtained can be isolated or reacted directly - without isolation step - in the carboxyalkylation, which is preferred.
  • the crosslinked polymers obtained after the crosslinking of the polymers preferably the polyalkyleneamines, preferably polyalkyleneamines, contain free amino groups which can be reacted in the subsequent carboxalkylation.
  • the carboxyalkylation is generally carried out by reacting the water-soluble, optionally containing partially crosslinked polymers containing amino groups with an aldehyde, preferably formaldehyde, and an alkali metal cyanide, preferably sodium cyanide.
  • an aldehyde preferably formaldehyde
  • an alkali metal cyanide preferably sodium cyanide.
  • carboxymethylated polyethyleneimines preference is given to using carboxymethylated polyethyleneimines. These are preferably obtained by carboxymethylation of polyethyleneimines with formaldehyde and sodium cyanide.
  • the carboxyalkylation of the water-soluble, crosslinked, amino-containing compounds is preferably carried out so far that 1 to 100% of the NH groups in polymers containing amino groups are carboxalkylated.
  • the aldehyde and the alkali metal cyanide are more preferably used in such an amount that 50 to 100% of the NH groups in the amino group-containing polymers are carboxalkylated.
  • the degree of carboxymethylation preferably carried out is usually 60 to 100%, based on the NH groups in the polymer.
  • a process for the preparation of the water-soluble, amino-containing polymers preferably used as component A, particularly preferably for the preparation of carboxyalkylated polyethyleneimines, very particularly preferably for the preparation of carboxymethylated polyethyleneimines are in WO 97/40087 disclosed.
  • the crosslinking of the polyalkyleneamines, preferably polyethyleneimines, with the crosslinkers mentioned is carried out by methods known to the person skilled in the art. In general, the crosslinking takes place at a temperature of 10 to 200 ° C, preferably 30 to 100 ° C.
  • the reaction is usually carried out at atmospheric pressure. The reaction times depend on the polyalkyleneamines and crosslinkers used. In general, the reaction time is 0.5 to 20 hours, preferably 1 to 10 hours.
  • the crosslinker is generally in aqueous solution added, so that the reaction is usually carried out in aqueous solution.
  • the product obtained can be isolated or reacted directly - without isolation step - in the carboxyalkylation, which is preferred. Suitable polymers are the abovementioned polymers.
  • the carboxyalkylation of the compounds containing crosslinked amino groups is carried out by methods known to those skilled in the art, for example as in WO 97/40087 disclosed.
  • the carboxyalkylation is carried out by simultaneously adding aldehyde and alkali metal cyanide to an aqueous solution of the polymer containing crosslinked amino groups within 0.5 to 10 hours, with a slight excess of alkali cyanide in the reaction mixture being preferred.
  • a small amount of alkali cyanide is present in the reaction mixture, for example 2 to 10 mole%, and then formaldehyde and alkali metal chloride are added in a molar ratio of about 1: 1 either separately or in admixture.
  • One mole of aldehyde and one mole of alkali cyanide react per mole of NH groups in the amino group-containing polymer. If a lower degree of carboxyalkylation is desired, it is possible, based on one mole of NH groups, to use a molar deficit of from 0.01 to 1 mol of aldehyde and from 0.01 to 1 mol of alkali metal cyanide.
  • the carboxyalkylation can be carried out continuously or batchwise or semicontinuously. Further suitable process conditions of the carboxyalkylation are, for example, in WO 97/40087 disclosed.
  • formulations used according to the invention may contain, in addition to the component A and water, further components B to G.
  • the formulations used according to the invention contain from 0.01 to 80% by weight, preferably from 0.01 to 30% by weight, particularly preferably from 0.01 to 20% by weight, very particularly preferably from 0.01 to 5% by weight.
  • Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 8 to 18, carbon atoms, for example C 9 -C 11 -alcohol sulfates, C 12 -C 13 -alcohol sulfates, C 14 -C 18 -alcohol sulfates such as lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsullfate, stearyl sulfate or tallow fatty alcohol sulfate.
  • Suitable anionic surfactants are sulfated ethoxylated C 8 -C 22 -alcohols (alkyl ether sulfates) or their soluble salts.
  • Compounds of this type are prepared, for example, by first alkoxylating a C 8-22 , preferably C 10-18, alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product.
  • Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 2 to 30, moles of ethylene oxide being used per mole of fatty alcohol.
  • the alkoxylation of the alcohols can also be carried out with propylene oxide alone and optionally butylene oxide.
  • alkoxylated C 8-22 alcohols containing ethylene oxide and propylene oxide or ethylene oxide and butylene oxide.
  • the alkoxylated C 8-22 alcohols may contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in random distribution.
  • alkanesulfonates such as C 8 -C 24 -, preferably C 10 -C 18 -alkanesulfonates and soaps such as the Na and K salts of C 8 -C 24 carboxylic acids.
  • anionic surfactants are C 8 -C 20 -linear alkylbenzenesulfonates (LAS), preferably linear C 9 -C 13 -alkylbenzenesulfonates and -alkyltoluenesulfonates.
  • LAS linear alkylbenzenesulfonates
  • anionic surfactants are C 8 -C 24 -olefin sulfonates and disulfonates, which may also be mixtures of alkene and hydroxyalkanesulfonates or -disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffin sulfonates having from 20 to 50 ° C.
  • Atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyltaurates, acylmethyltaurates, alkylsuccinic acids, alkenylsuccinic acids or their half-esters or hemiamides, alkylsulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids, acylscrcosinates, sulfated alkylpolyglycosides, alkylpolyglycolcarboxylates and hydroxyalkylsarcosinates ,
  • Suitable anionic surfactants are also alkyl phosphates.
  • the anionic surfactants may be added to the formulations used according to the invention in the form of salts.
  • Suitable salts are alkali metal salts such as sodium, potassium, lithium salts and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • anionic surfactants may be used singly or in combination of different anionic surfactants and in a mixture with the other surfactants mentioned become. It is possible to use anionic surfactants of only one class, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but also mixtures of different classes, for example a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.
  • Preferred anionic surfactants are alkyl ether sulfates, alkyl sulfates and alkyl phosphates.
  • Suitable nonionic surfactants are, for example, alkoxylated C 8 -C 22 -alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates.
  • the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide.
  • Usable as surfactants in this case are all alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide added.
  • block copolymers of ethylene oxide, butylene oxide and / or propylene oxide or adducts which contain the abovementioned alkylene oxides in random distribution. From 2 to 50, preferably from 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol.
  • the alkylene oxide used is preferably ethylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • nonionic surfactants are alkylphenol ethoxylates having C 6 -C 14 alkyl chains and from 5 to 30 moles of ethylene oxide units.
  • nonionic surfactants are alkyl polyglucosides having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5, glucoside units.
  • Another class of nonionic surfactants are N-alkylglucamides.
  • nonionic surfactants are alkylamine alkoxylates or alkylamide ethoxylates.
  • the formulations used according to the invention preferably contain ethoxylated C 10 -C 16 -alcohols with 3 to 12 mol of ethylene oxide, particularly preferably ethoxylated fatty alcohols. Further preferred are alkyl polyglucosides, alkylamine alkoxylates and amide ethoxylates.
  • nonionic surfactants or a combination of different nonionic surfactants or a mixture with other surfactants mentioned. It is preferable to use alkoxylated C 8 -C 22 -alcohols alone.
  • amphoteric surfactants are alkylbetaines, alkylamidbetaines, aminopropionates, aminoglycinates or amphoteric imidazolium compounds.
  • preferred examples are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate and cocoamphoacetate.
  • Suitable cationic surfactants are substituted or unsubstituted, straight-chain or branched quaternary ammonium salts, for example C 8-6 dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolium salts with a long-chain alkyl radical.
  • component B anionic surfactants, nonionic surfactants or combinations of anionic and nonionic surfactants.
  • component B is selected from fatty alcohol sulfates, alkyl ether sulfates, fatty alcohol alkoxylates and mixtures thereof.
  • the water-soluble organic solvent (component C) is generally used in an amount of 0 to 50% by weight, preferably 0.1 to 30% by weight, more preferably 0.5 to 15% by weight, most preferably 1 to 10 wt .-% used in the formulations according to the invention.
  • Suitable water-soluble organic solvents are C 1 -C 6 -alcohols and / or etherealcohols, mixtures of different alcohols and / or etherealcohols being preferred.
  • Suitable alcohols are ethanol, isopropanol and n-propanol. Furthermore, ethylene glycol, propylene glycol and glycerin are suitable.
  • Suitable ether alcohols are ether alcohols having up to 10 carbon atoms in the molecule, for example ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether. Particularly preferred are ethylene glycol monobutyl ether and propylene glycol monobutyl ether.
  • component C is selected from ethanol, isopropanol, n-propanol, ethylene glycol monobutyl ethers, propylene glycol monobutyl ethers and mixtures of two or more of said water-soluble organic solvents.
  • the weight ratio of alcohol and ether alcohol is preferably 1: 2 to 4: 1.
  • the weight ratio is preferably 1: 6 to 6: 1, more preferably 1 to 5 to 5 to 1, most preferably 4 to 1, more preferably the proportion of the ether alcohol having fewer carbon atoms being the higher of the two.
  • Ammonia and / or at least one alkanolamine (component D) are used in a proportion of generally 0 to 5 wt .-%, preferably 0.01 to 3 wt .-%, particularly preferably 0.02 to 1 wt .-%, completely particularly preferably 0.05 to 0.5 wt .-% used.
  • alkanolamines which contain 1 to 9 carbon atoms in the molecule.
  • the alkanolamines used are preferably ethanolamines, particularly preferably monoethanolamine.
  • the formulations used according to the invention may contain at least one carboxylic acid and / or sulfonic acid and / or inorganic acid.
  • Suitable carboxylic acids are carboxylic acids containing from 1 to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids. Examples of suitable carboxylic acids are formic acid, acetic acid, glycolic acid, lactic acid, citric acid, succinic acid and adipic acid, preferably acetic acid, citric acid and lactic acid, most preferably acetic acid and citric acid.
  • suitable sulfonic acids are amidosulfonic acid and methanesulfonic acid, preferably amidosulfonic acid.
  • suitable inorganic acids are hydrochloric acid and phosphoric acid.
  • the at least one carboxylic acid and / or sulfonic acid and / or inorganic acid (component E) is added in a proportion of generally 0 to 5 wt.%, Preferably 0.01 to 5 wt.%, Particularly preferably 0.02 to 3 Wt .-%, most preferably 0.05 to 1 wt .-% used.
  • the at least one builder is used in a proportion of generally 0 to 10 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.1 to 3 wt .-%.
  • Builders include inorganic builders and organic (co) builders.
  • Suitable inorganic builders are all customary inorganic builders, such as aluminosilicates, silicates, carbonates, phosphates and phosphonates.
  • Suitable inorganic builders are known to the person skilled in the art and are described, for example, in US Pat DE-A 101 60 993 disclosed.
  • polycarboxylates can be used.
  • salts of phosphonic acids and oligomeric or polymeric polycarboxylates are suitable.
  • copolymers and terpolymers of unsaturated C 4 -C 8 -dicarboxylic acids with monoethylenically unsaturated monomers which may additionally be modified, and polyglyoxylic acids, polyamidocarboxylic acids and modified polyamidocarboxylic acids, polyaspartic acid or cocondensates of aspartic acid with further amino acids, C 4 -C 25 -mono - or -Dicarbonklaren and / or C 4 -C 25 mono- or - diamines, condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds having molecular weights of generally up to 10,000, preferably up to 5000, suitable.
  • Suitable organic (co) builders are, for example, in DE-A 101 60 993 called.
  • formulations used according to the invention may contain, in addition to components A to F, further auxiliaries and additives as component G.
  • auxiliaries and additives may be present in an amount of from 0 to 5% by weight, preferably from 0.01 to 3% by weight, in the formulations used according to the invention.
  • auxiliaries and additives include all auxiliaries and additives conventionally used in hard surface treatment and cleaning compositions, preferably dyes, perfume oils, pH regulators, for example NaOH, preservatives, alkaline earth ion complexing agents, enzymes, bleach systems, soil release polymers, Foam boosters, foam suppressants or foam inhibitors, biocides, tarnish and / or corrosion inhibitors, suspending agents, fillers, inorganic adjusters, disinfectants, hydrotropes, antioxidants, solubilizers, dispersants, processing aids, solubilizers, plasticizers and antistatic agents.
  • Suitable auxiliaries and additives are, for example, in DE-A 101 60 993 called.
  • the formulations used according to the invention are generally prepared by mixing components A to G, if they are present in the formulations used according to the invention, and water. Suitable mixing methods are known to the person skilled in the art.
  • the formulations can be used anywhere where improved drainage of water and / or reduction of soil and salt deposition is desirable is.
  • the formulations may be used as hard surface pretreatment or after-treatment agents, particularly glass and ceramic or cleaning agents such as glass cleaners, floor cleaners, all-purpose cleaners, bathroom cleaners, rinse aids, dishwashing detergents for hand or machine cleaning of utensils, machine cleaners, metal degreasers, high pressure cleaners, alkaline cleaners, acid cleaners , Syringe degreasers, dairy cleaners and so on.
  • the formulations are preferably used as a pre- or post-treatment agent for hard surfaces, in particular glass and ceramic or as a cleaning agent, such as glass cleaners, floor cleaners, all-purpose cleaners and bathroom cleaners.
  • the pH of the formulations used according to the invention depends on the components used in the formulations and their amounts. In general, the pH in the formulations is 1 to 14, preferably 1 to 8, particularly preferably 1 to 6.
  • the formulations of the present invention are useful for treating hard surfaces while improving the drainage of water on the treated hard surfaces and reducing soil and salt deposition on the treated hard surfaces.
  • Suitable components A, B, C, D, E, F and G are the above-mentioned suitable components A to G.
  • the formulations according to the invention are suitable for pre- and post-treatment of the hard surfaces before or after cleaning and for treatment during cleaning. Furthermore, the treatment of the hard surfaces with the formulations according to the invention can be carried out independently of a cleaning process.
  • the formulations according to the invention can thus be used as pre- or post-treatment agents for hard surfaces, in particular glass and ceramic, or as cleaning agents such as glass cleaners, floor cleaners, all-purpose cleaners, bathroom cleaners, rinse aids, dishwashing detergents for hand or machine cleaning of dishes, machine cleaners, metal degreasers, high-pressure cleaners, alkaline cleaners , acid cleaners, syringe degreasers, whey cleaners, etc. can be used.
  • the inventive compounds are preferred Formulations used as a pre- or post-treatment agent for hard surfaces, especially glass and ceramic, or as a cleaning agent such as glass cleaner, floor cleaner, all-purpose cleaner and bathroom cleaner.
  • the formulations according to the invention preferably have no metal oxides and / or metal salts.
  • a further subject of the present application is a method for the treatment of hard surfaces, wherein the hard surfaces are brought into contact with the formulation according to the invention.
  • the "contacting” is generally done by rinsing, dipping, spraying or wiping or other methods known to those skilled in the art.
  • the "contacting” can be done as a pre- or post-treatment before or after a cleaning, during cleaning or independently of a cleaning.
  • a further subject of the present application is the use of the formulations according to the invention for the treatment of hard surfaces.
  • the formulations according to the invention are outstandingly suitable for this purpose, in particular because of their properties, namely an improvement in the flow behavior of water and a reduction in soil and salt deposits on the hard surfaces treated with the formulations according to the invention.
  • the formulations of the invention are generally prepared by mixing the components A to G, as far as they are present in the formulations according to the invention, and water. Suitable mixing methods are known to the person skilled in the art.

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  • Wood Science & Technology (AREA)
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  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processing Of Solid Wastes (AREA)
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  • Paints Or Removers (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Claims (10)

  1. Utilisation de formulations contenant
    a) au moins un polymère en tant que composant A contenant une ou plusieurs unités de répétition de formule (II), une ou plusieurs unités de répétition de formule (III) et une ou plusieurs unités de répétition de formule (IV), ainsi qu'éventuellement plusieurs unités de formule (VI)
    Figure imgb0025
    Figure imgb0026
    Figure imgb0027
    Figure imgb0028
     dans lesquelles
    R signifie l'hydrogène ou un radical organique substitué ou non substitué quelconque,
    M signifie l'hydrogène ou un cation métallique ;
    et de l'eau ;
    pour le traitement de surfaces dures en tant qu'agent pour l'amélioration du comportement d'écoulement de l'eau sur les surfaces dures traitées et pour la réduction des dépôts de salissures et de sels sur les surfaces dures traitées ; des polyalkylène polyamides, de préférence des polyalkylène polyamines, étant utilisés pour la fabrication du composant A, qui sont réticulés partiellement avec des agents de réticulation au moins bifonctionnels, qui comportent en tant que groupes fonctionnels une unité halogénohydrine, glycidyle, aziridine ou isocyanate ou un atome d'halogène.
  2. Utilisation selon la revendication 1, caractérisée en ce que les formulations contiennent les composants suivantes :
    a) au moins un composé soluble dans l'eau ou dispersible dans l'eau selon la revendication 1 en tant que composant A ;
    b) au moins un tensioactif choisi dans le groupe constitué par les tensioactifs anioniques, non ioniques, amphotères et cationiques, en tant que composant B ;
    c) éventuellement au moins un solvant organique soluble dans l'eau, en tant que composant C ;
    d) éventuellement de l'ammoniac et/ou au moins une alcanolamine, en tant que composant D ;
    e) éventuellement au moins un acide carboxylique et/ou un acide sulfonique et/ou un acide inorganique, en tant que composant E ;
    f) éventuellement au moins un adjuvant, en tant que composant F ;
    g) éventuellement des adjuvants et additifs supplémentaires, en tant que composant G ; et
    h) de l'eau.
  3. Utilisation selon la revendication 2, caractérisée en ce que les formulations contiennent les composants suivants :
    a) 0,01 à 40 % en poids, de préférence 0,05 à 20 % en poids, de manière particulièrement préférée 0,1 à 5 % en poids, du composant A ;
    b) 0,01 à 80 % en poids, de préférence 0,01 à 30 % en poids, de manière particulièrement préférée 0,01 à 20 % en poids, de manière tout particulièrement préférée 0,01 à 5 % en poids, du composant B ;
    c) 0 à 50 % en poids, de préférence 0,1 à 30 % en poids, de manière particulièrement préférée 0,5 à 15 % en poids, de manière tout particulièrement préférée 1 à 10 % en poids, du composant C ;
    d) 0 à 5 % en poids, de préférence 0,01 à 3 % en poids, de préférence 0,02 à 1 % en poids, de manière particulièrement préférée 0,05 à 0,5 % en poids, du composant D ;
    e) 0 à 5 % en poids, de préférence 0,01 à 5 % en poids, de manière particulièrement préférée 0,02 à 3 % en poids, de manière tout particulièrement préférée 0,05 à 1 % en poids, du composant E ;
    f) 0 à 10 % en poids, de préférence 0,1 à 5 % en poids, de manière particulièrement préférée 0,1 à 3 % en poids, du composant F ;
    g) 0 à 5 % en poids, de préférence 0,01 à 3 % en poids, du composant G ; et
    h) de l'eau,
    de manière à ce que la quantité totale des composants A à G et de l'eau soit de 100 % en poids.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la moyenne en poids du poids moléculaire du polymère (composant A) est de 200 à 10 000 000 g/mol.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que le composant B est choisi parmi les sulfates d'alcools gras, les alkyléther sulfates, les alcoxylates d'alcools gras et leurs mélanges.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que le composant C est choisi parmi l'éthanol, l'isopropanol, le n-propanol, les éthers monobutyliques d'éthylène glycol, les éthers monobutyliques de propylène glycol et les mélanges de deux ou plus des solvants organiques solubles dans l'eau cités.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que le composant D est l'ammoniac et/ou la monoéthanolamine et/ou le composant E est l'acide acétique, l'acide citrique, l'acide lactique ou l'acide amidosulfonique.
  8. Formulations pour le traitement de surfaces dures, contenant
    a) 0,05 à 20 % en poids, de préférence 0,1 à 5 % en poids, d'au moins un polymère en tant que composant A contenant
    une ou plusieurs unités de répétition de formule (II), une ou plusieurs unités de répétition de formule (III) et une ou plusieurs unités de répétition de formule (IV), ainsi qu'éventuellement plusieurs unités de formule (VI)
    Figure imgb0029
    Figure imgb0030
    Figure imgb0031
    Figure imgb0032
     dans lesquelles
    R signifie l'hydrogène ou un radical organique substitué ou non substitué quelconque,
    M signifie l'hydrogène ou un cation métallique ;
    des polyalkylène polyamides, de préférence des polyalkylène polyamines, étant utilisés pour la fabrication du composant A, qui sont réticulés partiellement avec des agents de réticulation au moins bifonctionnels, qui comportent en tant que groupes fonctionnels une unité halogénohydrine, glycidyle, aziridine ou isocyanate ou un atome d'halogène ;
    b) 0,01 à 30 % en poids, de préférence 0,01 à 20 % en poids, de manière particulièrement préférée 0,01 à 5 % en poids, d'au moins un tensioactif choisi dans le groupe constitué par les tensioactifs anioniques, non ioniques, amphotères et cationiques, en tant que composant B ;
    c) 0 à 50 % en poids, de préférence 0,1 à 30 % en poids, de préférence 0,5 à 15 % en poids, de manière particulièrement préférée 1 à 10 % en poids, d'au moins un solvant organique soluble dans l'eau, en tant que composant C ;
    d) 0 à 3 % en poids, de préférence 0,02 à 1 % en poids, de manière particulièrement préférée 0,05 à 0,5 % en poids, d'ammoniac et/ou d'au moins une alcanolamine, en tant que composant D ;
    e) 0,01 à 5 % en poids, de préférence 0,02 à 3 % en poids, de manière particulièrement préférée 0,05 à 1 % en poids, d'au moins un acide carboxylique et/ou un acide sulfonique et/ou un acide inorganique, en tant que composant E ;
    f) 0 à 10 % en poids, de préférence 0,1 à 5 % en poids, de manière particulièrement préférée 0,1 à 3 % en poids, d'au moins un adjuvant, en tant que composant F ;
    g) 0 à 5 % en poids, de préférence 0,01 à 3 % en poids, d'adjuvants et additifs supplémentaires, en tant que composant G ; et
    h) de l'eau,
    de manière à ce que la quantité totale des composants A à G et de l'eau soit de 100 % en poids.
  9. Formulation selon la revendication 8, caractérisée en ce que la moyenne en poids du poids moléculaire du polymère (composant A) est de 200 à 10 000 000 g/mol.
  10. Utilisation de formulations selon la revendication 8 ou 9 pour le traitement de surfaces dures.
EP05790952A 2004-09-13 2005-09-12 Utilisation de polymeres pour la modification de surfaces dans des produits nettoyants Expired - Lifetime EP1838831B1 (fr)

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DE102004044605A DE102004044605A1 (de) 2004-09-13 2004-09-13 Verwendung von Polymeren zur Modifizierung von Oberflächen in Reinigeranwendungen
PCT/EP2005/009788 WO2006029793A1 (fr) 2004-09-13 2005-09-12 Utilisation de polymeres pour la modification de surfaces dans des produits nettoyants

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EP2083067A1 (fr) * 2008-01-25 2009-07-29 Basf Aktiengesellschaft Utilisation de complexants organiques et/ou de liaisons contenant des groupes d'acides de carbone polymères dans une composition de produit de lavage ou de nettoyage
US10407594B2 (en) * 2011-03-22 2019-09-10 Basf Se Chemical mechanical polishing (CMP) composition comprising a polymeric polyamine
GB201107885D0 (en) 2011-05-12 2011-06-22 Reckitt Benckiser Nv Improved composition
EP2650352A1 (fr) * 2012-04-11 2013-10-16 Basf Se Composition de nettoyage pour surfaces dures
CN102747378B (zh) * 2012-07-24 2016-01-20 中国第一汽车股份有限公司 环保型水基金属清洗剂
WO2014093578A1 (fr) * 2012-12-14 2014-06-19 Basf Se Lingettes d'entretien des sols à récupération améliorée de la saleté
WO2015187757A1 (fr) * 2014-06-06 2015-12-10 The Procter & Gamble Company Composition détergente comprenant des polymères à base de polyalkylèneimine
CN106753854B (zh) * 2016-11-27 2019-02-01 湖南金裕化工有限公司 玻璃镜片清洗剂及其制备方法
CN106833950A (zh) * 2016-12-28 2017-06-13 于文 抗菌地板清洁剂及其制备方法
KR102560758B1 (ko) 2017-01-03 2023-07-28 삼성전자주식회사 이미지 센서
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DE10160993A1 (de) 2001-12-12 2003-06-18 Basf Ag Stickstoffhaltige Polymere umfassende Reinigungsmittelzusammensetzungen
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DE102004044605A1 (de) 2006-03-30
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WO2006029793A1 (fr) 2006-03-23
JP2008512531A (ja) 2008-04-24
JP4898684B2 (ja) 2012-03-21
ES2367442T3 (es) 2011-11-03
CA2579951A1 (fr) 2006-03-23
MX2007002457A (es) 2007-05-10
ATE517976T1 (de) 2011-08-15
US20080032911A1 (en) 2008-02-07
US7749331B2 (en) 2010-07-06

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