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
  • C11D3/16—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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • 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 compositions for treating hard surfaces containing a water-soluble compound and water, a process for preparing a water-soluble compound, water-soluble compounds preparable by the process of the invention and the use of water-soluble compounds according to the present application in compositions for treating hard surfaces for rapid and streak-free drying, facilitating the removal of soil, reducing or preventing the condensation of water and / or the formation of dried traces of water on the hard surfaces.
• the invention relates to the use of the water-soluble compounds (polymers), which allow in cleaning applications, the dispersion of dirt and in particular lime soaps.
• compositions for the treatment of hard surfaces which are capable of hard surfaces for a period of time to provide more than one moistening cycle with one or more of the aforementioned properties.
• insoluble lime soaps can be formed in conjunction with water hardness, which precipitate on hard surfaces and can form poorly soluble residues there. For example, this can occur on shower panels and sinks and bathtubs. It is therefore further desirable to facilitate facilitated delamination of lime soap soil.
• 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 appearance is maintained for a longer period of time, which is achieved by the glass cleaners contain 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).
• US 3,963,806 relates to compositions useful for applying a non-fogging coating to a substrate, e.g. As glasses of ski or goggles, mirrors or lenses are suitable. According to US 3,963,806 the coating should be durable.
• the compositions contain a water-insoluble polymer composed of a polyalkyleneimine crosslinked with a compound having at least two reactive groups.
• US 6,653,274 relates to hard surface cleaning compositions containing a so-called "dirty entrainment system”.
• This "soil entrainment system” comprises one or more modified polyamine compounds, specific molecular weight polyethylene glycols, one or more polyamide-acrylic compounds, or mixtures thereof.
• the modified polyamine compounds include a polyamine as the polymer backbone, an amide-forming crosslinking moiety based on polycarboxylic acids, and / or a non-amide-forming crosslinking moiety or mixtures thereof instead of the amide-forming crosslinking moiety.
• compositions known in the art it is desirable to further improve the properties of the hard surface treating compositions, especially for smooth surfaces such as glass, metal, ceramic or plastic, i. H.
• properties of the hard surface treating compositions especially for smooth surfaces such as glass, metal, ceramic or plastic, i. H.
• compositions containing said water-soluble compounds have excellent fast and streak-free drying properties, preventing or reducing the condensation of water, the formation of dried-on traces of water, in particular due to the water hardness in the form of traces of limescale and hard edges on hard surfaces and the easier soil removal, especially lime removal, have.
• the water-soluble compounds (polymers) in cleaning applications the dispersion of dirt and especially lime soap is possible.
• the polymer has properties that prevent lime soap soil from adhering to polymer-treated surfaces, thus promoting the effect. Lime soap dirt that is applied to these surfaces is significantly easier to peel off.
• 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, eg stainless steel, enamel, painted surfaces and plastic. 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.
• water-soluble condensation products are used as drainage, flocculation and retention aids in the manufacture of paper.
• the use of the water-soluble condensates in hard surface treatment compositions is disclosed in U.S. Pat DE-A 42 44 194 not revealed.
• WO 97/42285 refers to soil release polymers for cotton having water-soluble or water-dispersible modified polyamine compounds.
• the modified polyamines are preferably polyethyleneimines and polyethyleneamines which have a low molecular weight, generally below 600 daltons, and which are linked to one another via "oxy" units.
• the use of in WO 97/42285 disclosed polymers in hard surface cleaners is in WO 97/42285 not revealed.
• WO 00/49126 relates to detergent compositions comprising at least one modified polyamine compound and a surfactant.
• the modified polyamine compound is a grafted or ungrafted, modified or unmodified polyamine that is crosslinked.
• the polyamine used in one embodiment is polyethyleneimine.
• Crosslinkers which can be used are amide-forming crosslinkers and also other crosslinkers, for example epihalohydrins or epihalohydrins in combination with, for example, polyethylene glycol.
• the polyamine compounds are modified by grafting, for example with aziridine, or by so-called “capping" by reaction with monocarboxylic acids which have a C 1 -C 22 -alkyl radical which is linear or branched, and polyamine compounds which have been reacted with unsaturated carboxylic acids , are in WO 00/49126 not revealed. Furthermore, in WO 00/49126 the use of the modified polyamine compounds in hard surface cleaners is not disclosed.
• compositions which contain at least one surfactant (component B) in addition to the at least one water-soluble compound (component A) are suitable for achieving hard surfaces desired properties mentioned above simultaneously for cleaning these surfaces.
• the composition may contain other components commonly used in hard surface cleaners.
• Component A is generally present in the composition according to the invention in an amount of from 0.01 to 40% by weight, preferably from 0.05 to 20% by weight, particularly preferably from 0.1 to 5% by weight.
• Components B to F are generally contained in the composition of the invention in amounts known to those skilled in the art.
• ready-to-use compositions are ready-to-use compositions.
• ready-to-use compositions are aqueous
• concentrates ie compositions 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.
• compositions comprising the components A to G, which are in powder, granular, paste or gel form.
• 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 composition according to the invention in the various forms are known to the person skilled in the art.
• compositions of the present invention generally persist for a prolonged 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 behavior of water and at the same time less dirt and salt deposits on the hard surfaces.
• Component A is obtained by reacting components Aa, optionally Ab and Ac.
• the water-soluble compound can thus be present in crosslinked or uncrosslinked form, the component Aa in each case having been modified with the component Ac.
• the components Aa, optionally Ab and Ac can be used in any ratio to each other.
• the components Aa and Ab are preferably used in a molar ratio of 100: 1 to 1: 1000, more preferably 20: 1 to 1: 20.
• the molar ratio between the components Aa and Ac is preferably selected such that the molar of the hydrogen atoms on the nitrogen in Aa to the component Ac 1 to 0.2 to 1 to 0.95, preferably 1 to 0.3 to 1 to 0.9, more preferably 1 to 0.4 to 1 to 0.85.
• the polyethyleneimines preferably have an average molecular weight (M w ) of at least 300.
• M w average molecular weight of the polyethyleneimines is preferably from 800 to 2,000,000, more preferably 20,000 to 1,000,000, most preferably 20,000 to 75,000, determined by means of light scattering.
• the polyethyleneimines may be partially amidated. Products of this type are prepared, for example, by reaction of polyethylenimines with carboxylic acids, carboxylic esters, carboxylic anhydrides or carboxylic acid halides.
• the polyethyleneimines are preferably amidated according to the present application for the subsequent reactions to 1 to 30, more preferably up to 20%. It is necessary that the amidated polyethyleneimines still have free NH groups, so that they can be reacted with the compounds Ab and Ac.
• Suitable carboxylic acids for the amidation of the polyethyleneimines are C 1 -C 28 carboxylic acids, for example formic acid, acetic acid, propionic acid, benzoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid and behenic acid. It is also possible that the amidation is carried out by reacting the polyethylene imine with alkyl diketene.
• the polyethyleneimines may further be used in part in quaternized form as component Aa.
• Suitable quaternizing agents include, for example, alkyl halides such as methyl chloride, ethyl chloride, butyl chloride, epichlorohydrin, hexyl chloride, dimethyl sulfate, diethyl sulfate and benzyl chloride. If quaternized polyethyleneimines are used as component Aa, the degree of quaternization is preferably 1 to 30, more preferably up to 20%.
• polyamidoamines grafted with ethyleneimine are suitable as component Aa.
• the polyamidoamines are obtainable, for example, by reacting C 4 -C 10 -dicarboxylic acids with polyalkylenepolyamines, which preferably contain from 3 to 10 basic nitrogen atoms in the molecule.
• suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use mixtures of carboxylic acids, for example mixtures of adipic acid and glutaric acid or maleic acid and adipic acid.
• Adipic acid is preferably used to prepare the polyamidoamines.
• Suitable polyalkylenepolyamines which are condensed with the dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
• the Polyalkylenpolyarrüne can also be used in the form of mixtures in the preparation of polyamidoamines.
• the preparation of the polyamidoamines is preferably carried out in bulk, but may also be carried out in inert solvents, if appropriate.
• the condensation of the dicarboxylic acids with the polyalkylenepolyamines takes place at higher temperatures, for example in the range from 120 to 220.degree.
• the water formed during the reaction is distilled off from the reaction mixture.
• the condensation may optionally be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms.
• lactones or lactams of carboxylic acids having 4 to 8 carbon atoms In general, 0.8 to 1.4 mol of a polyalkylenepolyamine are used per mole of dicarboxylic acid.
• the polyamidoamines thus obtainable have primary and secondary NH groups and are soluble in water.
• the polyamidoamines grafted with ethyleneimine can be prepared by allowing ethyleneimine to act on the polyamidoamines described above in the presence of Bronsted acids or Lewis acids, for example sulfuric acid, phosphoric acid or boron trifluoride etherate. Under the conditions mentioned, ethyleneimine is grafted onto the polyamidoamine. For example, per basic nitrogen grouping in the polyamidoamine, one can graft 1 to 10 ethyleneimine units, i. H. to 100 parts by weight of a polyamidoamine is used about 10 to 500 parts by weight of ethyleneimine.
• polyetheramines can be used as component Aa.
• Compounds of this kind are for example made DE-A 29 16 356 known.
• the polyetheramines can be obtained by condensation of di- and polyamines with chlorohydrin ethers at elevated temperatures.
• the polyamines can contain up to 10 nitrogen atoms.
• the chlorohydrin ethers are prepared, for example, by reacting dihydric alcohols having 2 to 5 carbon atoms, the alkoxylation products of these alcohols with up to 60 alkylene oxide units, glycerol or polyglycerol containing up to 15 glycerol units, erythritol or pentaerythritol with epichlorohydrin.
• polyether polyamines can be prepared by condensing diethanolamine or triethanolamine according to known methods, as described, for example, in US Pat US 4,404,362 . US 4,459,220 and US 2,407,895 are disclosed.
• Polyethyleneimines are preferably used as component Aa, which are optionally amidated to a maximum of 20%. It is particularly preferable to use polyethyleneimines which very particularly preferably have an average molecular weight of from 800 to 2,000,000, more preferably from 20,000 to 1,000,000, most preferably from 20,000 to 75,000.
• At least bifunctional crosslinkers are suitable which have as functional groups a halohydrin, glycidyl, aziridine or isocyanate unit or a halogen atom.
• 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 molar masses (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.
• glycerol, ethoxylated or propoxylated glycerols, polyglycerols having 2 to 15 glycerol units in the molecule and optionally ethoxylated and / or propoxylated polyglycerols are used as the polyhydric alcohols.
• 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.
• monoethylenically unsaturated carboxylic acids selected from the group consisting of acrylic acid, methacrylic acid, dimethacrylic acid, ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, methylenemalonic acid and citraconic acid are suitable.
• the monoethylenically unsaturated carboxylic acids are preferably selected from the group consisting of acrylic acid, methacrylic acid and maleic acid.
• Suitable salts are generally the alkali metal, alkaline earth metal and ammonium salts of the abovementioned acids. Preferred are the sodium, potassium and ammonium salts.
• the ammonium salts can be derived from both ammonia and amines or amine derivatives such as ethanolamine, diethanolamine and triethanolamine.
• Suitable alkaline earth metal salts are generally magnesium and calcium salts of the abovementioned monoethylenically unsaturated carboxylic acids.
• Suitable esters of the abovementioned monoethylenically unsaturated carboxylic acids are derived from monohydric C 1 -C 20 -alcohols or divalent C 2 -C 6 -alcohols.
• Suitable esters are, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, Isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, palmithyl acrylate, lauryl acrylate, diaryl acrylate, lauryl methacrylate, palmithyl methacrylate, stearyl methacrylate, dimethyl maleate, diethyl maleate, isoprop
• Suitable amides of monoethylenically unsaturated carboxylic acids are, for example, acrylamide, methacrylamide and oleic acid amide.
• Suitable nitriles of the monoethylenically unsaturated carboxylic acids are preferably acrylonitrile and methacrylonitrile.
• suitable amides are to be understood as meaning the reaction products of the monoethylenically unsaturated carboxylic acids, in particular of (meth) acrylic acid, with amidoalkanesulfonic acids.
• chlorocarboxylic acids are, for example, chloroacetic acid, 2-chloropropionic acid, 2-chlorobutyric acid, dichloroacetic acid and 2,2'-dichloropropionic acid.
• Preferred compounds of the formula III are glycidyl acid, their sodium, potassium, ammonium, magnesium or calcium salts, glycidyl amide and glycidyl esters, such as methyl glycidylate, ethyl glycidylate, n-propyl glycidylate, n-butyl glycidylate, isobutyl glycidylate, 2-ethylhexyl glycidylate , Glycidylic acid 2-hydroxypropyl ester and 4-hydroxybutyl glycidylate. Particularly preferred are glycidylic acid, its sodium, potassium or ammonium salts or glycidylamide.
• a monoethylenically unsaturated carboxylic acid is preferably used as component Ac, particularly preferably acrylic acid, methacrylic acid or maleic acid, very particularly preferably acrylic acid.
• the water-soluble compounds (component A) can be prepared by methods known in the art. Suitable manufacturing processes are, for example, in DE-A 42 44 194 discloses wherein the component Aa is first reacted with the component Ac and only then the component Ab is added. Furthermore, it is according to DE-A 42 44 194 possible to react the components Ac and Ab simultaneously with the component Aa.
• This implementation of the invention differs from the in DE-A 42 44 194 disclosed reactions in that the order of the reaction was changed, that initially a cross-linking of the compounds of component Aa is made with crosslinkers of the component Ab and only then followed by a reaction of the product obtained with compounds of the component Ac
• the crosslinking of the compounds of component Aa with crosslinkers of the component Ac takes place 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 components Aa and Ab used. In general, the reaction time is 0.5 to 20 hours, preferably 1 to 10 hours.
• the crosslinker (component Ab) 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 step ii), which is preferred.
• step ii) the reaction of the product obtained in step i) with those compounds of the group Ac, which contain a monoethylenically unsaturated double bond, in the manner of a Michael addition, while chlorocarboxylic acids and glycidyl compounds of the formula I via the chlorine group or the epoxide group with the primary or secondary amino groups of the crosslinked product obtained in step i).
• the reaction is generally carried out at temperatures of 10 to 200 ° C, preferably 30 to 100 ° C. Usually, the reaction is carried out at atmospheric pressure.
• the reaction time depends on the components used. In general, the reaction time is 0.5 to 100 hours, preferably 1 to 50 hours.
• reaction is carried out in aqueous solution, wherein the product obtained in step i) is already present in aqueous solution.
• polyalkylenepolyamines according to the present application are understood to mean compounds which contain at least 3 nitrogen atoms, for example diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diaminopropylenethylenediamine, trisaminopropylamine and polyethylene imine.
• the polyethyleneimines preferably have an average molecular weight (M w ) of at least 300.
• the average molecular weight of the polyethyleneimines is preferably from 800 to 2,000,000, more preferably 20,000 to 1,000,000, most preferably 20,000 to 75,000, determined by means of light scattering.
• the polyalkylenepolyamines may be partially amidated. Products of this type are prepared, for example, by reaction of polyalkylenepolyamines with carboxylic acids, carboxylic esters, carboxylic anhydrides or carboxylic acid halides.
• the polyalkylenepolyamines are preferably amidated according to the present application for the subsequent reactions to 1 to 30, more preferably up to 20%. It is necessary that the amidated polyalkylenepolyamines still have free NH groups, so that they can be reacted with the compounds Ab and Ac.
• Suitable carboxylic acids for the amidation of the polyalkylenepolyamines are C 1 -C 28 -carboxylic acids, for example formic acid, acetic acid, propionic acid, benzoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid and behenic acid. It is also possible that the amidation is carried out by reaction of the polyalkylenepolyamines with alkyldiketene.
• the polyalkyleneamines may further be used in part in quaternized form as component Aa.
• Suitable quaternizing agents include, for example, alkyl halides such as methyl chloride, ethyl chloride, butyl chloride, epichlorohydrin, hexyl chloride, dimethyl sulfate, diethyl sulfate and benzyl chloride. If quaternized polyalkylenepolyamines are used as component Aa, the degree of quaternization is preferably 1 to 30, more preferably up to 20%.
• the polyamidoamines are obtainable, for example, by reacting C 4 -C 10 -dicarboxylic acids with polyalkylenepolyamines, which preferably contain from 3 to 10 basic nitrogen atoms in the molecule.
• suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use mixtures of carboxylic acids, for example mixtures of adipic acid and glutaric acid or maleic acid and adipic acid.
• Adipic acid is preferably used to prepare the polyamidoamines.
• Suitable polyalkylenepolyamines which are condensed with the dicarboxylic acids have already been mentioned above, for example diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine are suitable.
• the polyalkylenepolyamines can also be used in the form of mixtures in the preparation of the polyamidoamines.
• the Preparation of the polyamidoamines is preferably carried out in bulk, but can also be carried out in inert solvents, if appropriate.
• the condensation of the dicarboxylic acids with the polyalkylenepolyamines takes place at higher temperatures, for example in the range from 120 to 220.degree.
• the water formed during the reaction is distilled off from the reaction mixture.
• the condensation may optionally be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms.
• lactones or lactams of carboxylic acids having 4 to 8 carbon atoms In general, 0.8 to 1.4 mol of a polyalkylenepolyamine are used per mole of dicarboxylic acid.
• the polyamidoamines thus obtainable have primary and secondary NH groups and are soluble in water.
• monoethylenically unsaturated carboxylic acids are suitable which preferably have 3 to 18 carbon atoms in the alkenyl radical.
• Suitable monoethylenically unsaturated carboxylic acids are acrylic acid, methacrylic acid, dimethacrylic acid, ethylacrylic acid, allylacetic acid, vinylacetic acid, maleic acid, fumaric acid, ethaconic acid, methylenemalonic acid, citraconic acid, oleic acid and linolenic acid.
• the monoethylenically unsaturated carboxylic acids are preferably selected from the group consisting of acrylic acid, methacrylic acid and maleic acid.
• Suitable salts are generally the alkali metal, alkaline earth metal and ammonium salts of the abovementioned acids. Preferred are the sodium, potassium and ammonium salts.
• the ammonium salts can be derived from both ammonia and amines or amine derivatives such as ethanolamine, diethanolamine and triethanolamine.
• Suitable alkaline earth metal salts are generally magnesium and calcium salts of the abovementioned monoethylenically unsaturated carboxylic acids.
• Suitable esters of the abovementioned monoethylenically unsaturated carboxylic acids are derived from monohydric C 1 -C 20 -alcohols or divalent C 2 -C 6 -alcohols.
• Suitable esters include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, palmithyl acrylate, lauryl acrylate, diaryl acrylate , Lauryl methacrylate, palmithyl methacrylate, stearyl methacrylate, dimethyl maleate, diethyl maleate, isopropy
• Suitable amides of monoethylenically unsaturated carboxylic acids are, for example, acrylamide, methacrylamide and oleic acid amide.
• Suitable nitriles of the monoethylenically unsaturated carboxylic acids are preferably acrylonitrile and methacrylonitrile.
• suitable amides are to be understood as meaning the reaction products of the monoethylenically unsaturated carboxylic acids, in particular of (meth) acrylic acid, with amidoalkanesulfonic acids.
• chlorocarboxylic acids are, for example, chloroacetic acid, 2-chloropropionic acid, 2-chlorobutyric acid, dichloroacetic acid and 2,2'-dichloropropionic acid.
• Preferred compounds of the formula III are glycidyl acid, their sodium, potassium, ammonium, magnesium or calcium salts, glycidyl amide and glycidyl esters, such as methyl glycidylate, ethyl glycidylate, n-propyl glycidylate, n-butyl glycidylate, isobutyl glycidylate, 2-ethylhexyl glycidylate , Glycidylic acid 2-hydroxypropyl ester and 4-hydroxybutyl glycidylate. Particularly preferred are glycidylic acid, its sodium, potassium or ammonium salts or glycidylamide.
• a monoethylenically unsaturated carboxylic acid is preferably used as component Ac, particularly preferably acrylic acid, methacrylic acid or maleic acid, very particularly preferably acrylic acid.
• Another object of the present application are water-soluble compounds prepared by the novel process of the present application comprising the steps i) and ii).
• compositions according to the invention may contain, in addition to the component A and water, further components B to G.
• compositions of the invention contain from 0.01 to 80 wt .-%, preferably 0.01 to 30 wt .-%, particularly preferably 0.01 to 20 wt .-%, most preferably 0.01 to 5 wt .-% at least a surfactant selected from the group consisting of anionic, nonionic, amphoteric and cationic surfactants, as component B.
• 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, Palmitylsullfat, stearylsulfate 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 firstly treating a C 8-22, preferably C 10 - 18 alcohol, for example a fatty alcohol alkoxylated and subsequently sulfating the alkoxylation.
• 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 C 8 -C 24 -Olefinsulfonate and -disulfonate which may also represent mixtures of alkene and Hydroxyalkansulfonaten or -disulfonate, 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 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyltaurates, acylmethyltaurates, alkylsuccinic acids, alkenylsuccinic acids or their monoesters or hemiamides, alkylsulfosuccinic acids or their amides, mono- and
• Suitable anionic surfactants are also alkyl phosphates.
• the anionic surfactants are preferably added to the composition 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 can be used individually or in combination of different anionic surfactants and in admixture with the other surfactants mentioned. It is possible to use anionic surfactants of only one class, e.g. only fatty alcohol sulfates or only alkylbenzenesulfonates, but also mixtures of different classes, e.g. 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 contain usually 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 inventive compositions containing 3 to 12 moles of ethylene oxide ethoxylated C 10 -C 16 alcohols, more preferably ethoxylated fatty alcohols.
• ethylene oxide ethoxylated C 10 -C 16 alcohols more preferably ethoxylated fatty alcohols.
• 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.
• aphotere 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 having 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 compositions of 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 glycerol, propylene glycol, ethylene glycol, ethanol, isopropanol and n-propanol.
• 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) or at least one inorganic acid, carboxylic acid and / or sulfonic acid (component E) are in each case in a proportion of generally 0 to 5 wt.%, Preferably 0.01 to 3 wt. %, more preferably 0.02 to 1 wt .-%, most 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 composition of the invention may additionally contain at least one inorganic acid, carboxylic acid or sulfonic acid, wherein the molar ratio of ammonia and / or alkanolamine to carboxylic acid is preferably from 1 to 0.9 to 1 to 0.1 ,
• 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 formic acid, acetic acid, citric acid and lactic acid, most preferably acetic acid.
• suitable sulfonic acids are amidosulfonic acid and methanesulfonic acid, preferably amidosulfonic acid.
• suitable inorganic acids are HCl and H 3 PO 4 .
• 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.
• low molecular weight polycarboxylates can be used as the (co) builder.
• 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.
• compositions according to the invention may contain other 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 composition 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 citric acid, alkanolamines or NaOH, preservatives, complexing agents for alkaline earth ions, enzymes, bleaching systems, soil Polymers, foam boosters, foam inhibitors or foam inhibitors, biocides, tarnish and / or corrosion inhibitors, suspending agents, fillers, inorganic modifiers, 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.
• compositions according to the invention are generally prepared by mixing the components A to G, insofar as they are present in the composition according to the invention, and water.
• compositions can be used, for example, as hard surface pretreatment or after-treatment agents, in particular glass and ceramic or cleaning agents such as glass cleaners, floor cleaners, all-purpose cleaners, bathroom cleaners, rinse aids, dishwashing detergents for washing hands or machines, machine cleaners, metal degreasers, high-pressure cleaners, alkaline cleaners, acidic cleaners , Top degreasers, dairy cleaners and so on.
• glass and ceramic or cleaning agents such as glass cleaners, floor cleaners, all-purpose cleaners, bathroom cleaners, rinse aids, dishwashing detergents for washing hands or machines, machine cleaners, metal degreasers, high-pressure cleaners, alkaline cleaners, acidic cleaners , Top degreasers, dairy cleaners and so on.
• the compositions are preferably used as a pre- or post-treatment agent for hard surfaces, in particular glass and ceramic or cleaning agents such as glass cleaners, floor cleaners, all-purpose cleaners and bathroom cleaners.
• 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 composition according to the invention.
• the "contacting” is generally carried out by rinsing, spraying or wiping or other methods known 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.
• lime soap is precipitated on surfaces which have been pretreated with the water-soluble compounds (component A), they can then be cleaned much better than surfaces which have not been pretreated.
• compositions according to the invention for the treatment of hard surfaces for rapid and streak-free drying, facilitating the removal of soil, reducing or preventing the condensation of water and / or the formation of dried traces of water on the hard surfaces.
• Preferred compositions and Surfaces are already mentioned above.
• the compositions are preferably used in pre- or post-treatment agents for hard surfaces, in particular glass and ceramic or cleaning agents such as glass cleaners, floor cleaners, all-purpose cleaners and bathroom cleaners.
• Another object of the present application is the use of the inventive compositions according to the present application in cleaner applications for the dispersion of dirt and in particular lime soaps.
• Preferred compositions and surfaces are already mentioned above.
• the crosslinker is a reaction product of a medium molecular weight polyethylene glycol 1500 with epichlorohydrin. After completion of the addition, the mixture is stirred for 5 hours at 70 ° C.
• reaction solution is heated to 80 ° C and treated dropwise at this temperature within 3 hours with 259.4 g of acrylic acid. After completion of the addition, the solution is stirred at 95 ° C for an additional hour. After cooling, a viscous, yellow-orange solution of the product with a solids content of 44.1% (2 h, vacuum / 120 ° C) and a K value (1% in water) of 23.1.
• the K value according to Fikentscher represents a measure of the molecular weight of the polymer and is according to H. Fikentscher, Cellulose Chemistry, 13, 38-64, and 71-74 (1932 ) as a 1 wt .-% solution in water.
• the tiles are then placed vertically and sprayed in ten sprays with about 10.5 g of drinking water (hardness 10.4 ° dH).
• the appearance of the water film is evaluated (see Table 1).
• the time required for complete drying is checked (see Table 2).
• the appearance of the tiles after drying is also evaluated (Table 3).
• the contact angle is determined again (Table 4). The entire process (spraying / drying) is repeated 5 times). For comparison, an untreated tile is also sprayed, evaluated and measured.
• Table 1 Appearance of the water film polymer after 1st cycle after 2nd cycle after the 3rd cycle after the 5th cycle without runs streaky, drops Runs off streaky, drops runs streaky, drops runs streaky, drops 1 flat film flat film below 1/2 above surface, streaky surface, 1/3 above surface, below streaky 2 flat Film flat film 1/2 at the top, streaky at the bottom 1/3 above surface, below streaky 3 flat film flat film flat film, rips in the middle runs streaky, drops 4 flat film, tearing up streaky at the top, flat at the bottom streaky at the top, flat at the bottom 5 flat film flat film, rips in the middle runs streaky, drops Bathroom Cleaners flat film flat film Upper half flat, streaky below, drop Upper half flat, streaky below, drop Bath cleaner + polymer 1 flat film flat film flat film Upper half flat, streaky below, drop EVD after 1st cycle after 2nd cycle after the 3rd cycle after the 5th cycle Without 10-15 10-15 > 15 > 15 1 ⁇ 5 5-10 10-15 > 15 2 5-10 5-10 > 15 > 15
• each 1% solutions are prepared in water.
• a commercially available bath cleaner (biff ®) and this bath cleaner with 1% Polmyerzusatz be examined.
• the experiments are carried out on mirror glass tiles with a size of 15 x 15 cm.
• 0.3 g are placed on a tile and with a cloth over 30 sec evenly circling on the Surface blurred. Then let the tiles dry lying down. All solutions are good to apply.
• the bathroom cleaner containing solutions leave slight stains, the aqueous polymer solutions are invisible after drying. The comparison is an untreated tile.
• the tiles are set up vertically and sprayed with two sprays (about 0.4 g) of a 2.2% sodium oleate solution and then with a spray (about 0.2 g) of a 0.2 molar CaCl 2 solution. It forms visibly lime soap on the surface.
• the tiles are then tilted slightly and rinsed with 150 ml of drinking water (hardness 10.4 ° dH) (jet of glass water bottle led evenly along the upper tile edge).

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• 2004
  • 2004-01-30 DE DE102004005010A patent/DE102004005010A1/de not_active Withdrawn
• 2005
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