EP1572850A1 - Reinigungsmittel für harte oberflächen - Google Patents
Reinigungsmittel für harte oberflächenInfo
- Publication number
- EP1572850A1 EP1572850A1 EP03782393A EP03782393A EP1572850A1 EP 1572850 A1 EP1572850 A1 EP 1572850A1 EP 03782393 A EP03782393 A EP 03782393A EP 03782393 A EP03782393 A EP 03782393A EP 1572850 A1 EP1572850 A1 EP 1572850A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- agent according
- cleaning agent
- acid
- group
- preferably selected
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
Definitions
- the invention relates to aqueous, liquid, surfactant-containing cleaning agents for hard surfaces, in particular glass, which contain a colloidal silica sol and the use of which increases the negative charge on the surface.
- cleaning hard surfaces and especially cleaning glass also has an aesthetic side. It is desirable that a cleaned surface dries as quickly and evenly as possible in order to avoid the formation of unsightly droplet or strip-like residues ("noses"). However, these can not only be cleaned after cleaning, especially when using hard water, occur, but also between the cleaning processes when the surface comes into contact with water again, the so-called rain effect.This is the case, for example, in bathrooms, but especially in the case of surfaces exposed to the weather, such as windows, etc. This is generally why the surfaces dry quickly It is also advantageous if the surface is wetted over a longer period of time instead of the film tearing open, which likewise leads to "noses".
- noses unsightly droplet or strip-like residues
- the wetting with a thin film also contributes to quick drying; in addition, tiny dirt particles are evenly distributed instead of being concentrated in the "noses", so that the surface appears optically cleaner.
- Another aspect, again particularly in areas exposed to the weather, is the reduction of the tendency towards re-soiling of cleaned areas, since it is for it is desirable for the consumer to allow a long period of time to elapse between two cleaning processes without the surface appearing dirty to the viewer, and an anti-fogging effect is also desirable in order to minimize the condensation of water on the surface the cleaner should modify the surface to be cleaned in such a way that the wetting behavior changes compared to an untreated surface, so that it is less quickly soiled and dries quickly without the formation of "noses".
- EP 1 215 276 (Clariant) describes detergents and cleaning agents which contain microdisperse silicate-containing particles. These can also be colloidal silica sols. These particles are said to act as surface coating agents and lead to improved dirt detachment while reducing the tendency to re-soiling. About a further change in the surface No statement is made regarding the nature or about an anti-rain / anti-fog effect.
- the subject of published patent application DE 100 21 726 A1 is the use of nanoscale particles to improve the detachment of dirt and to reduce the possibility of re-soiling, especially of textile, but also hard surfaces.
- the particles used can in turn be SiO 2 sols.
- the particles increase the hydrophilicity of the surface and structure the surface, the latter point not being explained in more detail. Further changes in the surface quality are described as little as a possible anti-rain or anti-fog effect.
- the object of the present invention is therefore to provide a cleaning agent for hard surfaces, in particular glass, by means of which the surface to be cleaned is wetted over a wide area and dries quickly, and shows a low tendency to mist and re-soiling.
- cleaning agents to which certain colloidal, nanoparticulate silica sols are added bring about a change in the flow potential of the cleaned surface to more negative values, and that surfaces cleaned with such agents dry evenly without the formation of "noses" and fogging or soiling less quickly.
- the invention accordingly relates to a cleaning agent for hard surfaces, in particular glass, containing a colloidal nanoparticulate silica sol, characterized in that the flow potential of the surface is changed by -5 to -50 mV by its use compared to an untreated surface.
- cleaning agents preferably results in hydrophilization of the surface, which leads to long-term wettability of the surface as a flat film. This distributes the dirt particles evenly and does not form "noses", so that the appearance of the cleaned surface is clean over a longer period of time.
- These effects, as well as the lower tendency towards re-soiling and the anti-fogging effect, are preferably over a longer period of time after application of the agent for example for three weeks, but the aim is not to permanently equip the surface.
- the cleaning agent to be used should meet the usual technical and aesthetic requirements for a cleaning agent for hard surfaces; in particular, the agent should be transparent in a preferred embodiment and are also suitable for spraying and have good cleaning performance.
- Colloidal nanoparticulate silica sols in the sense of this invention are stable dispersions of amorphous particulate silicon dioxide SiO 2 with particle sizes in the range from 1 to 100 nm.
- the particle sizes are preferably in the range from 3 to 50 nm, particularly preferably 4 to 40 nm.
- An example of a silica sol that is suitable in the sense to be used in this invention, that available under the trade name Bindzil ® 30/360 from Akzo silica sol is suitable with a particle size of 9 nm.
- silica sols are Bindzf 15/500, 30/220, 40/200, 257/360 (Akzo), Nyacol ® 215, 830, 1430, 2034DI and Nyacol ® DP5820, DP5480, DP5540 etc.
- LevasiF 100/30, 100F / 30, 100S / 30, 200/30, 200F / 30, 300F / 30, VP 4038, VP 4055 (HC Starck / Bayer) or CAB-O-SPERSE ⁇ PG 001, PG 002 (aqueous dispersion of CAB-O-SIL ®, Cabot), Quartron PL-1, PL -3 (FusoChemical Co.), Köstrosol 0830, 1030, 1430 (Bad Köstritz Chemical Plant).
- the silica sols used can also be surface-modified silica which has been treated with sodium aluminate (alumina-modified silica).
- colloidal silica sol is suitable as an additive according to the invention. It has been shown that only those silica sols can be used in the sense of the invention, the application of which increases the mean micro-roughness by at least 5 nm to a maximum of 30 nm and a change in the flow potential by at least -5 mV to a maximum of -50 mV on the cleaned surface, compared to an untreated surface.
- Microroughness is a variable that is familiar to a person skilled in the art and can be measured by atomic force microscopy (AFM). It describes the distance deviation from an ideally smooth surface and is measured in ⁇ m or nm.
- hydrophilizing particles are adsorbed on the surface in such a way that the surface is 10 to 75% covered, so that at least 25% of the free space should remain.
- the agent according to the invention can also contain surface-active substances.
- Suitable surfactants for the agents according to the invention are surfactants, in particular from the classes of anionic and nonionic surfactants.
- the agents preferably contain anionic surfactants.
- the amount of anionic surfactant is usually not more than 10% by weight, preferably between 0.01 and 5% by weight, in particular between 0.01 and 1% by weight, for example 0.5% by weight. If the agents contain nonionic surfactants, their concentration is usually not more than 3% by weight, preferably between 0.001 and 0.3% by weight and in particular between 0.001 and 0.1% by weight. In a preferred embodiment, however, the agent according to the invention is free from nonionic surfactants.
- the total surfactant content in the ready-to-use composition is not more than 6% by weight. If the agent is offered as a concentrate for dilution before use, the total surfactant content is preferably not more than 15% by weight, particularly preferably 1 to 12% by weight, in particular 2 to 10% by weight.
- Suitable anionic surfactants are preferably C 8 -C 18 alkylbenzenesulfonates, in particular with about 12 C atoms in the alkyl part, C 8 -C 20 alkanesulfonates, C 8 -C 18 monoalkyl sulfates, C 8 -C 18 alkyl polyglycol ether sulfates with 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic acid mono- and -di-C 8 -C ⁇ 8 alkyl esters.
- EO ethylene oxide units
- the anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acidity, e.g. Dodecylbenzenesulfonic acid.
- surfactants examples include sodium cocoalkyl sulfate, sodium sec-alkane sulfonate with about 15 carbon atoms and sodium dioctyl sulfosuccinate. Fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates with 12 to 14 carbon atoms have proven to be particularly suitable.
- C 8 -C 18 alcohol polyglycol ethers ie ethoxylated and / or propoxylated alcohols having 8 to 18 carbon atoms in the alkyl part and 2 to 15 ethylene oxide (EO) and / or propylene oxide (PO), C
- EO ethylene oxide
- PO propylene oxide
- C are the nonionic surfactants in particular 8 -C 18 carboxylic acid polyglycol esters with 2 to 15 EO, for example tallow fatty acid + 6-EO esters, ethoxylated fatty acid amides with 12 to 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides with 14 to 20 C atoms and long-chain alkyl polyglycosides with 8 to 14 carbon atoms in the alkyl part and 1 to 3 glycoside units.
- surfactants examples include oleyl-cetyl alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, coconut alkyl dimethylamine oxide and coconut alkyl polyglucoside with an average of 1.4 glucose units.
- Fatty alcohol polyglycol ethers with in particular 2 to 8 EO, for example C 12 are particularly preferred.
- C 8 -C 18 alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants.
- R ' is a linear or branched, aliphatic alkyl and / or alkenyl radical having 8 to 18 carbon atoms
- p is 0 or numbers from 1 to 3
- e is numbers from 1 to 20.
- the C 8 -C 18 alkyl alcohol polyglycol ethers of the formula I can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to fatty alcohols.
- Typical examples are polyglycol ethers of the formula I in which R 'is an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7.
- end-capped C 8 -C 8 -alkyl alcohol polyglycol ethers ie compounds in which the free OH group in the formula I is etherified.
- the end-capped C 8 -C 18 alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry.
- C 8 -C 18 -Alkyl alcohol polyglycol ethers are preferably reacted with alkyl halides, in particular butyl or benzyl chloride, in the presence of bases.
- Typical examples are mixed ethers of the formula I in which R is a technical fatty alcohol radical, C 12/14 -Kokosal- preferably 'kylrest, p is 0 and e stand for 5 to 10 which are closed with a butyl group.
- Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula II, R ⁇ O [G] x , in which R ′′ for a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] for a glycosidically linked sugar radical and x stands for a number from 1 to 10.
- APG are non-ionic surfactants and are known substances which can be obtained by the relevant methods of preparative organic chemistry.
- the index number x in the general formula II indicates the degree of oligomerization (DP degree) , ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
- the alkyl or alkenyl radical R "(formula II) can be derived from primary alcohols having 8 to 18, preferably 8 to 14, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, as described, for example, in In the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from ROELEN's oxosynthesis.
- the alkyl or alkenyl radical R " is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
- Nitrogen-containing surfactants may be included as further nonionic surfactants, e.g. Fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides which have alkyl groups with 10 to 22 C atoms, preferably 12 to 18 C atoms.
- the degree of ethoxylation of these compounds is generally between 1 and 20, preferably between 3 and 10.
- Ethanolamide derivatives of alkanoic acids with 8 to 22 C atoms, preferably 12 to 16 C atoms, are preferred.
- the particularly suitable compounds include lauric acid, myristic acid and palmitic acid monoethanolamides.
- Agents which contain anionic and nonionic surfactant, in particular combinations of fatty alkyl sulfates and / or fatty alcohol polyglycol ether sulfates with fatty alcohol polyglycol ethers, are also particularly preferred.
- the agent according to the invention can also contain cationic surfactants and / or amphoteric surfactants.
- Suitable amphoteric surfactants are, for example, betaines of the formula (R i ) (R iv ) (R v ) N + CH 2 COO " , in which R Hi is an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms which is optionally interrupted by heteroatoms or heteroatom groups and R ⁇ v and R are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 8 -alkyl-dimethylcarboxymethylbetaine and C ⁇ C 17 -Alkylamidopropyl-dimethylcarboxymethylbetaine.
- the compositions contain amphoteric surfactants in amounts, based on the composition, of 0 to 10% by weight.
- Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X " , in which R vi to R ix represent four identical or different types, in particular two long and two short-chain, alkyl radicals and X "represent an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-decadyl-ammonium chloride and mixtures thereof.
- the compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10% by weight.
- the detergent contains only one or more anionic surfactants, preferably C 8 -C 18 alkyl sulfates and / or C 8 -C 8 alkyl ether sulfates, and / or one or more nonionic surfactants.
- the cleaning agents according to the invention can contain water-soluble organic solvents, for example lower alcohols and / or ether alcohols, but preferably mixtures of different alcohols and / or ether alcohols.
- Lower alcohols in the sense of this invention are straight-chain or branched C 1-4 alcohols.
- the amount of organic solvent is usually not more than 50% by weight, preferably 0.1 to 30% by weight, in particular 0.5 to 15% by weight, most preferably 1 to 10% by weight.
- ethanol, isopropanol and n-propanol are used as alcohols.
- Sufficiently water-soluble compounds with up to 10 carbon atoms in the molecule are suitable as ether alcohols.
- ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl butyl ether and propylene glycol monoethyl ether, of which in turn ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred.
- the weight ratio of the two is preferably between 1: 2 and 4: 1.
- the weight ratio of the two is preferably between 1: 6 and 6: 1 , in particular between 1: 5 and 5: 1, for example at 4: 1, the proportion of ether alcohol having fewer carbon atoms preferably being the higher of the two.
- the agents according to the invention can furthermore contain volatile alkali.
- ammonia and / or alkanolamines that contain up to 9 carbon atoms in the molecule can, used.
- the ethanolamines are preferred as alkanolamines, and the monoethanolamine of these in turn.
- the content of ammonia and / or alkanolamine is preferably 0.01 to 3% by weight, in particular 0.02 to 1% by weight, particularly preferably 0.05 to 0.75% by weight.
- alkaline agents can additionally contain carboxylic acid, the equivalent ratio of amine and / or ammonia to carboxylic acid preferably being between 1: 0.9 and 1: 0.1.
- Carboxylic acids with up to 6 carbon atoms are suitable, which may be mono-, di- or polycarboxylic acids.
- the carboxylic acid content is preferably between 0.01 and 2.7% by weight, in particular between 0.01 and 0.9% by weight.
- carboxylic acids examples include acetic acid, glycolic acid, lactic acid, citric acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid, of which preferably acetic acid, citric acid and lactic acid are used.
- Acetic acid is particularly preferably used.
- Acidic cleaning agents according to the invention can also contain acids instead of volatile alkali.
- Suitable acids are in particular organic acids such as the carboxylic acids already mentioned, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or also amidosulphonic acid.
- the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.
- Acids selected from the group comprising amidosulfonic acid, citric acid and formic acid are particularly preferred. They are preferably used in amounts of 0.1 to 5% by weight, particularly preferably 0.5 to 4% by weight, in particular 1 to 3% by weight.
- the acidic cleaning agents according to the invention can also contain small amounts of bases.
- bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is particularly preferred.
- Bases are used in the acidic agents in amounts of not more than 1% by weight, preferably 0.01 to 0.1% by weight.
- the agent preferably has a Brookfield viscosity (model DV-II +, spindle 31, rotational frequency 20 min "1 , 20 ° C.) of 0.1 to 200 mPa-s, in particular 0.5 to 100 mPa-s, extremely preferably 1 up to 60 mPa-s.
- the agent can gulators included.
- the amount of viscosity regulator is usually up to 0.5% by weight, preferably 0.001 to 0.3% by weight, in particular 0.01 to 0.2% by weight, most preferably 0.05 to 0.15% by weight .-%.
- Suitable viscosity regulators are, for example, organic natural thickeners (agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein), organic modified natural substances (carboxymethyl cellulose and other cellulose ethers , Hydroxyethyl and propyl cellulose and the like, core meal ether), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as montmorillonites, zeolites , Silicas).
- organic natural thickeners agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, de
- the polyacrylic and polymethacrylic compounds include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (/ ⁇ / C / designation according to the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA): Carbomer), also known as carboxyvinyl polymers.
- CFA Cosmetic, Toiletry, and Fragrance Association
- Such polyacrylic acids are obtainable inter alia from Fa. 3V Sigma under the trade name PolygeP such as Polygel ® DA, and by the company.
- CarbopoP such as CarbopoP 940 (molecular weight approximately 4,000,000), CarbopoP 941 (molecular weight ca. 1,250,000) or CarbopoP 934 (molecular weight approx.3,000,000).
- the following also include the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), which are preferably formed with C- M alkanols, to which, for example, the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (C / AS name according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) belong and which, for example, from Rohm & Haas under the trade names Aculyn ® and AcusoP as well as from Degussa (Goldschmidt) under the trade name Tego ® Polymer, for example the anionic non-associative polymers Aculyn ® 22, Aculyn ® 28, Aculyn ® 33 (crosslinked), AcusoP 810, AcusoP 823 and AcusoP
- Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carragenes and their salts, guar, guarane, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and theirs mixtures.
- polysaccharide gums for example gum arabic, agar, alginates, carragenes and their salts, guar, guarane, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, for example propoxylated guar, and theirs mixtures.
- polysaccharide thickeners such as starches or cellulose derivatives
- starches or cellulose derivatives can be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl or hydroxyethyl -; Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
- starches of various origins and starch derivatives for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl or hydroxyethyl -; Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
- a particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 * 10 ° and for example by Kelco under the trade names KeltroP and Kelzan ® or from the company Rhodia under the trade name RhodopoP is available.
- Layered silicates can also be used as thickeners. These include, for example, the magnesium or sodium-magnesium layer silicates from Solvay Alkali available under the trade name Laponite ® , in particular the Laponite ® RD or Laponite ® RDS, and the magnesium silicates from Süd-Chemie, especially the OptigeP SH.
- the cleaning agent according to the invention can also be formulated as a higher-viscosity liquid.
- the viscosity is then between 200 and 1000 mPa-s (Brookfield viscometer DV-II +, small sample adapter).
- the viscosity regulator (thickener) content can be up to 2% by weight.
- the agents according to the invention can contain further auxiliaries and additives as are customary in such agents. These include in particular dyes, perfume oils, preservatives, complexing agents for alkaline earth ions, enzymes, bleaching systems and antistatic substances.
- the Sokalan CP 9 ® the sodium salt can still for surface modification of polymers, particularly copolymers such as Sokalan® available from BASF ®, a maleic acid-olefin copolymer, can be used.
- the amount of such additives is usually not more than 2% by weight in the cleaning agent.
- the lower limit of use depends on the type of additive and can be up to 0.001% by weight and below, for example, for dyes.
- the amount of auxiliaries is preferably between 0.01 and 1% by weight.
- the pH of the agents according to the invention can be varied over a wide range, but a range from 2.5 to 12 is preferred.
- Glass cleaner formulations and all-purpose cleaners in particular have a pH of 6 to 11, most preferably from 7 to 10.5 and bath cleaners, in particular a pH of 2 to 5, most preferably 2.5 to 4.0.
- agents according to the invention are preferably formulated ready for use.
- Formulation as a concentrate to be diluted appropriately before use is also possible within the framework of the teaching according to the invention, the ingredients then being contained in the upper range of the quantity ranges indicated in each case.
- the agents according to the invention can be prepared by mixing them directly from their raw materials, then mixing them and then standing the agent until there are no bubbles.
- the agents according to the invention are preferably used for glass cleaning, both for windows and for mirrors and other glasses. However, they can also be used to clean hard surfaces, especially on surfaces that are occasionally or frequently flushed with dirty or clean water, for example showers, bathtubs and floors in bathrooms or kitchen surfaces. Another area of use of agents according to the invention are rinse aids for dishwashers. machines. However, textile surfaces can also undergo hydrophilization through the use of agents according to the invention. Yet another area of application is the hydrophilization of surfaces in the automotive sector, both of car paints and car windows.
- the agents according to the invention can of course also be used for lacquers in general, and metal surfaces can also be hydrophilized with them.
- the alkaline glass cleaners E1 to E3 according to the invention and the alkaline comparative V1 and the acidic bath cleaners E4 to E6 and the acid comparative V2 according to the invention were prepared by simply stirring the components according to Tables 1 and 2 together.
- E1 to E3 and E4 to E6 contained the nanoparticulate silica sol according to the invention, while V1 and V2 had no additive. All means were clear and colorless.
- Fatty alcohol sulfate sodium salt sodium lauryl sulfate (Texapon ® LS 35, Cognis)
- Fatty alcohol ether sulfate sodium salt sodium laureth sulfate (Texapon ® N70, Cognis) hydroxyethyl cellulase: Natrosol HHBR (Hercules)
- Nanoparticulate silica sol alkaline cleaner: Bindzil ® 30/360 (Akzo) acid cleaner: Bindzil ® CAT 80 (Akzo) Table 1: alkaline glass cleaner
- Citric acid 1 1 3 1
- the tiles treated with the comparative agent V2 like untreated tiles, showed the formation of drops after just two days when wetted with water. The residue was formed in the form of "noses", so that the tiles appeared dirty.
- the glass cleaners E1 to E3 and the comparison agent V1 were then examined for their anti-fogging and anti-rain effect:
- Anti-fog effect The treated mirror was held for 5 seconds over a dish (28 cm ⁇ 50 cm ⁇ 4 cm) with 1.5 liters of boiling water and immediately afterwards evaluated whether and how strongly the mirror was fogged up. Anti-rain effect.
- about 10 g of test rain prepared from tap water and 8 g / lw / Zc carpet pigment soil (55% by weight of kaolin, 43% by weight of quartz, 1.5% by weight of carbon black) were produced in about 4 seconds 101, 0.5% by weight iron oxide black; wfk code wfk-09 W) from w / c-Testgewebe GmbH (http://www.wfk.de), evenly sprayed onto the pretreated mirror surface.
- wetting and droplet formation were assessed and, after drying, dirt distribution and stain formation.
- the evaluation was carried out visually by a panel of five people, each person assigning the four means to positions 1 to 4 in order of decreasing effect.
- the respective mean is given together with an assessment in Table 3 as a grade. The lower the grade, the better the respective effect.
- V1 4.0 partially stains and "traces of drainage", dirt evenly in the upper part
- agents E1 to E3 show both an anti-rain effect and an anti-fog effect.
- Agents E1 to E3 were also used to produce the comparative agents V3 to V5 with the polymer poly (sodium p-styrene sulfonate) known as an anti-rain additive according to Table 4, based on V1 as a base formulation. These alkaline agents were also clear and colorless. Table 4
- agents V3 to V5 were also checked for an anti-fog effect.
- the agents V3 to V5 did not show any anti-fog effect.
- the surface roughness at the micrometer level was measured using an atomic force microscope (AFM; Nanoscope III).
- AFM atomic force microscope
- a white test tile (Villeroy & Boch toilet ceramics) was cleaned with the help of Pril solution and then ethanol, sprayed with a 1% solution of the respective additive in a glass cleaner base and the wet tile was rubbed dry with the help of a cellulose cloth.
- the tile treated in this way was measured in the AFM.
- Additi v 1 (Bindzil 30/360) 10 17 Addit v 2 (Bindzil CAT 80) 6 28 Addit v 3 * (Nanogate LSraB 0212) 9 12 Addit v 4 * (Klebosol 20 H 12) 8 11 Additi v 5 * (Klebosol 30 N 12) 6 9 Addit v 6 * (Klebosol 30 R 12) 9 10 * not according to the invention
- Increasing the micro-roughness results in easier dirt removal in parallel to the hydrophilization.
- the micro-roughness should accordingly increase by at least 5 nm to a maximum of 30 nm in order to achieve the desired hydrophilization effect. Increasing the roughness by only 3 nm is not sufficient. With an increase of more than 30 nm, freedom from residues and streaks is no longer guaranteed.
- the flow potential of treated tiles was measured using an EKA device (Anton Paar ElektroKinetikAnalyser).
- EKA device Anton Paar ElektroKinetikAnalyser
- a white test tile (Villeroy & Boch toilet ceramics) was cleaned with the help of Pril solution and then ethanol, sprayed with a 1% solution of the respective additive in a glass cleaner base and the wet tile was rubbed dry with the help of a cellulose cloth.
- the tile treated in this way was measured in the EKA device at 200 mbar and with 0.001 mol KCI as electrolyte.
- Additive 1 (Bindzil 30/360) -61
- Additive 2 (Bindzil CAT 80) -48
- Additive 3 * (Nanogate LSraB 0212) -23
- Additive 4 * (Klebosol 20 H 12) -34
- Additive 5 * (Klebosol 30 N 12) - 36
- Additive 6 * (Klebosol 30 R 12) -28 * not according to the invention
- the change in the negative flow potential proves the hydrophilization due to the increased amount of the surface charge.
- the flow potential should therefore change by at least -5 mV to a maximum of -50 mV in order to achieve the desired hydrophilization effect. Changing the flow potential by less than -5 mV does not result in sufficient hydrophilization. With a change of more than -50 mV, the surface energy is increased so much that the tendency towards re-soiling increases. This is also the case, for example, with colloidal TiO 2 particles.
- a black standard test tile (Villeroy & Boch bathroom ceramics, 18x12 cm) is sprayed with the respective test product.
- the damp tile is rubbed dry using a cellulose cloth.
- the tile is completely immersed in Demineralized water wetted and then brought into a vertical position.
- the drying tile is filmed on a camcorder.
- the dry area is calculated as a percentage of the area of the tile using digital image processing. This means that the drying process can be followed over time.
- Bindzil 30/360 leads to the best result at lower application concentrations.
- the shorter drying time leads to a directly visible benefit for the consumer.
- the contact angle of treated tiles with respect to water and ethylene glycol was measured using the drop contour analysis (contact angle measuring device Krüss DSA 10).
- a white test tile (Villeroy & Boch toilet ceramics) was cleaned with the help of Pril solution and then ethanol, sprayed with a 1% solution of the respective additive in a glass cleaner base and the wet tile was rubbed dry with the help of a cellulose cloth , The contact angle of water or ethylene glycol on the tile treated in this way was determined.
- the nanogate additive 3 not according to the invention only increases the contact angle in relation to ethylene glycol insufficiently.
- the contact angle should therefore decrease by at least 15 ° compared to water in order to achieve the desired hydrophilization effect.
- the contact angle with ethylene glycol should be increased by at least 5 °.
- the measurements of the microroughness and the flow potentials already prove that not every silica sol is suitable for use in cleaning agents according to the invention for the hydrophilization of surfaces. Furthermore, a degree of coverage of the surface of 10 to 75% is advantageous, i.e. even after adsorption of the hydrophilizing particles, at least 25% free surface should remain.
- the silica sol from Nanogate additive 3, LSraB 0212
- the silica sol from Nanogate achieved a degree of coverage of over 90%. The coverage was measured using an atomic force microscope (AFM; Nanoscope III) and optical image evaluation.
- Another criterion is the incorporation into a colorless, translucent, stable product.
- Some commercially available silica sols cannot meet this criterion.
- the adhesive hosol types 30 H 25 and 30 V 25, available from Clariant are opaque in the product.
- the Klebosol 30 V 50 is a white slurry, which is opaque in the product and does not form a stable formulation. laubt.
- the colloidal silica sols used in the document EP 1 215 276 already mentioned in the introduction are therefore not suitable for the use according to the invention.
- the agent is preferably diluted with water in a ratio of 1: 1 to 1: 100; a 1:10 dilution is particularly preferred.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Physical Vapour Deposition (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Glass Compositions (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Surface Treatment Of Glass (AREA)
- Silicon Compounds (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10258831 | 2002-12-17 | ||
DE10258831A DE10258831A1 (de) | 2002-12-17 | 2002-12-17 | Reinigungsmittel für harte Oberflächen |
PCT/EP2003/014203 WO2004055145A1 (de) | 2002-12-17 | 2003-12-13 | Reinigungsmittel für harte oberflächen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1572850A1 true EP1572850A1 (de) | 2005-09-14 |
EP1572850B1 EP1572850B1 (de) | 2010-11-03 |
Family
ID=32477697
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03782393A Revoked EP1572850B1 (de) | 2002-12-17 | 2003-12-13 | Reinigungsmittel für harte oberflächen |
Country Status (8)
Country | Link |
---|---|
US (1) | US7745383B2 (de) |
EP (1) | EP1572850B1 (de) |
JP (1) | JP2006509876A (de) |
AT (1) | ATE486922T1 (de) |
AU (1) | AU2003290037A1 (de) |
DE (2) | DE10258831A1 (de) |
ES (1) | ES2355722T3 (de) |
WO (1) | WO2004055145A1 (de) |
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-
2002
- 2002-12-17 DE DE10258831A patent/DE10258831A1/de not_active Ceased
-
2003
- 2003-12-13 WO PCT/EP2003/014203 patent/WO2004055145A1/de active Application Filing
- 2003-12-13 ES ES03782393T patent/ES2355722T3/es not_active Expired - Lifetime
- 2003-12-13 AT AT03782393T patent/ATE486922T1/de not_active IP Right Cessation
- 2003-12-13 DE DE50313244T patent/DE50313244D1/de not_active Expired - Lifetime
- 2003-12-13 EP EP03782393A patent/EP1572850B1/de not_active Revoked
- 2003-12-13 JP JP2004560400A patent/JP2006509876A/ja active Pending
- 2003-12-13 AU AU2003290037A patent/AU2003290037A1/en not_active Abandoned
-
2005
- 2005-06-13 US US11/151,635 patent/US7745383B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO2004055145A1 * |
Also Published As
Publication number | Publication date |
---|---|
ATE486922T1 (de) | 2010-11-15 |
US20050239674A1 (en) | 2005-10-27 |
DE50313244D1 (de) | 2010-12-16 |
JP2006509876A (ja) | 2006-03-23 |
WO2004055145A1 (de) | 2004-07-01 |
AU2003290037A1 (en) | 2004-07-09 |
ES2355722T3 (es) | 2011-03-30 |
EP1572850B1 (de) | 2010-11-03 |
US7745383B2 (en) | 2010-06-29 |
DE10258831A1 (de) | 2004-07-08 |
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