DE102014207172A1 - Siloxane-containing copolymers as hydrophobizing agents - Google Patents

Abstract

It is proposed to use siloxane-group-containing copolymers for the hydrophobic finishing of hard surfaces, in particular of glass, and hard surface cleaners, in particular for glass, containing such siloxane-containing copolymers.

Description

The invention relates to the use of certain polymeric siloxane-containing active ingredients for the hydrophobic finishing of hard surfaces, in particular of glass, and cleaning agents for hard surfaces, in particular for glass, containing such polymeric active ingredients.

The cleaning of hard surfaces and in particular the cleaning of glass has in addition to the hygienic aspect also an aesthetic side. Thus, it is desirable that a cleaned surface dries as quickly and evenly as possible in order to avoid the formation of unsightly drop or strip residues ("noses") wherever possible. However, these can arise not only after cleaning, especially when using hard water, but also between cleaning operations when the surface comes into contact with water again. This is the case for example in bathrooms, but especially in the weather and especially the rainfall exposed surfaces such as windows. Another aspect, again especially in weathered surfaces, is the reduction in the tendency of cleaned surfaces to become soiled, since it is desirable for the consumer to allow as long a period as possible to pass between two cleaning operations without the surface becoming dirty to the viewer. In addition, an anti-fog effect is desirable to minimize the condensation of water on the surface.

In order to achieve this, it has been proposed on various occasions to use cleaning agents which lead to the fastest possible surface wetting of the surface. The surface wetting with a thin film of water leads in comparison with the isolated presence of larger drops of water to faster drying, so that after this approach, the cleaning agent should modify the surface to be cleaned such that the wetting behavior compared to an untreated surface changes so that water on spread faster over a large area, making the surface more hydrophilic.

The present invention adopts a different approach and starts from the premise that water-borne traces on the surface would be avoided if water droplets could roll on the surface as it were, so that they fell away from it at lateral boundaries of the surface and not through Evasion of it would have to be removed.

Out ACS Appl. Mater. Interfaces, 2011, 3, 2179-2183 It is known that superhydrophobic surfaces can be generated by spraying solutions of poly (SiMA-co-MMA) onto substrates.

in denen
R¹ für -(CH₂)_nSi(OSi(CH₃)₃)_m(OH)_p(R₅)_q,
R², R³ und R⁴ unabhängig voneinander für H oder eine Alkylgruppe mit 1 bis 3 C-Atomen,
R⁵ für eine Alkylgruppe mit 1 bis 5 C-Atomen,
n für eine Zahl von 1 bis 3, und
m, p und q unabhängig voneinander für eine Zahl von 0 bis 3, wobei die Summe m + p + q = 3 beträgt, stehen,
zur hydrophoben Ausrüstung harter Oberflächen, insbesondere von Glas. The invention relates to the use of copolymers with the monomer unit of the general formula I and the monomer unit of the general formula II,

in which
R ^{1 is} - (CH ₂ ) _n Si (OSi (CH ₃ ) ₃ ) _m (OH) _p (R ₅ ) _q ,
R ² , R ³ and R ⁴ independently of one another are H or an alkyl group having 1 to 3 C atoms,
R ^{5 is} an alkyl group having 1 to 5 C atoms,
n is a number from 1 to 3, and
m, p and q independently of one another represent a number from 0 to 3, the sum being m + p + q = 3,
for the hydrophobic finishing of hard surfaces, in particular of glass.

Preferably, the surface after the equipment has a contact angle to water of at least 80 °, in particular from 90 ° to 120 °. Glass surfaces usually have contact angles of less than 10 °.

in denen R¹, R², R³ und R⁴ die vorgenannte Bedeutung aufweisen und x und y unabhängig voneinander für Zahlen von 2 bis 2000, insbesondere 10 bis 1000 stehen. The copolymers mentioned are accessible by radical polymerization of ethylenically unsaturated precursor compounds of the monomer units of the general formulas I and II. They may contain the two monomer units of the general formulas I and II in statistical distribution, or they have blocks I 'and II' composed of the monomer units I or II,

in which R ¹ , R ² , R ³ and R ^{4 have} the abovementioned meaning and x and y independently of one another represent numbers from 2 to 2000, in particular from 10 to 1000.

If desired, the siloxane-containing copolymers may contain, in addition to the monomer units I and II, further monomer units derived from ethylenically unsaturated compounds. Apart from components derived from conventional free-radical initiator and terminator compounds, they preferably consist only of the monomer units I and II.

In preferred copolymers, the molar ratio of monomer unit I to monomer unit II is in the range from 10: 1 to 1:10, in particular from 3: 1 to 1: 3 and particularly preferably 1: 1. The average molecular weight (here and hereinafter: weight average) of the copolymer is preferably in the range of 1000 g / mol to 1 000 000 g / mol, in particular from 2000 g / mol to 500 000 g / mol.

The use according to the invention can be carried out in a simple manner by a process for the hydrophobic finishing of hard surfaces, in particular of glass, such that the copolymer, in bulk or as a constituent of a liquid preparation, for example a solution, suspension or dispersion, for example in acetone, on the hard surface, in particular a glass surface applying, for example by casting or spraying, and if desired, excess material, for example by means of a cloth or sponge, removed from the surface. In this case, preferably 0.01 ml to 1 ml, in particular 0.05 ml to 0.5 ml of a 0.001 weight percent to 10 weight percent, in particular 0.02 weight percent liquid preparation, in particular solution, of the copolymer per cm ^{2 of} the surface, and Leaves this act at least 30 minutes, wherein the solvent, dispersant or suspending agent of the liquid preparation optionally, completely or partially, can evaporate. It is also possible to immerse objects with hard surfaces, in particular of glass, in a liquid preparation. However, the use of the present invention can also be carried out by the use of a detergent containing the siloxane group-containing copolymer, and embodiments of the method of the present invention can be practiced using such a detergent.

A further subject of the invention is therefore an especially liquid cleaning agent for hard surfaces, in particular glass, comprising a siloxane group-containing copolymer defined above. The agent preferably contains from 0.01% by weight to 10% by weight, in particular from 0.05% by weight to 1% by weight, of the siloxane-containing copolymer, with the details of% by weight being given here and below. % to the total amount.

By using the cleaning agent, a hydrophobing of the surface takes place, which leads to a long-lasting reduction of the wettability of the surface. As a result, water droplets emit from the surface and can not deposit any constituents, for example dirt particles, on the surface, so that the appearance of the cleaned surface is clean for a longer period of time. These effects are preferably observed over an extended period of time after application of the agent, for example for three weeks. However, a permanent equipment of the surface is not sought. Finally, the detergent to be used should meet the usual technical and aesthetic requirements for a hard surface cleaner; In particular, the agent should be transparent in a preferred embodiment and also suitable for spraying and have a good cleaning performance.

An agent according to the invention preferably contains at least 1 surfactant. Surfactants from the classes of anionic and nonionic surfactants are particularly suitable for the compositions according to the invention. Preferably, the compositions contain anionic surfactants. The amount of anionic surfactant is usually not more than 10 wt .-%, preferably between 0.01 and 5 wt .-%, in particular between 0.01 and 1 wt .-%, for example 0.5 wt .-%. If the compositions 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 of nonionic surfactants. It has furthermore proven particularly advantageous if the total surfactant content in the ready-to-use composition is not more than 6% by weight. Will that be Agent provided as a concentrate for dilution before use, the total surfactant content is preferably not more than 15 wt .-%, particularly preferably 1 to 12 wt .-%, in particular 2 to 10 wt .-%.

Suitable anionic surfactants are preferably C ₈ -C ₁₈ -alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C ₈ -C ₂₀ -alkanesulfonates, C ₈ -C ₁₈ -monoalkyl sulfates, C ₈ -C ₁₈ -alkylpolyglycol ether sulfates having 2 to 6 ethylene oxide units (EO) in the ether part as well as sulfosuccinic mono- and di-C ₈ -C ₁₈ -alkyl esters. Furthermore, C ₈ -C ₁₈ -α-olefinsulfonates, sulfonated C ₈ -C ₁₈ -fatty acids, in particular dodecylbenzenesulfonate, C ₈ -C ₂₂ -Carbonsäureamidethersulfate, C ₈ -C ₁₈ -Alkylpolyglykolethercarboxylate, C ₈ -C ₁₈ -N-Acyltauride , C ₈ -C ₁₈ -N sarcosinates and C ₈ -C ₁₈ -alkyl isethionates or mixtures thereof.

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 of their corresponding acid, for example dodecylbenzenesulfonic acid. Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkanesulfonate having about 15 carbon atoms and sodium dioctylsulfosuccinate. Fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates having 12 to 14 C atoms have proven to be particularly suitable.

Particularly suitable nonionic surfactants are C ₈ -C ₁₈ -alcohol polyglycol ethers, that is to say ethoxylated and / or propoxylated alcohols having 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and / or propylene oxide units (PO), C ₈ -C ₁₈ -Carbonsäurepolyglykolester with 2 to 15 EO, for example, tallow fatty acid + 6-EO ester, ethoxylated fatty acid amides having 12 to 18 carbon atoms in the fatty acid moiety and 2 to 8 EO, long-chain amine oxides having 14 to 20 carbon atoms and long-chain alkylpolyglycosides with 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units to mention. Examples of such surfactants are oleyl-cetyl-alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, Kokosalkyldimethylaminoxid and Kokosalkylpolyglucosid with an average of 1.4 glucose units. Particular preference is given to fatty alcohol polyglycol ethers having in particular 2 to 8 EO, for example C _12-14 -fatty alcohol + 4-EO ether.

C ₈ -C ₁₈ alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be described by the formula R ⁱ O- (CH ₂ CH (CH ₃ ) O) _p (CH ₂ CH ₂ O) _e -H (III) in which R ^{i 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 and e is numbers from 1 to 20. These C ₈ -C ₁₈ -alkyl alcohol polyglycol ethers 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 III in which R ^{i is} an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7. Preferred representatives are, for example, C ₁₀ -C ₁₄ fatty alcohol + 1PO + 6EO ether (p = 1, e = 6) and C ₁₂ -C ₁₈ fatty alcohol + 7EO ether (p = 0, e = 7) and mixtures thereof ,

It is also possible to use end-capped C ₈ -C ₁₈ -alkyl alcohol polyglycol ethers, ie compounds in which the free OH group in the formula III has been etherified. The end-capped C ₈ -C ₁₈ -alkyl alcohol polyglycol ethers can be obtained by relevant methods of preparative organic chemistry. Preferably, C ₈ -C ₁₈ alkyl alcohol polyglycol ethers are reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride. Typical examples are mixed ethers of the formula III, in which R ^{i is} a technical fatty alcohol radical, preferably C _12/14 cocoalkyl radical, p is 0 and e is 5 to 10, which are closed with a butyl group.

Preferred nonionic surfactants are also alkyl polyglycosides (APG) of the formula R ⁱⁱ O [G] _x in the R ⁱⁱ for a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] for a glycosidically linked sugar moiety and x for a Number from 1 to 10; the index number x indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides. Whereas x is always an integer in a given compound and can take on the values x = 1 to 6, the value x for a given alkyl glycoside is an analytically determined average value that can also be a fractional number. Preferably, alkyl glycosides having a mean degree of oligomerization x of 1.1 to 3.0 are used. From an application point of view, those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred. The glycosidic sugar used is preferably xylose, but especially glucose. The alkyl or alkenyl radical R ⁱⁱ can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, for example as obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis. Preferably, however, the alkyl or alkenyl radical R ⁱⁱ is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, Isostearyl alcohol or oleyl alcohol from. Also to be mentioned are elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.

Further nonionic surfactants may be nitrogen-containing surfactants, for example fatty acid polyhydroxyamides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides having 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. Preferred are ethanolamide derivatives of alkanoic acids having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. Particularly useful compounds include the lauric, myristic and palmitic monoethanolamides.

Also particularly preferred are 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.

In addition to the previously mentioned types of surfactant, the agent according to the invention may also contain cationic surfactants and / or amphoteric surfactants.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetain. The compositions contain amphoteric surfactants in amounts, based on the composition, of 0 to 10 wt .-%.

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 are} four identical or different, in particular two long and two short-chain, alkyl radicals and X ^{- are} an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. The compositions contain cationic surfactants in amounts, based on the composition, of 0 to 10 wt .-%.

In a particularly preferred embodiment, however, the agent contains as surfactant components only one or more anionic surfactants, preferably C ₈ -C ₁₈ -alkyl sulfates and / or C ₈ -C ₁₈ -alkyl ether sulfates, and / or one or more nonionic surfactants.

Furthermore, the cleaning agents according to the invention, especially if they are in liquid form, water and / or water-soluble organic solvents, for example lower alcohols and / or ether alcohols, but preferably mixtures of different alcohols and / or ether alcohols containing. Lower alcohols in the context of this invention are straight-chain or branched C _1-6 -alcohols. The amount of organic solvent is usually not more than 50% by weight, preferably 0.1 to 30% by weight, more preferably 0.5 to 15% by weight, most preferably 1 to 10% by weight.

The alcohols used are in particular ethanol, isopropanol and n-propanol. As ether alcohols are sufficiently water-soluble compounds having up to 10 carbon atoms in the molecule into consideration. Examples of such ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether, of which in turn ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred. If alcohol and ether alcohol are used side by side, the weight ratio of both is preferably between 1: 2 and 4: 1. If, on the other hand, mixtures of two different ether alcohols, in particular ethylene glycol monobutyl ether and propylene glycol monobutyl ether, are used, then the weight ratio of both is preferably between 1: 6 and 6: 1, in particular between 1: 5 and 5: 1, for example 4: 1, wherein preferably the proportion of Ether alcohol with fewer carbon atoms is the higher of the two.

Furthermore, the agents according to the invention may contain volatile alkali. As such, ammonia and / or alkanolamines, which may contain up to 9 C atoms in the molecule, are used. As alkanolamines, the ethanolamines are preferred and of these in turn the monoethanolamine. The content of ammonia and / or alkanolamine is preferably up to 3 wt .-%, in particular 0.01 to 1 wt .-%, particularly preferably 0.05 to 0.75 wt .-%.

Alkaline agents may additionally contain carboxylic acid in addition to the volatile alkali, wherein the equivalent ratio of amine and / or ammonia to carboxylic acid is preferably between 1: 0.9 and 1: 0.1. Suitable carboxylic acids having up to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids. Depending on the equivalent weight of amine and carboxylic acid, the content of carboxylic acid is preferably between 0.01 and 2.7% by weight, in particular between 0.01 and 0.9% by weight. Examples of suitable carboxylic acids are Acetic acid, glycolic acid, lactic acid, citric acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid, of which acetic acid, citric acid and lactic acid are preferably used. Particular preference is given to using acetic acid.

Acid detergents according to the invention may also contain acids instead of volatile alkali. Suitable acids are, in particular, organic acids such as the abovementioned carboxylic acids acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, it is also possible to use the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof. Particular preference is given to acids selected from the group comprising amidosulfonic acid, citric acid and formic acid. They are preferably used in amounts of 0.1 to 5 wt .-%, more preferably 0.5 to 4 wt .-%, in particular 1 to 3 wt .-%.

In addition, the acidic cleaning agents according to the invention may also contain small amounts of bases. Preferred bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is particularly preferred. In the acidic agents, bases are used in amounts of not more than 1% by weight, preferably 0.01 to 0.1% by weight.

The agent is preferably liquid and preferably has a viscosity according to Brookfield (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 , most preferably 1 to 60 mPa · s, on. For this purpose, the agent may contain viscosity regulators. The amount of viscosity regulator is usually up to 0.5 wt .-%, preferably 0.001 to 0.3 wt .-%, in particular 0.01 to 0.2 wt .-%, most preferably 0.05 to 0.15 wt .-%.

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 products (carboxymethylcellulose and other cellulose ethers, hydroxyethyl - and -propylcellulose and the like, core flour ethers), 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).

Examples of polyacrylic and polymethacrylic compounds include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are obtainable inter alia from Fa. 3V Sigma under the tradename Polygel ^® such as Polygel ^® DA, and by the company. BFGoodrich under the tradename Carbopol ^®, such as Carbopol ^® 940 (molecular weight about 4,000,000), Carbopol ^® 941 (molecular weight approximately 1,250,000) and Carbopol 934 ^® (molecular weight about 3,000,000). Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with C _1-4 alkanols, esters, such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or butyl acrylate and methyl methacrylate, and which are for example, by Fa. Rohm & Haas under the trade names Aculyn ^® and Acusol ^® and from Evonik under the trade name Tego ^® polymer obtainable, for example the anionic non-associative polymers Aculyn ^® 22, Aculyn ^® 28, Aculyn ^® 33 (crosslinked), Acusol ^® 810, Acusol ^® 823 and Acusol ^® 830; (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C _10-30 alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with C _1-4 alkanols formed, esters, and which are obtainable for example from the company. BFGoodrich under the tradename Carbopol ^®, Carbopol ^® example hydrophobized ETD 2623 Carbopol ^® and 1382 ^®, and Carbopol AQUA 30th

Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, may alternatively or preferably be used 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 carboxymethylcellulose or its sodium salt, methyl, ethyl, 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 ⁶ g / mol and, for example, of the Kelco under the trade name Keltrol ^® and Kelzan ^® or by the company Rhodia under the trade name Rhodopol ^{® is} available.

As thickeners, it is also possible to use phyllosilicates. These include, for example, available under the trade name Laponite ^® magnesium or sodium magnesium phyllosilicates from Solvay Alkali, in particular the Laponite ^® RD or Laponite ^® RDS, and the magnesium silicates Süd-Chemie, especially the Optigel ^® SH.

When selecting the suitable viscosity regulator is preferably to ensure that the transparent impression of the liquid detergent is maintained, that is, the use of the thickener should not lead to clouding of the agent as possible.

In one embodiment, 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 content of viscosity regulator (thickener) can be up to 2 wt .-% in these cases.

In addition to the components mentioned, the compositions according to the invention may contain further auxiliaries and additives, as are customary in such compositions. These include in particular dyes, perfume oils, preservatives, complexing agents for alkaline earth metal ions, enzymes, bleaching systems and antistatic agents. Furthermore, polymers, in particular copolymers such as those available from BASF Sokalan® ^®, are used as the Sokalan CP ^® 9, the sodium salt of a maleic acid-olefin copolymer.

The amount of such additives is usually not more than 2 wt .-% in the detergent. The lower limit of the use depends on the nature of the additive and can be up to 0.001 wt .-% and below, for example, in the case of dyes. Preferably, the amount of excipients is between 0.01 and 1 wt .-%.

The pH of the compositions according to the invention can be varied over a wide range, but is preferably in the range from 2.5 to 12. Glass cleaner formulations and all-purpose cleaners in particular have a pH of from 6 to 11, more preferably from 7 to 10.5 and bath cleaners in particular a pH of 2 to 5, most preferably from 2.5 to 4.0.

The agents according to the invention are preferably formulated ready for use. A formulation as concentrate to be diluted prior to use is likewise possible within the scope of the teaching according to the invention, the contents then being contained in the upper range of the respectively indicated quantitative ranges.

The compositions of the invention can be prepared by mixing directly from their raw materials, then mixing and final standing of the agent to freedom from bubbles.

The compositions of the invention are preferably used for glass cleaning, both for windows and for mirrors and other glasses. But they can also be used to clean hard surfaces of other materials, especially those surfaces that are occasionally or frequently washed out with dirty or even clean water, such as showers, baths and floors in bathrooms or kitchen surfaces. A further field of use of agents according to the invention are rinse aids for dishwashers.

Examples

Example 1: Polymer Synthesis

a) polymer P1

3.80 g of methyl methacrylate, 5.45 g of 3- [tris (trimethylsiloxy) silyl] propyl methacrylate, 0.05 g of butanethiol and 0.17 g of azobis (isobutyronitrile) were dissolved in 40 ml of toluene, the reaction solution was allowed to stand for 20 minutes Discharge of nitrogen in the ultrasonic bath degassed and then heated to 90 ° C for 6 hours.
Mol Weight (Mw) Polymer P1: 11000 g / mol

b) polymer P2

8.00 g of methyl methacrylate, 11.49 g of 3- [tris (trimethylsiloxy) silyl] propyl methacrylate, 0.022 g of butanethiol and 0.08 g of azobis (isobutyronitrile) were dissolved in 40 ml of toluene, the reaction solution was stirred for 20 minutes while introducing Degassed nitrogen in an ultrasonic bath and then heated to 90 ° C for 6 hours.
Mol Weight (Mw) Polymer P2: 62,000 g / mol

c) polymer P3

8.00 g of methyl methacrylate, 11.49 g of 3- [tris (trimethylsiloxy) silyl] propyl methacrylate, and 0.08 g of azobis (isobutyronitrile) were dissolved in 40 ml of toluene, the reaction solution was bubbled with bubbling nitrogen for 20 minutes degassed and then heated to 90 ° C for 6 hours.
Mol Weight (Mw) Polymer P3: 98000 g / mol

d) Polymer P4

7.58 g of methyl methacrylate, 8.43 g of methacryloxymethylbis (trimethylsiloxy) methylsilane, 0.045 g of butanethiol and 0.17 g of azobis (isobutyronitrile) were dissolved in 40 ml of toluene, the reaction solution was degassed for 20 minutes while introducing nitrogen in an ultrasonic bath and then for Heated to 90 ° C for 6 hours.
Molar weight (Mw) P4: 19,000 g / mol

f) polymer P5

7.57 g of methyl methacrylate, 8.77 g of methacryloxymethylbis (trimethylsiloxy) methylsilane, 0.045 g of butanethiol and 0.17 g of azobis (isobutyronitrile) were dissolved in 40 ml of toluene, the reaction solution was degassed for 20 minutes while introducing nitrogen in the ultrasonic bath and then for Heated to 90 ° C for 6 hours.
Mol Weight (Mw) P5: 150000 g / mol

g) comparative polymer V1

6.89 g of 3- [tris (trimethylsiloxy) silyl] propyl methacrylate and 0.125 g of azobis (isobutyronitrile) were dissolved in 20 ml of toluene, the reaction solution was degassed for 30 minutes while introducing nitrogen in an ultrasonic bath and then heated to 70 ° C for 24 hours C heated. A further 0.125 g of azobis (isobutyronitrile) in 20 ml of toluene were metered in and the temperature maintained at 70 ° C. for a further 6.5 hours.
Mol Weight (Mw) Comparative Polymer V1: 79000 g / mol

h) comparative polymer V2

7.99 g of methyl methacrylate and 0.06 g of azobis (isobutyronitrile) were dissolved in 50 ml of toluene, the reaction solution was degassed for 30 minutes while introducing nitrogen in an ultrasonic bath and then heated to 70 ° C for 24 hours. 0.06 g of azobis (isobutyronitrile) in 20 ml of toluene was then metered in and the temperature was maintained at 70 ° C. for a further 6.5 hours.
Mol Weight (Mw) Comparative Polymer V2: 36000 g / mol

The molecular weight of polymers P1 to V2 was measured by GPC in THF (PMMA calibration).

Example 2:

0.2% by weight solutions of each of the polymers prepared in Example 1 in acetone were sprayed onto glass plates (0.05 ml / cm ² ). The measurement of the contact angle of glass surfaces coated with the stated polymers was carried out after a drying time of 1 hour by means of a contact angle measuring device DSA 10 (Krüss, Hamburg). For this purpose, a drop of water with a volume of 10 .mu.l was applied by means of a capillary to the coated glass surface. Then, for 30 seconds every second, a picture of the drop on the surface was taken from the side by means of a camera, and the contact angle from the slope of the tangent to the drop was determined by the three-phase boundary. The mean value of the 30 measured values was formed. The measurement was carried out at 3 locations on the respective surface and the 3 values thus obtained were then averaged again to the values given in Table 1. Table 1: Contact angle of the synthesized polymers polymer Contact angle (°) P1 96 P2 94 P3 94 P4 94 P5 100 V1 94 V2 52 - 5

All polymers containing a silyl monomer showed a strong hydrophobization of the glass surface, which had a contact angle of only 5 ° without polymer coating. The mechanical properties of the coating with V1 were inferior to those of the coatings with the polymers P1 to P5. The molecular weight of the polymer had little effect on the contact angle.

QUOTES INCLUDE IN THE DESCRIPTION

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Cited non-patent literature

• ACS Appl. Mater. Interfaces, 2011, 3, 2179-2183 [0005]

Claims (9)

Use of copolymers with the monomer unit of the general formula I and the monomer unit of the general formula II,

in which R ^{1 is} - (CH ₂ ) _n Si (OSi (CH ₃ ) ₃ ) _m (OH) _p (R ₅ ) _q , R ² , R ³ and R ⁴ independently of one another are H or an alkyl group having 1 to 3 C atoms, R ^{5 is} an alkyl group having 1 to 5 C atoms, n is a number from 1 to 3, and m, p and q are each independently a number from 0 to 3, wherein the sum m + p + q = 3, stand for the hydrophobic finish of hard surfaces, especially glass. Cleaning compositions for hard surfaces, in particular of glass, containing a copolymer with the monomer unit of the general formula I and the monomer unit of the general formula II,

in which R ^{1 is} - (CH ₂ ) _n Si (OSi (CH ₃ ) ₃ ) _m (OH) _p (R ₅ ) _q , R ² , R ³ and R ⁴ independently of one another are H or an alkyl group having 1 to 3 C atoms, R ^{5 is} an alkyl group having 1 to 5 C atoms, n is a number from 1 to 3, and m, p and q are each independently a number from 0 to 3, wherein the sum m + p + q = 3, stand. Composition according to claim 2, characterized in that it contains 0.01 wt .-% to 10 wt .-%, in particular 0.05 wt .-% to 1 wt .-% of the copolymer. Process for the hydrophobic finishing of hard surfaces, in particular of glass, wherein a copolymer with the monomer building block of the general formula I and the monomer building block of the general formula II,

in which R ^{1 is} - (CH ₂ ) _n Si (OSi (CH ₃ ) ₃ ) _m (OH) - (R ₅ ) _q , R ² , R ³ and R ⁴ independently of one another are H or an alkyl group having 1 to 3 C atoms, R ^{5 is} an alkyl group having 1 to 5 C atoms, n is a number from 1 to 3, and m, p and q are each independently a number from 0 to 3, wherein the sum m + p + q = 3, are, in substance or as part of a liquid preparation, such as a solution, suspension or dispersion applied to the hard surface, in particular a glass surface and, if desired, excess material removed from the surface. A method according to claim 4, characterized in that 0.01 ml to 1 ml, in particular 0.05 ml to 0.5 ml of a 0.001 wt% to 10 wt%, in particular 0.02 wt% liquid preparation, in particular solution, of the copolymer per cm ^{2 of} the surface on the surface. Use according to claim 1 or agent according to claim 2 or 3 or method according to claim 4 or 5, characterized in that the Copolymer of the monomer units I or II comprises composite blocks I 'and II',

in which x and y independently of one another represent numbers from 2 to 2000, in particular from 10 to 1000. Use, means or method according to one of the preceding claims, characterized in that the copolymer consists only of the monomer units I and II. Use, means or method according to one of the preceding claims, characterized in that in the copolymer, the molar ratio of monomer unit I to monomer II in the range of 10: 1 to 1:10, in particular from 3: 1 to 1: 3. Use, agent or process according to any one of the preceding claims, characterized in that the average molecular weight of the copolymer in the range of 1000 g / mol to 1 000 000 g / mol, in particular from 2000 g / mol to 500 000 g / mol.