DE19901973A1 - Coating for skis and snowboards contains polyions of a polyelectrolyte and oppositely-charged ions of an ionic fluorinated surfactant in the form of a complex in the coating - Google Patents

Abstract

A coating for skis and snowboards contains polyions of at least one polyelectrolyte and oppositely-charged ions of at least one ionic fluorinated surfactant to charge the polyions, with the polyions and at least part of the surfactant ions forming complexes contained in the coating. Independent claims are also included for: (a) a composition containing polyions as above and oppositely charged ions of ionic fluorinated surfactant(s) which form complexes together in the coating, together with (i) fluorinated organic solvent(s) or (ii) organic solvent plus anions of an acid or cations of a base, or (iii) alcohols (in which case the complex is in the form of dispersed particles); (b) a process for the production of a coating composition by (i) slow addition of an aqueous polyelectrolyte solution to an aqueous fluoro-surfactant solution, (ii) filtration of the precipitate obtained, (iii) drying (if the solvent to be used is immiscible with water), (iv) dissolution in acid or alkaline liquid and (v) addition of organic solvent; (c) a similar process in which stage (i) involves the slow addition of an aqueous fluoro-surfactant solution to an aqueous polyelectrolyte solution with vigorous stirring; (d) a similar process starting from the unquaternized base of a polyelectrolyte, which is mixed in solution with a fluoro-surfactant solution and then treated with a suitable acid so that the ionic activity of the polyelectrolyte is increased to the point where a precipitate with the required stoichiometry is obtained, after which steps (ii)-(iv) are carried out as above; (e) a process for the production of a coating composition in the form of a dispersion, starting from alcohol-soluble polyelectrolytes and fluoro-surfactants, by slow addition of a well-homogenized solution of fluoro-surfactant(s) to an alcoholic solution of polyelectrolyte with vigorous stirring.

Description

The invention relates to a coating of skis and snow boards, a coating material for the production of the Be layering and method for producing the coating materials.

To reduce sliding friction for cross-country skis, alpine skis and snowboards are numerous materials from different manufacturers on the market. It is paraffin wax se, fluorinated waxes or fluorocarbon powder.

Classic cross-country skis are wider for the climbing area different materials to reduce snow accumulation tion with high sliding friction known. find here e.g. B. so-called. Klisterwachsse.

The waxes are in different formulations before and are therefore also applied to the Treads of the skis applied: On the one hand, the materia lien be dissolved in organic solvents. With such Lö coatings produced by solutions are usually not very stable and are therefore only used in the leisure sector puts. On the other hand, the waxes can be solid or waxy tiger form and become hot on the treads melted. These substances also meet higher demands, and are therefore called z. B. in performance used sport.

Also coatings based on PTFE (polytetrafluor thylene), which have a low surface energy known, but such coatings are only suitable for one very narrow temperature range.  

The materials according to the prior art are, however, in vie unsatisfactory in all respects:

The area of application of a wax formulation is usually highly limited. An optimal effect is only in one narrow range for snow temperature, humidity and Snow quality reached. Therefore, every race must be very many different substances compared on test skis to choose the best material. Change briefly Stig temperature and / or humidity parameters, so starts the racer with a "wrong waxed" ski.

In addition, many parameter areas are considered unsolved, d. H. the wax technician is often unable to Sports skis with a satisfactory gliding effect for ver to provide.

The application of the existing materials for competition sprüche is very time consuming and know-how intensive. For the Coating a pair of cross-country skis is done at multilayer takes about 45 minutes to build up the coating. Special The wax technician needs more experience to achieve the desired Sliding effect through choice of material and application method (Layer thickness of the coating, temperature, polishing quality, Matching primer to covering wax) can also be achieved. High are quality coatings with the higher quality materials therefore hardly accessible to the recreational athlete.

If the substances are melted hot, they damage the the application of the waxes and fluorocarbon powder necessary high temperatures the polyethylene ski coverings because of the melt point of polyethylene just a little above the melting point of the Waxes and fluorocarbon powder.  

Fluorocarbon powder may still only be put on with a protective mask will be worn, as the vapors generated are particularly unintentional overheating are extremely harmful to health.

The object of the invention is to provide a coating for skis, such as e.g. B. cross-country skis, alpine skis or jump skis, and snowboards like that such as a coating composition for making the Be to provide stratification, the existing disadvantages. ver avoids.

The task of providing a coating is overwhelmed solved by a coating containing poly Ions of at least one polyelectrolyte and to charge the Po lyions of oppositely charged surfactant ions at least one ionic fluorinated surfactant, the polyions and little least part of the surfactant ions contained in the coating Form complexes.

Ski coverings provided with the coatings according to the invention usually lead to at least equally good, but mostly improved sliding properties compared to established Be high quality coatings. It is also surprising that the Coatings, one of which is a rather low mechanical Would have expected stability, have abrasion resistance, which is higher than that of waxes. In particular, the Be durability of coatings applied with solvents gene waxes significantly exceeded.

It is also surprising that with an inventive Coating compared to conventional wax coating broader temperature, humidity and snow quality range is covered. This will solve the problems greatly reduced when selecting suitable coatings.  

In this application, polyelectrolytes are polymers understood the charged polyions and opposite have charged counterions.

The stoichiometry of the coating is preferably in the rear view of the polyelectrolytes and the fluorinated surfactants drew on the charge of the polyion and the surfactant ion (s) between 1: 0.5 and 1: 1.5. Be is particularly preferred rich between 1: 0.9 and 1: 1.1, very particularly preferably 1: 0.98 and 1: 1.02, most preferred is stoichiometry of 1: 1. It is assumed to indicate the loads, that both the polyion and the surfactant ion are fully charged (or dissociated).

The coating preferably has a mesomorphic structure which is detectable by small-angle X-ray scattering.

The coatings of the invention can still the Cotensi de, if necessary, for the formulation of the manufacture of the complexes used surfactants were used.

In principle, the complexes of the Be layering on polycations in combination with anions ioni shear fluorinated surfactants or polyanions in combination with Cations of ionic fluorinated surfactants are based.

In principle, all polyelectrolytes are ge as polyelectrolytes is suitable, preference being given to those which are not very hygroscopic pical because they lead to coatings that are not strong Absorb water. Strongly hygroscopic polyelectrolytes are e.g. As polyacrylic acid, polymethacrylic acid and poly (diallyl dimethylammonium chloride) and their salts. Are therefore preferred otherwise any combination of polyelectrolytes and fluorinated ionic surfactants. The polyelectrolytes should be particularly preferred such that the coating formed  low water absorption, preferably a maximum of 20% (w / w), particularly preferably at most 10% (w / w) and most preferably at most 5% (w / w) based on the weight of the complex xes at 20 ° C and 100% humidity of the complex.

In principle, the coatings according to the invention can also Contain mixtures of the polyions of polyelectrolytes, be preferably either mixtures of polycations or mixtures of polyanions.

A preferred class of cationic polyelectrolytes are polymers which preferably contain at least 20% of one or more of the following monomer units, with the proviso that the resulting polyelectrolyte is not very hygroscopic in the sense of the present invention:

• - Positively charged nitrogen groups, e.g. B. quaternary ammo nium groups or N-substituted heteroaromatic group pen-bearing ethylenically unsaturated monomers either as salts, such as those produced by the reaction of basic amino radio ions with mineral acids, e.g. B. hydrochloric acid, sulfuric acid or nitric acid, or obtained in quaternary Form (e.g. by reaction with dialkyl sulfates such as Dimethyl sulfate, diethyl sulfate etc., alkyl chlorides such as such as methyl chloride, ethyl chloride etc. or benzyl chloride), e.g. B. Dimethylaminoethyl acrylate hydrochloride, diallyldi methylammonium chloride, dimethylaminoethyl acrylate methosulfate, dimethylammonium chloride, dimethylaminopro pylmethacrylamide methochloride, Dimethylaminopropylacrylamide methochloride, dimethyla minopropyl methacrylamide methosulfate, dimethylaminopropy acrylamide methosulfate, vinyl pyridinium salts or 1- Vinyl imidazolium salts.

Optionally, the cationic polyelectrolyte in addition to the cationic monomer units also one or more nonioni  cal monomer units, e.g. B. contain up to 80 mol%. The An The presence of nonionic monomer units is in some cases len, e.g. B. in poly (diallyl-dimethylammonium chloride) for Ver reduction in hygroscopicity required.

Examples of suitable nonionic monomers are

• - C ₁ - to C ₂₀ alkyl and hydroxyl alkyl esters and especially amides and N-substituted amides of monoethylenically unsaturated C ₃ - to C ₁₀ - monocarboxylic acids or C ₄ - to C ₁₀ - dicarboxylic acids, e.g. B. acrylamide, methacrylamide, N-alkyl acrylamides or N, N-dialkylacrylamides each having 1 to 18 carbon atoms in the alkyl group such as N-methylacrylamide, N, N-dimethylacrylamide, N-tert-butylacrylamide or N-octadecylacrylamide, maleic acid monomethylhexylamide, Times monodecylamide, dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide or acrylamidoglycolic acid, furthermore alkylaminoalkyl (meth) acrylates, e.g. B. dimethyla minoethyl acrylate, dimethylaminomethacrylate, ethylaminoethyl acrylate, diethylaminoethyl methacrylate, further vinyl esters, e.g. B. vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, 1-vinylimidazole, 1-vinyl-2-methylimidazole or N-methylvinylacetamide.

An example of cationic polyelectrolytes consisting of cationic and nonionic monomer units is as follows:

• - Copolymers of dialkenyl-dialkylammonium salts, e.g. B. Dially dimethylammonium chloride, with nonionic mono meren, e.g. B. N-methyl-vinyl-acetamide, the proportion of nonionic monomer preferably at least 20 mol% is.

Other preferred classes of cationic polyelectrolytes are:

• - polyethyleneimines and alkyl-substituted polyethyleneimines, e.g. B. Poly (ethyleneimine-co-N-docosylethylimine);  
• - Ionene, i.e. H. Polymers with multiple quaternary ammonium groups, for example, by implementing di tertiary amines with α-, ω-dihaloalkenes are formed, e.g. B. Ions-6.3 and
• - Polysaccharides containing cationic groups, in particular their β-glycosidically linked polysaccharides, such as Chitosan.

Some of the polyelectrolytes mentioned can be in base form neutralized or completely neutralized to manufacture of the complexes according to the invention can be used.

In addition, are also for the coating according to the invention the polyions of anionic polyelectrolytes suitable, which in Can be used in conjunction with cationic surfactants.

A preferred class of such anionic polyelectrolytes are polymers which preferably contain at least 20 mol% of one or more of the following monomer units, with the proviso that the resulting polyelectrolyte is not very hygroscopic in the sense of the present invention:

• - Ethylenically unsaturated carboxylic acids and salts and derivatives thereof, e.g. B. C ₃ - to C ₁₀ monocarboxylic acids, their Al potassium metal and / or ammonium salts, for example dimethyl acrylate or ethyl acrylic acid, C ₄ - to C ₁₀ - dicarboxylic acids, their half esters, anhydrides, alkali metal salts and / or ammonium salts, for. B. maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylmalonic acid, citra consic acid, maleic anhydride, itaconic anhydride or methylmalonic anhydride;
• - Ethylenically unsaturated sulfonic acid groups Monomer units, for example allylsulfonic acid, Sty rolsulfonic acid, vinyl sulfonic acid, acrylic acid-3 sulfopropyl ester or 3-sulfopropyl methacrylic acid  
• - Contain phosphine, phosphonic or phosphoric acid groups de monoethylenically unsaturated monomers, e.g. B. Vinylphos phonic acid, allylphosphonic acid or acrylamidomethylpro panphosphonic acid.

If necessary, these anionic polyelectrolytes or more of the aforementioned nonionic monomer units ten, for example in a proportion of up to 80 mol% ten. The use of copolymers of anionic and nich ionic monomer units is used for some of the anionic Monomer units to reduce hygroscopicity before moves.

Another preferred class of anionic polyelectrolytes are polysaccharides containing anionic groups.

The anionic polyelectrolytes can partly in the acid form neutralized or used completely neutralized the.

Ionic fluorinated surfactants are substances which contain at least one fluorine atom bonded to a carbon atom, preferably at least one -CF ₂ - and / or CF ₃ group and at least one charge carrier. The proportion of the -CF ₂ - and / or CF ₃ group is preferably high.

In the coating and the complexes in the coating can of course, mixtures of ions from ionic fluorinated surfactants, preferably either mixtures of the ions cationic fluorinated surfactants or such anionic flu orated surfactants can be used.

Are particularly preferred, especially for coatings with a polyion fluorosurfactant stoichiometry of about 1: 1, hetero  disperse surfactants, d. H. Mixtures of surfactants with the same Head group but different chain lengths.

Anionic fluorinated surfactants include at least one fluorine containing hydrophobic group and at least one negative Charge carrier.

Examples of such compounds are fluorinated carboxylic acids as well as their salts with inorganic or organic cations, fluorinated sulfonic acids and their salts with inorganic or organic cations, fluorinated organosulfuric acids such as their salts with inorganic or organic cations, fluorinated phosphinic, phosphonic or organophosphoric acids so such as their salts with inorganic or organic cations.

Preferred of these classes of compounds are as follows:

• - Perfluorocarboxylic acids and their preferably water-soluble salts, such as perfluoroalkanoic acids, e.g. B. in particular perfluoroalkanoic acids of the formula CF ₃ (CF ₂ ) _n -COOH, where n is preferably greater than or equal to 7;
• - Partially fluorinated carboxylic acids and carboxylic acid salts, such as et wa partially fluorinated alkanoic acids, partially fluorinated alkene acid ren, perfluoroalkoxyalkanoic acids, perfluoroalkylethylene oxyalkanoic acids, perfluoroalkoxybenzoic acids and sulfide, Sulfonic acid, carboxamide, hydroxy, oxo and / or ether partially fluorinated carboxylic acids and salts containing groups from that; e.g. B. Lithium-3 - [(1H, 1H, 2H, 2H, fluoroalkyl) thio] - propionate, Zonyl FSA®, Du Pont);
• - Perfluorosulfonic acids and their preferably water-soluble salts, such as perfluoroalkanesulfonic acids of the formula: CF ₃ (CF ₂ ) _m -SO ₃ H with m greater than or equal to 1;
• - Partially fluorinated sulfonic acids and what preferably water soluble salts such as partially fluorinated alkanesulfone acids, e.g. B. Perfluoroalkylethanesulfonic acids, Perfluorpro pylethanesulfonic acids, partially fluorinated alkenesulfonic acids,  as well as sulfide, carboxamide, hydroxy, oxo or / and Partially fluorinated sulfonic acids containing ether groups, fluorinated sulfoesters, e.g. B. sulfosuccinic acid esters, Perfluoroalkyl sulfopropionates, perfluoroalkyl sulfobutyrates and salts thereof; e.g. B. Perfluoroalkylethylsulfonic acid Ammonium salt, Zonyl TBS ® Du Pont, sodium [succinic acid diperfluoroalkylethyl diester 2-sulfonate], Fluowet SB®, Clariant GmbH;
• - Fluorinated organic sulfuric acids and their salts such as such as perfluoroalkylated methyl sulfates, fluorinated sulfa topoly (oxyethylene), perfluoropropoxylated sulfates and Salts thereof;
• - Fluorinated phosphinic and phosphonic acids and their before preferably water-soluble salts, e.g. B. Fluowet PL80®, Hoe S 2746, Clariant GmbH;
• - Fluorinated organic phosphoric acids and their salts, such as about perfluoroalkylethyl phosphoric acids, mono- and Bis (fluoroalkyl) (ethyl) phosphoric acids, perfluoroalkylphos phosphoric acids, fluorinated phosphate alkyl esters, e.g. B. Phophore acid perfluoroalkyl ester ammonium salt, Zonyl FSE® and Zonyl FSP®, Du Pont.

Complexes with anionic polyelectrolytes contain cationi tensides.

Preferred classes of such compounds are:

• Fluorinated amines and ammonium salts such as fluoroalkylam monium salts, optionally carboxamide, sulfone contain acid amide, sulfide, ester, and / or hydroxy can, or heterocyclic nitrogen compounds, e.g. B. Perfluoroalkenylethyltrialkylammonium methosulfate, Hoe-L- 3658-1, Clariant GmbH.

Other useful ionic fluorinated surfactants are in the book by Erik Kissa (Fluorinated Surfactants, Surfactant Science  Series Vol. 50, Marcel Dekker, Inc. New York, 1994) ben.

The coating can also contain mixtures of complexes keep that preferred either only on polycations or only based on polyanions.

Also preferred are coatings that additionally wax contain. The waxes can e.g. B. paraffin wax se, fluorocarbon waxes and / or polyethylene waxes. The These coatings are particularly suitable for the sliding area. By simply varying the mixing ratios of wax and complex fraction, as well as by choosing the complex composition a wide range of mixtures (depending on the weather and snow conditions).

Also suitable are coatings that also have clisters contain. The coatings are primarily suitable for the Climbing area. By simply varying the mixing ratio of clister and complex parts, as well as the choice of Complex composition can be a wide range of mixtures (ent speaking of the weather and snow conditions) will be.

The task of a material for producing the Providing our coating is solved by a Be Layer composition containing polyions at least egg nes polyelectrolyte and to charge the polyions sets charged surfactant ions of at least one ionic flu orated surfactant, the polyions and at least part the complexes of the surfactant ions contained in the coating bil den, and at least one organic fluorinated solvent.  

For the poly contained in the coating composition Ions and surfactant ions of at least one ionic fluorinated The explanations for the coating above apply to surfactants.

The percentage by weight of organic fluorinated solvents is preferably greater than 50% by weight, particularly preferably larger more than 90% by weight.

The weight fraction of the polyions together with that of the flu orated surfactants is preferably 0.3 wt.% to 20 % By weight, particularly preferably 0.6 to 2.5% by weight.

The fluorinated organic solvents can be fluorinated alcohols or acids such as B. perfluoroacetic acid act.

The task of a material for producing the Providing our coating is still solved by a coating composition containing polyions least a polyelectrolyte and ent to charge the polyions oppositely charged surfactant ions of at least one ionic fluorinated surfactant, the polyions and at least one Part of the surfactant ions in the coating complexes form, as well as at least one organic solvent and anio an acid or cations of a base.

Surprisingly, they usually don't resolve themselves non-fluorinated alcohol-soluble complexes when in the Lö sufficient quantities of anions from acids or cations of bases are present. The anions or cations can also be ions of salts.

It is preferred that the solutions contain the anions of acids not included as anions of a salt. The same applies to Bases.  

Anions of organic acids are preferred, in particular of acetic acid and / or propionic acid. Typically included the compositions 1 to 3 parts by weight of acid to one Weight percentage of dry complex.

Cations of bases, preferably amines, are also preferred particular of butylamine, 2-amino-2-methylpropanol, dimethyla minoethanol and diethanolamine. Typically they contain Compositions 1 to 3 parts by weight of base on one Ge percentage by weight of dry complex.

For the poly contained in the coating composition Ions and surfactant ions of at least one ionic fluorinated The explanations for the coating above apply to surfactants. The weight fraction of the organic solvent is before increases greater than 50% by weight, particularly preferably greater than 90 % By weight.

Preferably, the solution contains a maximum of so much water that the Freezing point of the solution below 0 ° C, better below -5 ° C lies. The solution preferably contains less than 10 wt .-% Was ser, particularly preferably less than 5 wt .-%.

The weight fraction of the polyions together with that of the flu orated surfactants is preferably 0.3% by weight to 10 % By weight, particularly preferably 0.6 to 2.5% by weight.

Coating materials which are preferred as organic Solvent alcohols, preferably aliphatic, especially before moves alkyl alcohols, very particularly preferably ethanol and / or Contain isopropanol.  

An easy to manufacture and therefore preferred solution contains in addition to alcohols, anions of organic acid are also preferred ren, especially acetic acid and / or propionic acid. Typi Usually they contain 1 to 3 parts by weight of acid on egg dry complex.

Coating compositions whose Complex surfactant ions from sulfide and / or sulfone groups ent holding partially fluorinated carboxylic acids and salts thereof, such as. B. Lithium 3 - [(1H, 1H, 2H, 2H, fluoroalkyl) thio] propionate, zonyl FSA®, Du Pont) included.

An easy to manufacture and therefore preferred solution contains in addition to alcohols, cations of bases, preferably ami NEN, in particular of butylamine, 2-amino-2-methylpropanol, Di methylaminoethanol and diethanolamine. Typically included they add 1 to 3 parts by weight of base to one part by weight dry complex.

Coating compositions whose Complex surfactant ions from sulfide and / or sulfone groups ent holding partially fluorinated carboxylic acids and salts thereof, such as. B. Lithium 3 - [(1H, 1H, 2H, 2H, fluoroalkyl) thio] propionate, zonyl FSA®, Du Pont) or fluorinated phosphinic and phosphonic acids or which preferably contain water-soluble salts.

The task of providing a coating composition is further solved by a composition containing Dispersion particles containing polyions of at least one Po lyelectrolytes and to charge the polyions charged surfactant ions of at least one ionic fluorinated Surfactants, the polyions and at least part of the Ten form complexes contained in the coating, and Alcohols.  

Surprisingly, dispersions of the invention Complexes can be prepared in alcohols, although a solution from Com plexes in simple alcohols is usually not possible.

For the poly contained in the coating composition Ions and surfactant ions of at least one ionic fluorinated The explanations for the coating above apply to surfactants.

The proportion by weight of the alcohols is preferably greater than 50% by weight, particularly preferably greater than 90% by weight.

Preferably, the solution contains a maximum of so much water that the Freezing point of the solution below 0 ° C, better below -5 ° C lies. The solution preferably contains less than 10 wt .-% Was ser, particularly preferably less than 5 wt .-%.

The weight fraction of the polyions together with that of the flu orated surfactants is preferably 0.3% by weight to 5% by weight. % particularly preferably 0.6 to 2.5% by weight.

Coating compositions which are aliphatic are preferred cal, preferably alkyl alcohols, very particularly preferably etha nol and / or isopropanol included.

Also preferred are alcohols that are not fluorinated because fluorinated alcohols usually to solutions of the complex to lead.

The coating compositions according to the invention can continue waxes, e.g. B. paraffin and / or polyethylene waxes, dissolved or emulsified. The resulting coating are particularly suitable for the gliding area.

The coating compositions according to the invention can continue to contain klister.  

The coating composition according to the invention is also used union procedures, e.g. B. with a brush or sponge applicator or by spraying, applied to the ski base.

The surface to be coated is preferred before the application of the Coating with suitable alcohols and / or non-polar solvents means, e.g. B. Mixtures of petroleum ether and isopropanol, ge cleans to remove any dirt, especially Remove wax residue. Alternatively, this can be done carefully Brush out with a brass brush.

Application is preferably carried out at room temperature However, temperature can be below freezing z. B. at -10 ° C lie. This means that the application itself is still on the ski slope possible.

It is preferred to slightly over the ski base before coating To warm up to room temperature, particularly preferably Temperatures between 20 ° C and 50 ° C, because of this the long-term The stability of the coating is increased. Can be used for heating usual methods, such as heating with an electric Hair dryer, an iron or a warming bag, ver be applied.

After drying, the resulting ski covering is also known polished methods. Z are particularly suitable. B. commercially available Brushes made of horse hair, brass or nylon, rotating Brushes made of horse hair or nylon, nylon stockings or ver different fleeces that have a polishing effect.

The coating according to the invention can therefore be very easily within a short time, usually in the range of approx. 5 min, at room temperature or below from the invention Make coating compositions. The application  is satisfactorily possible even for a layperson. This are all significant advantages over conventional Be layers and coating materials.

Furthermore, the formulation is in harmless alcohols like ethanol or isopropanol possible, so that no special Health precautions, such as wearing Masks are necessary.

Another object of the invention is to manufacture processes To provide the coating composition.

The task is solved by a method with the steps:

• - Slow addition of an aqueous polyelectrolyte solution in a aqueous fluorosurfactant solution,
• - filtering off the precipitate that forms,
• - Drying the filtered precipitate if the or ganic solvents of the coating composition to be formed tongue does not mix with water,
• - Heating the solid formed in an acidic or al potash liquid until the solid has dissolved,
• - Mix in the organic solvent.

By adding the polyelectrolyte solution to the fluorosurfactant solution, it is achieved that as many of the complex bil suitable centers on the polyion by surfactant ions be plexed, d. H. there will be a substantial saturation of the Polyelectrolyte reached.

The filtered precipitate is preferred before drying or if this does not apply before demineralizing with loosening water washed until the conductivity of the wash water is less than 10 mS.  

The process uses the ionic fluorinated surfactants and the polyelectrolytes according to a stoichiometry of 1: 1 up to 1: 1.05 of the coating composition. In principle, z. B. the above Polyelectrolytes and the above-mentioned ionic fluorinated Suitable for surfactants.

The polyelectrolyte should preferably be introduced in such a way that he as high a charge as possible in the resulting complex Polyion educates; this can occur when using ionic flu orated surfactants in salt form z. B. done in that the Polyelectrol solution is at least partially neutralized. That be indicates that e.g. B. in polycations such. B. Polyethyleniminpo Lyations, possibly the pH z. B. with mineral acids such as B. HCl should be reduced. Due to the im concentration range according to the ion product the water's not very large number of charges are here too small amounts of mineral acids needed. This measure me is z. B. in the case of polycations then not necessary if the surfactants used are sufficiently strong acids. Ana loges applies to polyanions, which are corresponding measures known to the expert.

As mentioned above, the solutions of the ionic fluorier ten surfactants still contain cosurfactants which, for. B. the solution ver keep the ionic fluorinated surfactants improve. This can especially at higher concentrations of ioni be preferred surfactants. Co-surfactants are preferred turns that only a weak or, particularly preferred none, have a surfactant effect.

Preferably, in particular for the production of coating compositions according to the invention with a stoichiometry of approximately 1: 1, the ratio c _P / c _{T of} the concentrations of the poly ions of the polyelectrolyte solution c _{P used} and of the surfactants of the surfactant solution c _{T used} , expressed by the equivalent charge based on the weight of the respective solution above 1.2.

The precipitation can in principle be carried out at any temperature in which the solutions used are not highly viscous or solidify or evaporate. Temperatures are preferred between 10 ° C and 80 ° C, particularly preferably from room temperature to 80 ° C. The space is very particularly preferred temperature elevated temperatures.

The filtered precipitate is when the final product is none Water should contain more, first known to the expert dried process.

The solution in acidic liquid is preferred for coating tion compositions, the complexes of which are surfactant ions from sulfide and / or partially fluorinated carboxylic acids containing sulfone groups and salts thereof, e.g. B. Lithium 3 [(1H, 1H, 2H, 2H, fluoroalkyl) thio] propionate, Zonyl FSA®, Du Pont) included.

Preferred to dissolve the solid in acidic liquids are organic acids, particularly preferably glacial acetic acid or pro pionic acid.

The solution in alkaline liquids is preferred for Be coating compositions whose complexes of surfactant ions Partially fluorinated car containing sulfide and / or sulfone groups Bon acids and salts thereof, such as. B. Lithium 3 [(1H, 1H, 2H, 2H, fluoroalkyl) thio] propionate, Zonyl FSA®, Du Pont) or fluorinated phosphinic and phosphonic acids or their preferably contain water-soluble salts.

Particularly preferred for dissolving the solid in alkaline Liquids are amines, particularly preferably butylamine, 2-  Amino-2-methylpropanol, dimethylaminoethanol and diethanola min.

The solid is, preferably with stirring, as long as in the leave acidic or alkaline liquid until dissolved is. Depending on the liquid, the temperature is too high len that as complete a solution as possible. Prefers high temperatures (below the boiling point of the rivers liquid), which allow a quicker release.

The final step is the desired organic solvent added to the resulting solution.

If a neutral coating composition is desired, can the resulting solution with suitable bases or acids be neutralized.

The task is further solved by a process comprising the steps:

• - Slow addition of an aqueous fluorosurfactant solution to one aqueous polyelectrolyte solution with strong ver mixture,
• - filtering off the precipitate that forms,
• - Drying the filtered precipitate if the or ganic solvents of the coating composition to be formed tongue does not mix with water,
• - Heating the solid formed in an acidic or al potash liquid until the solid has dissolved,
• - Mix in the organic solvent.

This method tends to reduce the number of com plex formation suitable centers occupied by surfactant ions as in the procedure above, d. H. they are more complex with one Stoichiometry with regard to the polyelectrolytes and the  fluorinated surfactants based on the charge of the polyion and of the surfactant ion or more than 1: 1 formed.

In principle, z. B. the above Polyelectrolytes and the above-mentioned ionic fluorinated Suitable for surfactants.

The polyelectrolyte should preferably be introduced in such a way that he as high a charge as possible in the resulting complex Polyion educates; this can occur when using ionic flu orated surfactants in salt form z. B. done in that the Polyelectrol solution is at least partially neutralized. That be indicates that e.g. B. in polycations such. B. Polyethyleniminpo Lyations, possibly the pH z. B. with mineral acids such as B. HCl should be reduced. Due to the im concentration range according to the ion product the water's not very large number of charges are here too small amounts of mineral acids needed. This measure me is z. B. then not necessary in the case of polycations, if the surfactants used are sufficiently strong acids. The same applies to polyanions, the corresponding measures are known to the person skilled in the art.

As mentioned above, the solutions of the ionic fluorier ten surfactants still contain cosurfactants which, for. B. the solution ver keep the ionic fluorinated surfactants improve. This can especially at higher concentrations of ioni be preferred surfactants. Co-surfactants are preferred turns that only a weak or, particularly preferred none, have a surfactant effect.

With regard to washing and solution, the same applies here Comments on the first procedure.  

If the polyelectrolyte material is not present as a quaternized base, the task of providing a process for the production of a coating composition according to the invention can also be achieved by the following process for the production:

• - Production of a homogeneous mixture of polyelectrolyte solution solution and fluorosurfactant solution,
• - Add a suitable acid so that the ionic activity of the Polyelectrolyte is increased so that a precipitate with the desired stoichiometry fails,
• - filtering off the precipitate that forms,
• - Drying the filtered precipitate if the or ganic solvents of the coating composition to be formed tongue does not mix with water,
• - Heating the solid formed in an acidic or al potash liquid until the solid has dissolved,
• - Mix in the organic solvent.

Complexes with an excess of polyelectrolyte can thus preferably be used be preserved.

With regard to washing and solution, the same applies here Comments on the first procedure.

The coating compositions of the invention, the flu orated organic solvents can be obtained ten be that a ge after one of the above precipitation Dried solid is produced, which in the fluorinated Solvent is dissolved.

The object is further surprisingly achieved by a method comprising the steps:
Placing the polyelectrolyte in a suitable alcoholic solution,
Slow addition of a well homogenized solution of the fluorotides or the fluorosurfactants with strong mixing.

This process creates a dispersion of the complex. Due to the direct production, the precipitation step is omitted; In addition, the use of acids or bases for the Lö precipitation should be avoided.

Surprisingly, the affect in one after the colloidal according to the invention Dispersion contained counterions in the starting materials Formation and properties of a formed with the dispersion coating not or not essential.

The distribution of the surfactant molecules must be as homogeneous as possible. Form above the critical micelle concentration with appropriate treatment micelles, which is possible should be as small as possible. Under homogeneous distribution then understood that only small, evenly distributed Form micelles. The homogeneous distribution can be with the expert known methods such. B. sonication with ultrasound or Shear and mix in suitable mixing devices such as e.g. B. with stirrers, static or dynamic mixers, d. H. Entry of high shear energies.

The mixture can be prepared by methods known to those skilled in the art, such as Stir or use static or dynamic mixers respectively.

The addition is so slow that always go far de or sufficient mixing of the system can take place, before due to strong concentration inhomogeneities or gradients served the risk of large complex particles failing arises.

In principle, the above-mentioned polyes are used as starting materials electrolytes and the above-mentioned ionic fluorinated ten  side suitable. They are preferably in alcoholic solution used.

The polyelectrolyte should preferably be introduced in such a way that he as high a charge as possible in the resulting complex Polyion educates; this can occur when using ionic flu orated surfactants in salt form z. B. done in that the Polyelectrol solution is at least partially neutralized. That be indicates that e.g. B. in polycations such. B. Polyethyleniminpo Lyations, possibly the pH z. B. with mineral acids such as B. HCl should be reduced. This measure is e.g. B. in In the case of polycations not necessary if the inserted set surfactants are sufficiently strong acids. The same applies for polyanions, the appropriate measures are the subject man known.

The polyelectrolytes used and the surfactants used as free acids or bases.

The solutions of the ionic fluorinated surfactants can still Co contain surfactants, e.g. B. the solution behavior of the ionic improve fluorinated surfactants. This can be particularly the case with high heren concentrations of the ionic surfactant or preferred his. Preference is given to using cosurfactants which alone only weak or, particularly preferably none, surfactant action to have.

The object is further achieved by a method for producing a mixture of complex compositions with waxes, which contains the steps:
Preparation of a complex composition according to one of the above processes,
Dissolving or emulsifying the waxes in a suitable non-polar solvent,
Mixing the complex composition with the wax composition.

Suitable solvents are known to the person skilled in the art, e.g. B. Mixing gene from aliphatic and cycloaliphatic hydrocarbon fen, such as B. Petroleum ether.

Milky, partly stable, partly to pha develop Senseparation-prone emulsions that after homogenization by shaking, directly as a coating composition can be placed.

If a wax emulsion is used, the addition of is often effective Complex composition stabilizing on the wax emulsion.

The object is further achieved by a method for producing a mixture of complex composition with clusters, which contains the steps:
Preparation of a complex composition according to one of the above processes,
Dissolving or emulsifying the klister in a suitable non-polar solvent,
Mixing the complex composition with the wax composition.

Milky, partly stable, partly to pha develop Senseparation-prone emulsions that after homogenization by shaking, directly as a coating composition can be placed.

Suitable solvents are known to the person skilled in the art, e.g. B. Mixing gene from aliphatic and cycloaliphatic hydrocarbon fen, such as B. Petroleum ether.  

If a klister emulsion is used, the addition is often effective the complex composition stabilizing on the Klisteremul sion.

Fig. 1 shows a diagram in which the results of the same measurements Ver lubricity different beschich Teter skis are shown,

Fig. 2 shows a bar diagram in which the results are shown by comparative measurements of the different gliding be-coated ski,

Fig. 3 shows a bar graph in which the results of comparative measurements of the lubricity of differently coated skis are shown, and

Fig. 4 shows a diagram in which the results of comparison measurements of the lubricity of differently coated skis are shown.

Embodiments example 1  Preparation of a coating composition with a stoichiometry of 1: 1 over precipitation and solution

73 g of a 25% by weight solution of lithium 3 [(1H, 1H, 2H, 2H, fluoroalkyljthio] propionate (Zonyl FSA®, Du- Pont) are diluted to 200 g in deionized water. To this solution are stirred vigorously within 5 min 2 g polyethyleneimine alkoxylated with 10% ethylene oxide, (Lupasol LU209 (94.1%), Mw = 25000 g / mol, BASF AG, Ludwigsha fen) dissolved in 200 g of water and a pH of 4 added drips. After lowering the pH to 2 with hydrochloric acid the complex precipitates. This is filmed and washed thoroughly with deionized water until the conductivity of the wash water is less than 20 mS. On finally the complex is solved as follows: 5% of the  separate dry matter are in 5% glacial acetic acid at a tempe rature of 80 ° C, and made up with 90% isopropanol.

Example 2  Preparation of a coating composition with a stoichiometry of 1: 1 over precipitation and solution

73 g of a 25% by weight solution of lithium 3 [(1H, 1H, 2H, 2H, fluoroalkyl) thio] propionate (zonyl FSA ©, Du- Pont) are diluted to 200 g in deionized water. To this solution are stirred vigorously within 5 min 1.75 g polyethyleneimine (Lupasol WF, Mw = 25000 g / mol, BASF AG, Ludwigshafen) dissolved in 200 g water and a pH of 4 dripped. After increasing the pH to 2 with hydrochloric acid the complex precipitates. This is filmed and washed thoroughly with deionized water until the conductivity of the wash water is less than 20 mS. On finally the complex is solved as follows: 5% of the separate dry matter are in 5% glacial acetic acid at a tempe rature of 80 ° C, and made up with 90% isopropanol.

Example 3  Preparation of a coating composition in Form of a dispersion

0.64 g of the polyelectrolyte Lupasol WF (polyethyleneimine, M _w = 25000 g / mol, BASF AG, Ludwigshafen), made up to 100 g with isopropanol, are introduced. A solution of 3.66 g of Fluowet PL80® (Clariant GmbH, Frankfurt am Main, 80% by weight aqueous solution of a mixture of perfluorinated phosphinic / phosphonic acids), which is made up to 54 g with isopropanol, is added to this solution with vigorous stirring and was homogenized for 2 minutes in an ultrasonic bath, added within 5 minutes. The result is a 2.5% by weight, highly viscous, slightly cloudy dispersion which can already be used for surface coating.

Example 4  Preparation of a mixture of a complex dispersion with waxes

0.52 grams of the polyelectrolyte Lupasol WF (polyethyleneimine, M _W = 25,000 g / mol, BASF AG, Ludwigshafen), made up to 60 g with isopropanol, to be submitted. A solution of 5.49 g of Fluowet PL80® (Clariant GmbH, Frankfurt am Main, 80% by weight aqueous solution of a mixture of perfluorinated phosphinic / phosphonic acids), which is made up to 60 g with isopropanol, is added to this solution with vigorous stirring filled and homogenized for 2 minutes in an ultrasonic bath, added over 5 minutes. A 5% by weight dispersion is formed which is milky.

A second solution is made from 5 g of racing wax P1 (HWK, 84508 Burgkirchen, Germany) with 95 g of petroleum ether 40/60 under Stirring prepared and the dispersion prepared as above mixed in a ratio of 1: 1. There is a 2.5 each % By weight dispersion of wax and complex.

Example 5  Preparation of a mixture of a complex dispersion with klisterns

0.86 g of the polyelectrolyte Polyrnin P (polyethyleneimine, M _w = 750,000 g / mol, BASF AG, Ludwigshafen, Germany), made up to 100 g with isopropanol, are introduced. A solution of 9.15 g of Fluowet PL80® (Clariant GmbH, Frankfurt am Main, 80% by weight aqueous solution of a mixture of perfluorinated phosphinic / phosphonic acids), which is made up to 100 g with isopropanol, is added to this solution with vigorous stirring and homogenized for 2 minutes in an ultrasonic bath, added over 5 minutes. A 5% by weight dispersion is formed which is milky.

A second solution is made from 5 g of the "Black Magic" (START, 158608 Hollola, Finland) with 95 g petroleum ether 40/60  prepared with stirring and the Dis persion mixed in a ratio of 1: 1. One arises in each case 2.5% by weight dispersion of wax and complex.

Example 6 Coating of ski coverings made of polyethylene for Increase in lubricity

The following materials were produced in accordance with the examples described above:

The substances according to the invention were applied with a brush to various test skis (Fischer cross-country ski scating) and dried. The glide of the skis prepared in this way was measured on an approx. 50 m route by time measurement with an optical / electronic timer. Other skis were coated with commercially available products which, according to experts, represent the state of the art and are used in World Cup races. The measurements were repeated four times in order to achieve statistical significance. The mean values of the measured times were then compared. The results of the test series, which were carried out on 4 different days, are shown in FIGS. 1 to 4, with the mean values being normalized by multiplication by 100 and division by a normalization factor which is valid for a series, in order to make it easier to recognize the differences . In Figs. 1 to 3 the results are as Balkendia program, shown in Fig. 9, however, as data points with ge estimated error bars.

The specified comparison waxes are commercially available products from the following companies:

Briko, italy,
Dominator, Velocity Ventures Inc., New York, USA,
Holmenkol, Loba GmbH & Co KG, 71254 Ditzingen, Germany),
Rex, 04300 Tusby, finland,
Swix, Lillehammer, Norway,
TOKO, 9450 Altstätten, Switzerland.

The measurements, the results of which are shown in the figures, were carried out under the conditions given in the following table.

Then the skis coated according to the invention were over a 60 km run by world-class runners. Then The gliding quality was again one of the best products on the market (Cera F from Swix, Lille hammer, Norway). Even after 60 km there was another slightly better effect achieved.

Example 7  Coating of classic cross-country skis on the climb area for reducing the adhesion of snow

The following coating composition was produced:
Material D was prepared analogously to Example 3, but using four times the amount of surfactant and polyelectrolyte.
Material E was also produced analogously to Example 3, except that twice the amount of surfactant and polyelectrolyte was used.

Classic cross-country skis were coated with the substances D and E using brush application in the climbing area. The skis were not polished after drying. The skis were then run over 8 km by an experienced wax technician. The snow temperature was -8 ° C, the air temperature -7 ° C and the relative humidity 71%. The result of the evaluation up to 5 km shows the following table:

The result of the evaluation up to 8 km is shown in the following table:

Claims (19)

1. Coating for skis and snowboards containing polyions at least one polyelectrolyte and to charge the poly Ions of oppositely charged surfactant ions at least one ionic fluorinated surfactant, the polyions and at least some of the surfactant ions in the coating form contained complexes. 2. Use of the coating according to claim 1, as coating device for the running surfaces of skis and snowboards. 3. Composition containing polyions of at least one Po lyelectrolytes and to charge the polyions sets charged surfactant ions of at least one ionic flu orated surfactant, the polyions and at least one Part of the surfactant ions contained in the coating Form plexes, as well as fluorinated organic solvents. 4. Composition containing polyions of at least one Po lyelectrolytes and to charge the polyions sets charged surfactant ions of at least one ionic flu orated surfactant, the polyions and at least one Part of the surfactant ions contained in the coating Form plexes, as well as organic solvents and anions ner acid or cations of a base. 5. Composition containing dispersion particles Polyions of at least one polyelectrolyte and for charging of the oppositely charged surfactant ions least an ionic fluorinated surfactant, the poly ions and at least some of the surfactant ions in the loading form complexes, as well as alcohols.   6. Composition according to claim 3, 4 or 5, characterized draws, that the weight fraction of the complexes is between 0.3 and 10 % By weight. 7. Composition according to claim 6, characterized in that the weight fraction of the complexes between 0.6 and 2.5 % By weight. 8. Composition according to one of claims 5, 6 or 7, because characterized in that the alcohols are not fluorinated are. 9. Composition according to one of claims 4 to 8, including tend aliphatic alcohols. 10. The composition according to claim 9, containing ethanol. 11. The composition according to claim 9, containing isopropyl alcohol fetch 12. The composition according to any one of claims 3 to 11 tend waxes. 13. The composition according to claim 12, containing fluorinated Waxes. 14. Composition according to one of claims 3 to 12, containing klister. 15. A method for producing a coating composition comprising the steps:

• Slow addition of an aqueous polyelectrolyte solution into an aqueous fluorosurfactant solution,
• - filtering off the precipitate that forms,
• Drying the filtered precipitate if the organic solvent of the coating composition to be formed does not mix with water,
• Dissolving the solid formed in an acidic or alkaline liquid,
• - Mix in the organic solvent.

16. A process for the preparation of a coating composition comprising the steps:

• - Slow addition of an aqueous fluorosurfactant solution to an aqueous polyelectrolyte solution with simultaneous strong mixing,
• - filtering off the precipitate that forms,
• Drying the filtered precipitate if the organic solvent of the coating composition to be formed does not mix with water,
• Dissolving the solid formed in an acidic or alkaline liquid,
• - Mix in the organic solvent.

17. The method according to claim 15 or 16, characterized in net that the filter cake before drying or if the This is not necessary before dissolving with demineralized water is washed. 18. A process for the preparation of a coating composition based on a polyelectrolyte which is not quaternized as the base, comprising the steps:

• - preparation of a homogeneous mixture of polyelectrolyte solution and fluorosurfactant solution,
• Addition of a suitable acid, so that the ion activity of the polyelectrolyte is increased to such an extent that a precipitate with the desired stoichiometry fails,
• - filtering off the precipitate that forms,
• Drying the filtered precipitate if the organic solvent of the coating composition to be formed does not mix with water,
• Dissolving the solid formed in an acidic or alkaline liquid,
• - Mix in the organic solvent.

19. A process for the preparation of a coating composition in the form of a dispersion, starting from a polyelectrolyte soluble in at least one alcohol and each containing fluorosurfactant soluble in at least one alcohol, comprising the steps:

• - Submitting the polyelectrolyte in a suitable alcoholic solution,
• - Slow addition of a well homogenized solution of the fluorosurfactant or fluorosurfactants with strong mixing.