Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/58—Metal-containing linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
  • C09D5/1637—Macromolecular compounds

Definitions

• Inorganic coating composition a process for its production and its use
• the present invention relates to inorganic coating compositions based on cyclic carbosiloxanes, inorganic polycondensates and ⁇ , ⁇ -functional linear oligosiloxanes and a process for their preparation and their use.
• Silicone resin varnishes which are composed essentially of statistically distributed T, D, M and partly also from Q units, are produced from the corresponding chlorosilanes via direct or indirect hydrolysis.
• the hydrolysis of the silanes to oligosiloxanes is followed by the condensation to organopolysiloxane resins, the so-called "bodying".
• bodying The production processes are described, for example, in W. Noll, Chemistry and Technology of Silicones, VCH-Verlag, 1968 and in Chemistry in Our Time, 23, (1989 ), 86-99, which also summarizes the technology and properties of silicone resins.
• pure methyl silicone resins can be used to produce hard, mechanically resilient, but brittle coatings.
• silicone resin paints must be used at temperatures of 180 to 230 ° C can be branded.
• sol-gel process uses hydrolysis and polycondensation of alkoxysilanes without subsequent "bodying" to produce an oligosiloxane sol.
• the sols have a much larger number of reactive SiOH or SiOR groups and have a high number of them Q units have a higher crosslink density.
• Sol-gel coating systems have the well-known positive properties of silicone resins, such as high temperature resistance, resistance to solvents and many service fluids, non-stick effect and weather stability. Vitat and crosslinking density, sol-gel coatings can be hardened at lower temperatures of approx. 80 ° to approx. 130 ° C and exceed silicone resin coatings in hardness and mechanical stability
• condensation-crosslinking sol-gel coating systems are their low solids content or their high VOC content.
• the solids content of sol-gel lacquers is generally between 10 and 50% by weight, mostly at a maximum of 30% by weight, from the coating industry however, increasingly, partly due to legal regulations, the reduction of volatile organic compounds (VOC) is required.
• VOC volatile organic compounds
• Another disadvantage of the existing sol-gel coating systems is their tendency to crack due to low flexibility. They can therefore only be applied in thin layers of a few ⁇ m for Many applications, for example as graffiti protection for buildings as well as for large and rail vehicles, it would also be advantageous if inorganic sol-gel systems already had their properties
• the object of the present invention was therefore to provide an inorganic sol-gel coating which does not have the disadvantages described above.
• a further object of the invention was then to provide a suitable process for producing the coating composition according to the invention
• the invention is based on the surprising observation that the combination of cyclic carbosilanes and / or carbosiloxanes, inorganic polycondensates and ⁇ , ⁇ -functional linear ohgosiloxanes provides inorganic coating compositions which fulfill the object on which the invention is based / composition has a solvent content of a maximum of 0% by weight, preferably of a maximum of 40% by weight.
• a solvent content of a maximum of 0% by weight, preferably of a maximum of 40% by weight.
• R 1 Ci-Cig-alkyl and / or C 6 -C 2 o-aryl, where R 1 can be the same or different within the molecule,
• X is a radical selected from the group OH, -C-alkoxy, C ⁇ -C 20 -
• W is either a linear, cyclic or branched silane or siloxane
• Y is a hydrolyzable group, preferably Q - C 8 alkoxy or C 2 -
• a 0 to 3 preferably 0 or 1
• R is alkyl or alkenyl, where R can be the same or different within the molecule.
• c 1 to 60 preferably 3 to 25.
• Catalysts selected from the group of acidic, basic or metal catalysts, preferably from the group of acids, such as hydrochloric acid, Schvve- Feic acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acetic acid or formic acid,
• acids such as hydrochloric acid, Schvve- Feic acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acetic acid or formic acid
• Multifunctional carbosilanes or siloxanes of the general formula (I) suitable for the purposes of the invention are silanes of the general formula (IV)
• R 1 Ci - C ⁇ 8 alkyl and / or C 6 - C 20 aryl, where R 1 may be the same or different within the molecule,
• X is a radical selected from the group OH, Ci - C 4 alkoxy, C - C 2 aryloxy,
• C () acyloxy preferably OH, methoxy or ethoxy
• multifunctional carbosilanes and / or siloxanes of the general formula (I) are siloxanes in which W is composed of at least two building blocks, selected from monofunctional units M or difunctional units D and to a small extent additionally trifunctional units T or tetrafunctional units Q and / or their condensation and / or (partial) condensation products.
• the siloxanes according to the invention preferably have a number average molecular weight between 300 and 5000.
• the multifunctional carbosilane and or -siloxane of the general formula (I) is a cyclic siloxane of the general formula (V)
• X is a radical selected from the group OH, Ci - C 4 alkoxy, C ( , - C 2 n-aryloxv, Ci - C (, - acyloxy, preferably OH, methoxy or ethoxy, 3 to 6, preferably 4
• the multifunctional carbosilane and / or siloxane is a compound of the formula (VI) and / or (VII) or its (partial) condensation product.
• d is 3 to 6, preferably 4.
• Condensation or (partial) condensation products are to be understood as oligomers or polymers which are formed from at least two molecules of the general formula (I) after optionally hydrolysis and subsequent condensation of group X to form an Si-O-Si bond.
• a plurality of multifunctional carbosilanes and / or siloxanes of the general formula (I) can also be present in the coating composition according to the invention.
• Hydrolyzable compounds of the general formula (II) are preferably alkoxysilanes R ⁇ d S ⁇ (Y) (h ⁇ (with a preferably 0 or 1 and R ⁇ , Y the meaning given above tion) or their mixtures.
• Particularly preferred alkoxysilanes are tetraethoxysilane, methyltriethoxysilane and / or phenyltriethoxysilane.
• Preferred ⁇ , ⁇ -functional linear oligosiloxanes of the general formula (III) are hydroxy-terminated polydimethylsiloxanes, those with an OH content of 0.8 to 9% being particularly preferred.
• the present invention also relates to polycondensation products of hydrolyzable compounds of the general formula (II) and an ⁇ , ⁇ -functional linear oligosiloxane of the general formula (III).
• preferred hydrolyzable compounds of the general formula (II) are alkoxysilanes R a Si (Y) (t>) (with a preferably 0 or 1 and R, Y have the meaning given above) or mixtures thereof, very particularly preferably used tetraethoxysilane. It is also possible to add only a part of the ⁇ , ⁇ -functional linear oligosiloxane contained in the coating composition to the
• the polycondensation products contained in the coating composition according to the invention have a solids content of at least 40% by weight, preferably of at least 50% by weight.
• OH-functional solvents with a boiling point greater than 110 ° C. and a flash point greater than 30 ° C. are preferred as solvents.
• Suitable solvents are, for example, 1-butanol, 1-pentanol, 2-pentanol, 1-methoxy-2-propanol or diacetone alcohol.
• Suitable catalysts are, for example, organic metal compounds, such as carboxylic acid salts, alcoholates and phenates, complex compounds of chelate character, basic catalysts, such as alkali metal hydroxides, amines, alkali metal silanolates, quaternary ammonium hydroxides and acidic catalysts.
• Acidic catalysts can be Lewis acids or protonic acids, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acetic acid or formic acid.
• the catalyst is preferably an acid, particularly preferably ⁇ -toluenesulfonic acid.
• the catalyst can also be used as a solution, preferably in the same solvent that is already contained in the composition.
• inorganic fillers or inorganic nanoparticles can be added as component (V). It is known to the person skilled in the art that by adding inorganic nanoparticles, e.g. Metal or semimetal oxides or oxide hydrates of the elements Si, Al or Ti improve the mechanical properties of coatings.
• component (VI) in coating technology can be component
• auxiliaries customary in coating technology are added.
• Typical auxiliaries are, for example, inorganic and / or organic pigments, paint additives, such as dispersants, leveling agents, thickeners, defoamers and other auxiliaries, adhesives, fungicides, bactericides, stabilizers or inhibitors.
• conventional auxiliaries also include the release or slip additives known from the prior art. These are generally hydrophobic, non-functional additives that stick to the coating during the service life
• Suitable release or slip additives are, for example, silicone oils, organic oils, waxes, paraffins or petroleum jelly. A mixture of the aforementioned components can of course also be added.
• the coating composition according to the invention contains
• Amounts customary in coating technology mean a ratio of components (V) and (VI) to components (I) to (IV) of not more than 1: 1.
• An advantage of the coating composition according to the invention is that the components (I) to (IV) at least contained in the coating composition can be mixed with one another in any ratio within the limits according to the invention.
• the properties of the coatings that can be produced from the coating composition can thus be easily adapted to the respective requirements by varying the individual components.
• By increasing the proportion of ⁇ , ⁇ -functional linear oligosiloxane, flexibility and hydrophobicity can be increased.
• An increased proportion of polycondensation products of hydrolyzable compounds of the general formula (II) improves the mechanical properties of the coating.
• components (I), (II) and (III) of the coating composition contain hydrolyzable and condensable groups, the components in the fully cured coating differ in their structure and their percentage from the coating additive used to produce the coating. composition.
• Another object of the invention is a process for the preparation of the coating composition according to the invention, characterized in that in the first process step by means of a sol-gel process, a polycondensation product of hydrolyzable compounds of the general formula (II) and optionally ⁇ , ⁇ -functional linear oligosiloxane general formula (III) in an OH-functional solvent with a solids content of at least 40% by weight, preferably of at least 50% by weight.
• the polycondensation product produced from component (II) and optionally (III) with components (I) optionally (III) and (IV) and the other components (V) and (VI) are stirred homogeneously.
• One synthesis route runs via hydrogen-functional silanes or siloxanes as the starting compound W.
• vinyl-functional silanes or siloxanes serve as the starting compound W.
• Suitable hydrogen- or vinyl-functional silanes and siloxanes are commercially available or can be prepared from the suitable silanes or siloxanes by direct or indirect hydrolysis or equilibration processes known in silicone technology .
• the [(CH) rn SiR 1 n X ( - n) ] group according to general formula (I) is added to W under platinum catalysis as a corresponding alkenyl-functional silane.
• a vinyl-functional silane or siloxane serves as the starting compound W, a corresponding hydrogen silane is used.
• radical X can then be introduced in a further process step by a direct or indirect hydrolysis known to the person skilled in the art.
• the principle of the synthesis is explained in more detail in EP-A 866086, WO 94/06 807 and DE-A 196 03 241.
• multifunctional carbosilanes of the general formula (IV) is described in EP-A 743313
• multifunctional carbosiloxanes of the formulas (V) and (VI) are preferably according to those in EP-A 866086, DE-A 196 03 241 and WO / 9S '52992 available procedures described.
• the polycondensation product according to the invention is prepared from hydrolyzable compounds of the general formula (II) in such a way that in the first
• the hydrolyzable compounds of the general formula (II) are hydrolyzed and condensed by adding water, catalyst and optionally solvent in a manner customary in sol-gel technology.
• the molar ratio of added water to hydrolyzable groups Y is in the range from 0.3 1 to 0.7 1, preferably in the range from 0.45 1 to 0.55 1, as the catalyst, based on the reaction mixture, preferably between 250 and 1000 ppm of an acid are added.
• the polycondensation product is neutralized with a base and an OH-functional solvent with a boiling point greater than 110 ° C. and a flash point of at least 30 ° C.
• Suitable solvents are, for example, 1-butanol, 1-pentanol, 2-pentanol, 1-
• Methoxy-2-propanol or diacetone alcohol is then distilled to the desired solids content of at least 40% by weight, preferably at least 50% by weight.
• the salt formed by the neutralization is filtered off
• Another embodiment of the process according to the invention is the production of a polycondensation product from preferably alkoxysilanes R a S ⁇ (Y) ( b) (with a preferably 0 or 1 and R, Y have the meaning given above) or mixtures thereof, very particularly preferably from tetraethoxysilane and an ⁇ , ⁇ -functional linear oligosiloxane.
• R a S ⁇ (Y) ( b) with a preferably 0 or 1 and R, Y have the meaning given above
• R, Y have the meaning given above
• Oligosiloxane used in the preparation of the polycondensation product It is advantageous to thin the mixture of alkoxysilanes R d S ⁇ (Y) (b) and ⁇ , ⁇ > -functional linear oligosiloxane with a solvent, preferably with ethanol
• a solvent preferably with ethanol
• a storage-stable two-component formulation is prepared from components (I) to (IV) according to the invention and optionally further components (V) and / or (VI).
• the multifunctional carbosilane and / or siloxane of the general formula (I) is a cyclic siloxane of the general formula (V) in which X represents a methoxy or ethoxy group.
• the invention furthermore relates to the use of the coating composition according to the invention for the production of coatings on inorganic or organic materials or objects.
• the invention also relates to non-stick layers obtained by applying the coating composition according to the invention to inorganic or organic materials or objects in order to effectively protect them from dirt, graffiti or marine growth.
• Suitable intermediate layers are, for example, those described in the teaching of DE-A 197 15 427 water 2-component polyurethane binder
• coating composition already cures at room temperature, materials or objects that cannot or must not be exposed to an elevated temperature can also be coated
• the coating composition according to the invention as an anti-rust coating or when used as an anti-graffiti coating not applied at the factory.
• the coating can also be forced hard at elevated temperature
• the surface to be protected is very hydrophobic and has good non-stick properties. This means that on the one hand the graffiti is not or only poorly wetted and thus loses its attractiveness for the sprayer, and secondly with both graffiti cleaning agents and water using a High-pressure cleaner can be removed without residue.
• the surfaces coated with the coating compositions according to the invention are also effectively protected against damage by solvents, which extends the maintenance interval
• the coating composition can also be used in many areas in which the VOC guidelines limit the solvent content.
• the application of the coating composition according to the invention can be carried out according to the usual methods, such as spraying, Sticks, diving, flooding, spinning or squeegees
• the present invention is to be explained in more detail with the aid of the following examples.
• Example 2 The same procedure as in Example 1 with the difference that n-pentanol is added after the neutralization.
• the solids content of the clear polycondensation product is 48% by weight.
• the polycondensation product is several
• a mixture of 1000 g (4.8 mol) of tetraethoxysilane and 480 g of an ⁇ , ⁇ -hydroxy-functional polydimefhylsiloxane with an OH content of approx. 7.5% are dissolved in 400 g of ethanol and by adding 620 ppm of HC1 and 173 g (9.6 mol) H 2 O hydrolyzed and precondensed.
• the initially cloudy reaction mixture warms up from room temperature to approx. 65 ° C within a few minutes.
• the mixture is allowed to cool to room temperature with stirring, the added acid is neutralized, 760 g of n-butanol are added and the mixture is stirred at 70 ° C. for a further hour.
• Solvent is distilled off at reduced pressure up to 70 ° C. After filtration, the polycondensation product is obtained as a clear liquid with a solids content of 50.7% by weight.
• the polycondensation product can be stored for several months at room temperature.
• Example 6 The same procedure as in Example 6. However, 53.2% by weight of the ethoxy-functional siloxane, 12.8% by weight of a polycondensation product from Example 1, 10.6% by weight of an ⁇ -hydroxy-functional polydimethylsiloxane an OH content of approx. 7.5%, 1.0% by weight 3-mercaptopropyltriethoxysilane, 0.3% by weight Byk 306, 3.2% by weight n-butanol and 18.9% by weight % of an approx. 2% solution of para-toluenesulfonic acid mixed in 2-ethylhexanol. The mixture has a solids content of 54% by weight.
• Example 6 The same procedure as in Example 6. However, 53.7% by weight of the clhoxy-functional siloxane, 40.3% by weight polycondensation product from Examples 5 and 6 were obtained
• Gevv.- an approx. 2% solution of para-toluenesulfonic acid in n-butanol mixed together
• the mixture has a solvent content of 26% by weight and a solids content of 55.5% by weight.
• the coating is clear.
• the coating is not wetted by a permanent marker from Edding (Edding 850). The marker can be used 24 hours after application Remove a cloth without the aid of cleaning agents
• Example 6 The same procedure as in Example 6, but 57.4% by weight of the ethoxy-functional siloxane, 30.9% by weight of polycondensation product from Example 5 and
• Example 6 The same procedure as in Example 6, but 22.5% by weight of the ethoxy-functional siloxane, 67.4% by weight polycondensation product from Example 5 and 10.1% by weight of an approx. 2% solution of para-toluenesulfonic acid in n- Butanol mixed together
• the mixture has a solvent content of 44% by weight and a solids content of 49% by weight.
• the coating is clean. From a permanent marker from Edding (Edding 850) and the coating is not wetted
• Example 6 The same procedure as in Example 6. However, 48.2% by weight of the ethoxy-functional siloxane, 1 1.6% by weight polycondensation product from Example 5, 38.6% by weight of an ⁇ , ⁇ -hydroxy-functional polydimethylsiloxane with an OH
• Example 6 The same procedure as in Example 6. However, 30.8% by weight of the ethoxy-functional siloxane, 55.4% by weight polycondensation product from Example 1 and 13.8% by weight of an approximately 2% solution of para-toluenesulfonic acid mixed together in n-butanol. The mixture has a solvent content of 41.5% by weight and a solids content of 48% by weight. A clear crack formation can be observed 24 hours after application.
• Example 6 The same procedure as Example 6, but instead of an ⁇ , o) -hyd ⁇ oxy- functional polydimethylsiloxane with an OH content of about 7.5 " ( > the dykes Amount of an ⁇ , ⁇ -hydroxy-functional polydimethylsiloxane with an OH content of approx. 0.1% is used.
• the mixture is incompatible.
• a high-quality aqueous 2K PUR topcoat is used for comparison, which is used in large-scale and rail vehicle painting.
• Polyol 43.3% by weight Bayhydrol VPLS 2235/1 2.
• Polyisocyanate 13.3% by weight Bayhydur VPLS 2319
• Re 2 polyisocyanate: hydrophilized, aliphatic polyisocyanate based on hexamethylene diisocyanate,
• Irgazinrot BO Ciba Specialty Chemicals / Basel
• Paliogen orange L 2930 HD BASF AG / Ludwigshafen
• the coating composition from Example 7 shows a very long processing time compared to standard coating systems for large and rail vehicles.
• the coating composition from Example 7 shows very rapid drying in comparison to standard coating systems for large and rail vehicles.
• Example 7 The paints formulated according to Example 7 and Comparative Example 6 are applied by means of air pressure spray application (nozzle 1.3 mm diameter, spray pressure 3.5 bar) to glass plates or steel sheets which are coated with a primer or a solid-color lacquer.
• the coating composition from Example 7 can effectively protect the surface to be protected against damage by solvents
• Alkyd spray paint, acrylic spray paint and felt-tip pen are applied to the substrates coated in accordance with Example 14 and then stored for 48 hours at 50 ° C. in order to simulate aging of the graffiti

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Paints Or Removers (AREA)
• Silicon Polymers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Aftertreatments Of Artificial And Natural Stones (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)

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