Silicone resin compositions which can be cured at room temperature

Abstract

The present invention relates to compositions comprising a binder which comprises at least one alkoxy-functional polysiloxane, and at least one crosslinking catalyst, the crosslinking catalyst representing a silicon-containing guanidine compound, and also, optionally, an alkoxysilane as crosslinker.

Claims

1. A composition, comprising: (a) a binder comprising at least one alkoxy-functional polysiloxane; and (b) at least one crosslinking catalyst which is a silicon-containing guanidine moiety of formula (IVa), (IVb) or (IVc): ##STR00003## wherein: R.sup.3 are divalent radicals which, independently of one another, are identical or different linear or branched hydrocarbon radicals containing 1 to 50 carbon atoms, and which may be interrupted by at least one heteroatom, and/or may be substituted by at least one hydroxyl radical, at least one amino radical, or a mixture thereof; R.sup.11, R.sup.12, R.sup.21, R.sup.22 and R.sup.31 independently of one another, are identical or different and are hydrogen, linear or branched or cyclic hydrocarbons containing 1 to 15 carbon atoms, it being possible for the hydrocarbons also to contain 1 or 2 heteroatoms; a silicon compound is bonded to R.sup.3 via a Si atom, wherein component b) further comprises at least one crosslinking catalyst of the formula (I):
M.sub.aM.sup.G.sub.bD.sub.cD.sup.G.sub.dT.sub.eQ.sub.f  (I), wherein: a=0 to 10, b=0 to 10, c=0 to 350, d=0 to 50, e=0 to 50, f=0 to 10, where the sum of the indices b and d is greater than or equal to 1 to 20, with the proviso that when the index a is 2 and at the same time the sum of the indices b, c, e and f is zero, the index d is other than 1, M=[R.sub.3SiO.sub.1/2] M.sup.G=[R.sup.GR .sub.2SiO.sub.1/2], D=[R.sub.2SiO.sub.2/2], D.sup.G=[R.sup.G.sub.2SiO.sub.2/2], T=[RSiO.sub.3/2], Q=[SiO.sub.4/2], R are, independently of one another, identical or different and are OR.sup.a groups and/or linear or branched, saturated or else mono- or polyunsaturated hydrocarbon radicals, which may be interrupted by heteroatoms and/or may be substituted one or more times by hydroxyl, amino, carboxyl or aryl radicals, R.sup.a is identical or different and is hydrogen and/or alkyl groups having 1 to 12 carbon atoms, R.sup.G is a radical containing guanidine groups and of the formula (IVa), (IVb) or (IVc), the tautomers and/or salts thereof, ##STR00004## R.sup.3 are divalent radicals which, independently of one another, are identical or different, linear or branched hydrocarbon radicals containing 1 to 50 carbon atoms, and may be interrupted by heteroatoms, and R.sup.11, R.sup.12, R.sup.21, R.sup.22 and R.sup.31 are, independently of one another, identical or different and are hydrogen, linear or branched or cyclic hydrocarbons containing 1 to 15 carbon atoms, it being possible for the hydrocarbons also to contain 1 or 2 heteroatoms, wherein the alkoxy-functional polysiloxane of component (a) satisfies the general formula (II):
R.sub.aSi(OR′).sub.bO.sub.(4-a-b)/2  (II), wherein: a and b independently of one another are greater than 0 to less than 2, R are, independently of one another, identical or different, linear or branched, saturated or else mono- or polyunsaturated or aromatic hydrocarbon radicals, and R′ is an alkyl group consisting of 1 to 8 carbon atoms.

2. The composition of claim 1, further comprising: (c) an alkoxysilane as a crosslinker component.

3. The composition according to claim 2, wherein the alkoxysilane (c) is a silane of the formula (III):
R.sub.aSi(OR′).sub.b  (III), wherein: a and b independently of one another are greater than 0 to less than 2, and the sum of a+b is 4, R is an alkyl group or cycloalkyl group consisting of 1 to 8 carbon atoms, or an aromatic moiety having 6 to 20 carbon atoms, and R′ is an alkyl group consisting of 1 to 8 carbon atoms.

4. The composition of claim 1, further comprising at least one additive.

5. A coating material, comprising the composition of claim 1.

6. A method, comprising curing the composition of claim 1 at room temperature and without addition of a metal-containing catalyst.

7. The method of claim 6, wherein the curing occurs in the presence of moisture.

Description

EXAMPLES

General Methods and Materials

(1) TABLE-US-00001 Hexamethyldisiloxane, 98% Cat. No. AB111176 ABCR, Karlsruhe Decamethylcyclopentasiloxane, 97% Cat. No. AB111012 ABCR, Karlsruhe Phenylmethylcyclosiloxane, 95% Cat. No. AB153228 ABCR, Karlsruhe Allyl glycidyl ether (AGE) Cat. No. A32608 Sigma-Aldrich Chemie GmbH, Munich Bis(aminopropyl)tetramethyldisiloxane, 97% Cat. No. AB110832 ABCR, Karlsruhe N-Ethylmethallylamine (NEMALA), 98% Cat. No. 291439 Sigma-Aldrich Chemie GmbH, Munich Trifluoromethanesulphonic acid, >99% Cat. No. 347817 Sigma-Aldrich Chemie GmbH, Munich 1,1,3,3-Tetramethylguanidine (TMG), 99% Cat. No. 241768 Sigma-Aldrich Chemie GmbH, Munich Tetramethylammonium hydroxide*5H.sub.2O, Cat. No. T7505 Sigma-Aldrich Chemie >97% GmbH, Munich Butyl titanate TYZOR ® TBT Dorf Ketal B. V., Eindhoven, Netherlands Dioctyltin diketonate TIB KAT ® 223 TIB Chemicals, Mannheim Karstedt catalyst preparation, 1% Pt.sup.0 in Evonik Industries AG, decamethylcyclopentasiloxane Essen Lewatit ® K 2621 LANXESS Deutschland GmbH, Leverkusen Dynasylan ® 1505 Evonik Industries AG N,N-Dicyclohexylcarbodiimide (DCC), 99% Cat. No. D80002 Sigma-Aldrich Chemie GmbH, Munich Dynasylan ® 9165, Evonik Industries AG Phenyltrimethoxysilane, PTMS, >98% Dynasylan ® MTMS, Evonik Industries AG Methyltriethoxysilane, >98% Dynasylan ® 9265 Evonik Industries AG Phenyltriethoxysilane, PTEOS, >97% Dynasylan ® A, Evonik Industries AG Tetraethoxysilane Dynasylan PTEO, Evonik Propyltriethoxysilane Phenyltrichlorosilane, PTS Wacker Dow Corning Methyltrichlorosilane, MTS Wacker Dow Corning Decamethylcyclopentasiloxane (D5) Dow Corning Dow Corning 245 Fluid
Spectroscopic Analyses:

(2) The recording and interpretation of NMR spectra is known to the skilled person. References include the book “NMR Spectra of Polymers and Polymer Additives”, A. Brandolini and D. Hills, 2000, Marcel Dekker, Inc. The spectra were recorded at room temperature with a Bruker Spectrospin spectrometer, with measurement frequencies when recording the proton spectra of 399.9 MHz, when recording the .sup.13C spectra of 100.6 MHz and when recording the .sup.29Si spectra of 79.5 MHz. Owing to the basicity of the guanidinosiloxanes prepared, the use of chlorinated deuteriated solvents was avoided, and instead acetone-d.sub.6 or methanol-d.sub.4 (Sigma-Aldrich) was used.

(3) The guanidines were identified by monitoring the formation of product in the .sup.13C NMR. Thus, for example, the signal of the carbodiimide carbon (RN═C═NR) is found at .delta.=140 ppm and the signal of the guanidine group, depending on the guanidine substitution pattern HRN—C(═NR)—NRH, is found at .delta.=150-160 ppm. Reference may be made again at this point to the publication by Xuehua Zhu, Zhu Du, Fan Xu and Qi Shen (J. Org. Chem. 2009, 74, 6347-6349) and to the textbooks by Frederick Kurzer, K. Douragh-Zader—“Advances in the Chemistry of Carbodiimides” (Chemical Reviews, Vol. 67, No. 2, 1967, p. 99 ff.) and Henri Ulrich—“Chemistry and Technology of Carbodiimides” (John Wiley & Sons Ltd., ISBN 978-O-470-06510-5, 2007).

(4) Determination of Total Nitrogen Content:

(5) Basic nitrogen was determined by potentiometric titration with perchloric acid in a non-aqueous medium.

(6) Determination of Relative Molar Mass of a Polymer Sample by Gel Permeation Chromatography (GPC):

(7) The gel permeation chromatography analyses (GPC) took place with a Hewlett-Packard 1100 instrument, using an SDV column combination (1000/10 000 Å, each 65 cm, internal diameter 0.8 cm, temperature 30° C.), THF as mobile phase with a flow rate of 1 ml/min and with an RI detector (Hewlett-Packard). The system was calibrated against a polystyrene standard in the 162-2 520 000 g/mol range.

(8) Drying Time Measurements:

(9) A suitable means of assessing the catalytic activity of catalysts in a binder is to determine the drying time using a Drying Recorder. A test method of this kind is described by ASTM D5895. In analogy to this test method, drying time measurements were conducted using a BK3 Drying Recorder (The Mickle Laboratory Engineering Co. Ltd., Goose Green, Gomshall, Guildford, Surrey GU5 9LJ, UK). In this procedure, binder films were applied to standard glass strips (30×2.5 cm×2 mm) using a four-way bar coater (Erichsen Model 360, wet film thickness 80 μm). Beforehand, the standard glass strips were freed from adhering dust, dirt and grease with acetone and subsequently with an ethanol/DI water mixture. Using a lever on the reverse, the slide was then shifted leftwards into the start position. The scoring scribes were then folded down onto the sample glass plates. The tests were conducted at 23° C. and a RM of 30%. The test duration was set to 6, 12 or 24 hours, and measurement was commenced. After the end of the test duration, the scoring scribes were folded up and the glass plates were removed from assessment. The instants of initial drying and volume drying were read off using the associated timescale.

(10) Inert Method:

(11) Under “inert” conditions is meant that the gas space within the apparatus is filled with an inert gas, e.g. nitrogen or argon. This is achieved by the flooding of the apparatus, with a gentle inert gas stream ensuring inert conditions.

Example 1: Synthesis Examples

(12) S1 (E6): Preparation of an aminopropylmethyldimethoxysilane Condensate

(13) A 250 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 100 g (520 mmol) of aminopropylmethyldiethoxysilane (Dynasilan® 1505) and this initial charge was heated to 80° C. Then 18.8 g (1.04 mol) of DI water were added in portions and the mixture was maintained at 75-85° C. for two hours. After the end of hydrolysis, the mixture was concentrated on a rotary evaporator at 80° C. and 10-25 mbar. This gave a clear product, with a viscosity much higher than that of the reactant, of the general formula HO—[Si.sup.(CH2)3NH2Me].sub.n—OH with n=11-16.

(14) S2 (E1): Preparation of a Linear Aminosiloxane by Equilibration of a Condensate Prepared According to S1 with HMDS

(15) A 250 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 75.1 g of a condensate according to S1 having a nitrogen value of N.sub.tot.=11.5 wt % and a viscosity of 807 mPas (Brookfield), and 74.9 g of hexamethyldisiloxane were added. With stirring of the reaction mixture, 80 mg (=0.05 wt %) of tetramethylammonium hydroxide were then added, and the mixture was heated to 90° C. After an hour, the two-phase reaction mixture, which was turbid and colourless, became homogeneous and clear, but becomes slightly turbid again over the total reaction time of 6.5 hours. After the end of the reaction time, the catalyst was destroyed on a rotary evaporator at 150° C. and 1 mbar for three hours. The fraction of volatile constituents found in this case was 31.8 wt %. .sup.29Si NMR analysis of the end product confirmed the structure of M—[D.sup.(CH2)3NH2].sub.3.3—M, and a nitrogen value of N.sub.tot=8.5 wt % was found.

(16) S3 (H1): Hydrosilylation of Allyl Glycidyl Ether (AGE) Over a Pendant Hydrogensiloxane

(17) A 1000 ml multi-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor, dropping funnel and heating hood was charged under inert conditions with 95.4 g (0.84 mol) of allyl glycidyl ether (AGE), and this initial charge was heated to 70° C. Subsequently, in a counter-current stream of nitrogen, 198 mg of a Karstedt catalyst preparation (corresponding to 5 ppm of Pt.sup.0) were added. Then, over the course of 30 minutes, 300 g of a pendant hydrogensiloxane (2.23 mol SiH/kg) were added from a dropping funnel. The dropping rate was regulated so as to achieve an exothermic temperature of not more than 90° C. After three hours, the SiH conversion was found to be 82% by gas volumetry. In order to complete the reaction, a further 20 g (0.18 mol) of allyl glycidyl ether and 99 mg of the Karstedt catalyst preparation (corresponding to 2.5 ppm of Pt.sup.0) were added, and the reaction was carried out to an SiH conversion >99% at 70° C. over a further seven hours. The product obtained was distilled on a rotary evaporator at 130° C. and a pressure <1 mbar for a number of hours. This gave the epoxy-functional siloxane as a clear, pale yellowish liquid. Investigation by means of .sup.29Si NMR confirmed the target structure.

(18) S4 (N1): Ring Opening of Epoxide S3 with Ammonia

(19) The resulting product S3 was subjected in analogy to WO 2011095261 (US 2012/282210) to an epoxidic ring opening by means of ammonia. This was done by taking up 50 g of the epoxysiloxane into 100 g of isopropanol and transferring the mixture to an autoclave tube. Using a mixture of ethanol and dry ice, the outer wall of the autoclave tube was cooled down such that 10.9 g of ammonia were condensed in by simple introduction using a glass frit over 30 minutes. The tube was sealed and was heated at 100° C. for four hours. The isopropanol and excess ammonia were then distilled off on a rotary evaporator within an hour at 60° C. and <1 mbar. Wet-chemical determination of the primary nitrogen value was 2.8 wt %, in agreement with the theoretical value.

(20) S5 (G1): Preparation of a Guanidine by Reaction of Synthesis Product S4

(21) A 250 ml four-necked flask equipped with KPG stirrer, distillation bridge with vacuum attachment, nitrogen blanket, temperature sensor and heating hood was charged under inert conditions with 71.1 g (147.34 mmol/—NH.sub.2) of the amino-functional siloxane from the preliminary stage, and 28.9 g (139.92 mmol) of N,N-dicyclohexylcarbodiimide, and this initial charge was reacted at 90° C. for 10 hours. After the end of the reaction time, all of the volatile constituents were distilled off within an hour at 90° C. and 20 mbar under a diaphragm pump vacuum. Investigation by .sup.29Si and .sup.13C NMR confirmed the target structure of the clear, pale yellowish product.

(22) S6 (H2): Hydrosilylation of Allyl Glycidyl Ether (AGE) Over a Cyclic Hydrogensiloxane

(23) A 1000 ml multi-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor, dropping funnel and heating hood was charged under inert conditions with 93.3 g (0.82 mol) of allyl glycidyl ether (AGE), and this initial charge was heated to 70° C. Subsequently, in a counter-current stream of nitrogen, 197 mg of a Karstedt catalyst preparation (corresponding to 5 ppm of Pt.sup.0) were added. Then, over the course of 30 minutes, 300 g of a cyclic hydrogensiloxane (2.18 mol SiH/kg) were added from a dropping funnel. The dropping rate was regulated so as to achieve an exothermic temperature of not more than 90° C. After three hours, the SiH conversion was found to be 74% by gas volumetry. In order to complete the reaction, a further 19 g (0.17 mol) of allyl glycidyl ether (AGE) and 197 mg of the Karstedt catalyst preparation (corresponding to 5 ppm of Pt.sup.0) were added, and the reaction was carried out to an SiH conversion >99% at 70° C. over a further seven hours. The product obtained was distilled on a rotary evaporator at 100° C. and a pressure 15 mbar for a number of hours. This gave the epoxy-functional siloxane as a clear, pale yellowish liquid. Investigation by means of .sup.29Si NMR confirmed the target structure, with a theoretical epoxy value of 2.79%.

(24) S7 (N2): Ring Opening of Epoxide S6 with Ammonia

(25) The resulting product (S6) was further subjected in analogy to WO 2011095261 (US 2012/282210) to an epoxidic ring opening by means of ammonia. For this purpose, 250 g of the epoxysiloxane (theoretical epoxy value 2.79%) were taken up in 500 g of isopropanol, and transferred to an autoclave tube. Using a mixture of ethanol and dry ice, the outer wall of the autoclave tube was cooled down such that 60 g of ammonia (710% excess) were condensed in by simple introduction using a glass frit over 30 minutes. The tube was closed and heated to 100° C. for four hours, during which a pressure increase up to 22 bar was recorded. After the end of the reaction time, the mixture was cooled to room temperature and the pressure vessel was let down. The isopropanol and excess ammonia were then distilled off on a rotary evaporator within an hour at 60° C. and <1 mbar. Wet-chemical determination of the primary nitrogen value was 2.8 wt %, in agreement with the theoretical value.

(26) S8 (G2): Preparation of a Cyclic Siloxane Having Guanidine Groups

(27) A 250 ml four-necked flask equipped with KPG stirrer, distillation bridge with vacuum attachment, nitrogen blanket, temperature sensor and heating hood was charged under inert conditions with 75.7 g (156.84 mmol/—NH.sub.2) of the amino-functional siloxane from the preliminary stage, and 24.3 g (117.67 mmol) of N,N-dicyclohexylcarbodiimide, and this initial charge was reacted at 90° C. for 10 hours. After the end of the reaction time, all of the volatile constituents were distilled off within an hour at 90° C. and 20 mbar under a diaphragm pump vacuum. Investigation by .sup.29Si and .sup.13C NMR confirmed the target structure of the clear, pale orange-coloured product.

(28) S9 (E3): Equilibration of the Condensate S1 to Form a Cyclic Aminopropylsiloxane

(29) A 1000 ml multi-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor, dropping funnel and heating hood was charged under inert conditions with 61.2 g (522 mmol/—NH.sub.2) of a condensate prepared according to S1, and with 38.8 g (523 mmol/D) of octanomethylcyclotetrasiloxane, 400 g of xylene and 2.5 g of tetrametylammonium hydroxide*pentahydrate (TMAH*5H.sub.2O) were added. The reaction mixture was heated at 90° C. for 6 hours and then heated at reflux for eight hours to destroy the catalyst. The continuous reduction in amine level during this procedure was measured using a pH paper in a stream of nitrogen. When destruction of the catalyst was at an end, the solvent was removed on a rotary evaporator and intensive distillation took place on the rotary evaporator at 100° C. and <1 mbar for one hour. The slightly turbid product, finally, was filtered through a fluted filter, giving a clear and colourless product.

(30) S10 (G3): Preparation of a Cyclic Guanidine by Reaction of a Cyclic Aminosiloxane with DCC

(31) A 250 ml multi-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 80 g of the cyclic aminopropylsiloxane S9 and admixed with 82.6 g (400 mmol) of N,N-dicyclohexylcarbodiimide (DCC). The mixture was reacted at 90° C. for six hours, after which volatile constituents were removed by distillation under 15 mbar for an hour. The product was obtained as a clear, slightly yellowish product, which was solid at room temperature. Analysis by means of .sup.13C NMR spectroscopy showed the complete conversion of the carbodiimide.

(32) S11 (E4): Equilibration of the Condensate S1 to Form a Cyclic Aminopropylphenylmethylsiloxane

(33) A 250 ml multi-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor, dropping funnel and heating hood was charged under inert conditions with 11.6 g (99 mmol/—NH.sup.2) of a condensate prepared according to S1, and with 13.5 g (99 mmol/D.sup.PhiMe) of phenylmethylcyclotetrasiloxane, (CAS 546-45-2), 100 g of xylene and 0.6 g of tetrametylammonium hydroxide*pentahydrate (TMAH*5H.sub.2O) were added. The reaction mixture was heated at 90° C. for 6 hours and then heated at reflux for eight hours to destroy the catalyst. The continuous reduction in amine level during this procedure was measured using a pH paper in a stream of nitrogen. When destruction of the catalyst was at an end, the solvent was removed on a rotary evaporator and intensive distillation took place on the rotary evaporator at 100° C. and <1 mbar for one hour. The slightly turbid product, finally, was filtered through a fluted filter, giving a clear and colourless product.

(34) S12 (G4): Preparation of a Cyclic Siloxane Containing Guanidine Groups by Reaction of a Cyclic Aminopropylphenylmethylsiloxane with DCC

(35) A 100 ml multi-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 21.4 g (84.5 mmol/—NH.sub.2) of the cyclic aminopropylphenylmethylsiloxane (S11) and admixed with 16.6 g (80.5 mmol) of N,N-dicyclohexylcarbodiimide (DCC). The mixture was reacted at 90° C. for six hours, after which volatile constituents were removed by distillation under 15 mbar for an hour. The product was obtained as a clear, slightly yellowish product, which was solid at room temperature. Analysis by means of .sup.13C NMR spectroscopy showed the complete conversion of the carbodiimide.

(36) S13 (G5): Synthesis of a Cyclotetrasiloxane Containing Guanidino Groups by Reaction of Tetra(Chloropropyl)Tetramethylcyclosiloxane with Tetramethylguanidine

(37) A 500 ml multi-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 50 g (0.37 mol) of tetra(chloropropyl)tetramethylcyclosiloxane D.sub.4.sup.(CH2)3Cl, which was obtained by preceding aqueous hydrolysis/condensation of a chloropropyldichloromethylsilane, and this initial charge was heated to 60° C., and a quantity of 126.4 g (1.1 mol) of tetramethylguanidine was added over 30 minutes. The reaction temperature was raised to 130° C. and maintained for six hours, during which substantial salt formation was observed as the reaction time moved forward. After the end of the reaction time, the batch was cooled to room temperature and diluted with 100 ml of toluene. The product was then freed from the salt using a filter press (Seitz K300) and then freed from the unreacted tetramethylguanidine on a rotary evaporator at 100° C. and a pressure <1 mbar for an hour. Following distillation, the tetraguanidinopropylcyclotetrasiloxane was obtained as a turbid, slightly yellowish product. Analysis by .sup.1H and .sup.29Si NMR confirmed the structure.

(38) S14 (G6): Synthesis of a Cyclic Guanidinosiloxane by Reaction of 2,4,6,8-Tetrakis(3-Chloropropyl)-2,4,6,8-Tetramethylcyclotetrasiloxane [D.sub.4.sup.(C3H6Cl)] with TMG

(39) A 500 ml multi-necked flask equipped with KPG stirrer, dropping funnel, internal temperature measurement sensor and inert gas feed line was copiously inertized with nitrogen and then charged with 100 g (183 mmol=732 mmol/—C.sub.3H.sub.6Cl) of 2,4,6,8-tetrakis(3-chloropropyl)-2,4,6,8-tetramethylcyclotetrasiloxane [CAS 96322-87-1], which was heated to 60° C. Then 252.8 g (2.2 mol) of tetramethylguanidine were metered in, and the mixture was heated at 130° C. for six hours. After the onset of copious precipitation of salt, 200 ml of toluene were added in order to keep the batch stirrable. After the end of the reaction, the salt was separated using a filter press over a Seitz K300 filter. Unreacted tetramethylguanidine was subsequently removed from the filtrate by distillation under an intensive oil pump vacuum (<1 mbar) at 100° C. for an hour. The viscous, slightly yellowish and turbid product obtained was discharged under inert gas.

(40) S15 (E5): Equilibration of Phenylmethylcyclosiloxane and 2,4,6,8-Tetrakis(3-Chloropropyl)-2,4,6,8-Tetramethylcyclotetrasiloxane

(41) A 250 ml multi-necked flask equipped with KPG stirrer, dropping funnel, internal temperature measurement sensor and inert gas feed line was copiously inertized with nitrogen and then charged with 20 g (147 mmol) of phenylmethylcyclosiloxane (CAS 546-45-2). Then 20 g (36.6 mmol=147 mmol/—C.sub.3H.sub.6Cl) tetrakis(3-chloropropyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 160 g of toluene and 12 g of Lewatit® K2621 were added. Equilibration was then carried out at 60° C. for six hours, and the Lewatit® catalyst was separated off on a fluted filter. The filtrate was freed from toluene on a rotary evaporator, and then distilled fully at 70° C. and <1 mbar for an hour. The clear, colourless product thus obtained was discharged under inert gas.

(42) S16 (G7): Synthesis of a Cyclic Guanidinosiloxane by Reaction of S15 with Tetramethylguanidine

(43) A 500 ml multi-necked flask equipped with KPG stirrer, dropping funnel, internal temperature measurement sensor and inert gas feed line was inertized copiously with nitrogen and then charged with 30 g (55 mmol=110 mmol/—C.sub.3H.sub.6Cl) of S15 equilibrate, and 38 g (330 mmol) of tetramethylguanidine and 40 g of xylene were added. The reaction mixture was heated and held at a reaction temperature of 130° C. for six hours. After the end of reaction, a Seitz K300 filter in a filter press was used to separate off the precipitated tetramethyl hydrochloride. Unreacted tetramethylguanidine and the solvent were subsequently removed from the filtrate by distillation under an intense oil pump vacuum (<1 mbar) at 100° C. for an hour. The highly viscous, slightly yellowish and clear product obtained was discharged under inert gas.

(44) S17 (G8): Synthesis of 2′,2′-((1,1,3,3-Tetramethyldisiloxane-1,3-Diyl)Bis(Propane-3,1-Diyl))Bis(1,3-Dicyclohexylguanidine)

(45) A 250 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen blanketing, temperature sensor and heating hood was charged under inert conditions with 24.85 g (100 mmol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 40.44 g (196 mmol) of N,N-dicyclohexylcarbodiimide were added. With continuing stirring, the reaction mixture was reacted at 90° C. for six hours, after which all of the volatile constituents were distilled off over 30 minutes under a diaphragm pump vacuum. This gave a clear, viscous product, which after analysis by means of .sup.13C NMR showed complete conversion of the carbodiimide.

(46) S18 (G9): Reaction of the Condensate 51 with DCC

(47) A 500 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen blanketing, temperature sensor and heating hood was charged under inert conditions with 128.09 g of a condensate according to S1 (N value=11.3 wt %, 122.5 g/eq —NH.sub.2, =1.05 mol NH.sub.2), and 71.91 g (348.52 mmol) of N,N-dicyclohexylcarbodiimide were added. With continuing stirring, the reaction mixture was reacted at 90° C. for six hours, after which all of the volatile constituents were distilled off over 30 minutes under a diaphragm pump vacuum. This gave a clear, viscous product (S18) which after analysis by means of .sup.13C NMR showed complete conversion of the carbodiimide.

(48) S19 (G10): Reaction of the Condensate S1 with DCC

(49) A 500 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen blanketing, temperature sensor and heating hood was charged under inert conditions with 94.2 g of a condensate according to S1 (N value=11.3 wt %, 122.5 g/eq —NH.sub.2, =769.1 mmol) and 105.8 g (512.72 mmol) of N,N-dicyclohexylcarbodiimide were added. With continuing stirring, the reaction mixture was reacted at 90° C. for six hours, after which all of the volatile constituents were distilled off over 30 minutes under a diaphragm pump vacuum. This gave a clear product, highly viscous in the hot state, which after analysis by means of .sup.13C NMR showed complete conversion of the carbodiimide. After cooling to RT, the product solidified to form a clear mass, which was reversibly meltable, however.

(50) S20 (E7): Preparation of a Linear Siloxane of the Formula MD.sub.3D.sup.C3H6ClM

(51) A 250 ml single-necked flask was charged with 39.3 g (288 mmol/D.sup.C3H6Cl) of a cyclic chloropropyldichloromethylsilane hydrolysis condensate of the general formula [D.sup.C3H6Cl].sub.4 64 g (863 mmol/D) of decamethylcyclopentasiloxane and 46.7 g (288 mmol/MM) of hexamethyldisiloxane. With magnetic stirring, 0.15 g of trifluoromethanesulphonic acid was added and the batch was stirred overnight. The next day, the equilibration was completed on a rotary evaporator at 90° C. for four hours, after which the acid was deactivated by addition of 8 g of sodium hydrogencarbonate. Filtration on a fluted filter gave 158 g of a clear, colourless liquid. Analysis by .sup.29Si spectroscopy confirmed the structure [MD.sub.3D.sup.C3H6ClM].

(52) S21 (G11): Preparation of a Linear Siloxane Containing Guanidinopropyl Groups:

(53) A 250 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 80 g (153 mmol/D.sup.C3H6Cl) of S20, and this initial charge was heated to 100° C. Then 53 g (460 mmol) of tetramethylguanidine were metered in via a dropping funnel over an hour, and the mixture was held at 130° C. for a further eight hours. After the end of reaction, the precipitated tetramethylguanidine hydrochloride was filtered off and the product was distilled under an oil pump vacuum at 6 mbar and 130° C. for an hour. A further filtration gave 55 g of a clear product. .sup.29Si and .sup.13C NMR analyses confirmed the structure.

(54) S22 (E8): Preparation of a Linear Siloxane of the Formula MD.sub.3D.sup.C3H6NH2M

(55) A 250 ml multi-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor, dropping funnel and heating hood was charged under inert conditions with 35 g (300 mmol/—NH.sub.2) of a condensate according to S1 with a nitrogen value of N.sub.tot.=11.5 wt % and a viscosity of 807 mPas (Brookfield), and 66.6 g (900 mmol/D) of octomethylcyclotetrasiloxane, 48.5 g (300 mmol/MM) and 60 mg of tetrametylammonium hydroxide pentahydrate (TMAH*5H.sub.2O) were added. The reaction mixture was heated at 90° C. for 6 hours and then heated on a rotary evaporator at 130° C. for three hours in order to destroy the catalyst. When destruction of the catalyst was at an end, the solvent was removed on a rotary evaporator and residue was subjected to intensive distillation on the rotary evaporator at 100° C. and <1 mbar for an hour. Lastly, the slightly turbid product was filtered through a fluted filter, to give a clear, colourless product which according to .sup.29Si NMR had an approximate structure of M(DD.sup.C3H6NH2).sub.7.4M.

(56) S23 (G12): Preparation of a Linear Siloxane, Carrying Guanidine Groups, of the Formula MD.sub.3D.sup.C3H6-GUAM

(57) A 100 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 50 g (135 mmol/—NH.sub.2) of the linear aminosiloxane prepared above (S22) (N.sub.theor.=3.787%) and this initial charge was admixed with 26.5 g (128 mmol) of N,N-dicyclohexylcarbodiimide. The resulting reaction mixture was reacted at 90° C. for six hours, giving a colourless, slightly turbid product. Analysis by .sup.13C NMR spectroscopy showed complete conversion of the carbodiimide. Subsequently, .sup.29Si NMR spectroscopy found a siloxane chain length of N=5.6, indicating a structure of M (DD.sup.C3H6GUA).sub.3.6M.

(58) S24 (E9): Preparation of a Linear Aminopropylsiloxane by Equilibration of S1 with HMDS

(59) A 250 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 90 g of a condensate according to S1 with a nitrogen value of N.sub.tot.=11.5 wt % and a viscosity of 807 mPas (Brookfield), and 60 g of hexamethyldisiloxane were added. Then, with the reaction mixture being stirred, 80 mg (=0.05 wt %) of tetramethylammonium hydroxide were added, and the mixture was heated to 90° C. After a reaction time of one hour, the two-phase, turbid and colourless reaction mixture became homogeneous and clear. After the end of the reaction time, the catalyst was destroyed on a rotary evaporator at 150° C. and 1 mbar for three hours. A volatile constituents fraction of 20 wt % was ascertained here. The .sup.29Si NMR analysis of the end product confirmed the structure of M-[D.sup.(CH2)3NH2].sub.3.5—M, and a nitrogen value of N.sub.tot.=8.7 wt % was found.

(60) S25 (G14): Preparation of a Linear Siloxane Containing Guanidinopropyl Groups

(61) A 250 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 104.1 g (646 mmol/—NH.sub.2) of the above S24-prepared linear aminosiloxane (N.sub.theor.=8.7%), and 126.8 g (614 mmol) of N,N-dicyclohexylcarbodiimide were added. The resulting reaction mixture was reacted at 90° C. for six hours, giving a slightly yellowish product, colourless in the hot state, which became solid on cooling, but was reversibly meltable. Analysis by .sup.13C NMR spectroscopy showed complete conversion of the carbodiimide. Moreover, .sup.29Si NMR spectroscopy found a siloxane chain length of N=5.5, suggesting a structure of M(D.sup.C3H6GUA).sub.3.5M

(62) S26 (G14): Preparation of a Linear Siloxane Containing Guanidinopropyl and Aminopropyl Groups

(63) A 100 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 49.2 g (299 mmol/—NH.sub.2) of a linear aminosiloxane in analogy to S24 with a nitrogen value of N.sub.theor.=8.5 wt %, and 30.8 g (149 mmol) of N,N-dicyclohexylcarbodiimide were added. The reaction mixture thus obtained was reacted at 90° C. for six hours, giving a colourless, clear product. Analysis by .sup.13C NMR spectroscopy showed complete conversion of the carbodiimide. Moreover, .sup.29Si NMR spectroscopy found a siloxane chain length of N=5.6, suggesting a structure of M(D.sup.C3H6NH2).sub.˜1.8(D.sup.C3H6-GUA).sub.˜1.8M.

(64) S27 (G15): Preparation of a Siloxane Containing Linear Guanidinopropyl Groups

(65) A 100 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor and heating hood was charged under inert conditions with 37.7 g (215 mmol/—NH.sub.2) of a linear aminosiloxane prepared above in analogy to S24 (N=8.7 wt %), and 42.2 g (204 mmol) of N,N-dicyclohexylcarbodiimide were added. The reaction mixture thus obtained was reacted at 90° C. for eight hours, giving a slightly yellowish, clear and viscous product. Analysis by .sup.13C NMR spectroscopy showed complete conversion of the carbodiimide. Moreover, .sup.29Si NMR spectroscopy found a siloxane chain length of N=4.7, suggesting a structure of M(DD.sup.C3H6GUA).sub.2.7M.

(66) S28: Preparation of a Linear, Hydroxyl-Terminated Siloxane Condensate Containing Guanidine Groups

(67) A 250 ml four-necked flask equipped with KPG stirrer, reflux condenser, nitrogen blanketing, temperature sensor and heating hood was charged under inert conditions with 102.1 g (232.24 mmol —NH.sub.2) of a linear siloxane condensate which has propyl and aminopropyl groups and is hydroxyl-terminated (N.sub.prim.=3.64 wt %, M.sub.w=˜730 g/mol), and 47.9 g (232.24 mmol) of N,N-dicyclohexylcarbodiimide were added. With stirring continuing, the reaction mixture was reacted at 90° C. for six hours, after which all of the volatile constituents were removed by distillation within 30 minutes under a diaphragm pump vacuum. This gave a clear, viscous product, which according to analysis by .sup.13C NMR showed complete conversion of the carbodiimide.

(68) S29 (H3): Hydrosilylation of N-Ethylmethylallylamine (NEMALA) Over a Cyclic Hydrogensiloxane

(69) A 2000 ml multi-necked flask equipped with KPG stirrer, reflux condenser, nitrogen inlet, temperature sensor, dropping funnel and heating hood was charged under inert conditions with 756.3 g of a cyclic hydrogensiloxane (0.1332 wt %, corresponding to 756.3 g/eq SiH), 4.43 g of sodium carbonate were added, and the mixture was heated to a reaction temperature of 130° C. Shortly before the reaction temperature was reached, 48 mg of di-μ-chlorodichlorobis(cyclohexene)diplatinum(II) catalyst were added, and then in portions 885.3 g of N-ethylmethylallylamine (NEMALA, CAS 18328-90-0) were added via a dropping funnel in such a way that the reaction temperature did not exceed 145° C. The reaction was taken over seven hours at 130° C. to an SiH conversion >99%, with the reaction monitored hourly by means of a determination by gas volumetry. The resulting reaction mixture was cooled to room temperature and filtered overnight, giving 881.5 g (theoretical 885.25 g). The subsequent multi-hour distillation under an oil pump vacuum at 130° C. and <1 mbar afforded 403.5 g (theoretical 406.24 g) of product, and 474 g (theoretical 478.96 g) of volatile compounds were condensed out under cooling with liquid nitrogen. The amino-functional cyclic siloxane was obtained as a clear, slightly yellowish liquid. Analysis by .sup.1H, .sup.13C and .sup.29Si NMR confirmed the target structure.

(70) S30 (G16): Preparation of a Guanidine by Reaction of the Synthesis Product S29

(71) A 500 ml four-necked flask equipped with KPG stirrer, distillation bridge with vacuum attachment, nitrogen blanketing, temperature sensor and heating hood was charged under inert conditions with 203.1 g (500 mmol/—NH—) of the amino-functional siloxane from the preceding stage, S29, and with 59.9 g (475 mmol) of N,N,-diisopropylcarbodiimide, and this mixture was reacted at 90° C. for 10 hours. After the end of the reaction time, all of the volatile constituents were distilled off over a further hour at 100° C. and 20 mbar under a diaphragm pump vacuum. Analysis by .sup.29Si and .sup.13C NMR confirmed the target structure of the clear, slightly yellowish product.

(72) S31: Preparation of a Reaction Product of Dynasylan® AMEO and DCC

(73) A 500 ml four-necked flask equipped with KPG stirrer, distillation bridge with vacuum attachment, nitrogen blanketing, temperature sensor and heating hood was charged under inert conditions with 221.4 g (1 mol) of an amino-functional silane (Dynasylan® AMEO, Evonik Degussa GmbH) and 200.1 g (970 mmol) of N,N-dicyclohexylcarbodiimide, and this initial charge was reacted at 90° C. for 10 hours. After the end of the reaction time, all of the volatile constituents were distilled off over 30 minutes at 90° C. and 20 mbar under a diaphragm pump vacuum. The colourlessly clear to yellowish product was then stored in the absence of moisture. Spectroscopic analysis by means of .sup.13C NMR revealed the quantitative conversion of the carbodiimide, with the further analysis of the reaction mixture being in line with expectations.

Synthesis of Resins 1 to 10

Resin 1

(74) In a method based on EP 0157318, a methoxy-functional methyl-silicone resin was prepared by hydrolysis and subsequent condensation of 559.7 g (3.74 mol) of trichloromethylsilane with a methanol/water mixture [373.1 g (11.64 mol) MeOH/67.2 g H.sub.2O (3.71 mol)]. After the end of addition of the methanol/water mixture, the reaction mixture was distilled at 16 mbar. Analysis by .sup.1H NMR gave a methoxy functionality of 35 wt %; the molar masses were found to be M.sub.w=746 g/mol, M.sub.n=531 g/mol, M.sub.w/M.sub.n=1.4.

Resin 2

(75) An ethoxy-functional methyl-silicone resin was prepared by condensation of trimethoxymethylsilane with an ethanol/water mixture. For this purpose, 600 g (0.94 mol) of trimethoxymethylsilane were introduced with 30 g of ethanol, and then a water/HCl mixture was added dropwise at 60° C. [67.7 g H.sub.2O (3.76 mol) admixed with 0.03 g HCl (37.5% strength), 20 ppm] dropwise. After the reaction mixture had been held under reflux for an hour, it was distilled at 90° C. and then held under vacuum for 30 minutes more. Analysis by .sup.1H NMR gave an ethoxy functionality of 42 wt %; the molar masses were found to be M.sub.w=784 g/mol, M.sub.n=581 g/mol, M.sub.w/M.sub.n=1.4.

Resin 3

(76) In a method based on EP 1142929, a methoxy-functional methyl-phenyl-silicone resin was prepared. For this purpose, 606.3 g (2.86 mol) of phenyltrichlorosilane were introduced, and a methanol/water mixture [59.4 g (1.80 mol) methanol and 18.07 g (1.00 mol) water] was added dropwise. Then 70.6 g (0.19 mol) of decamethylcyclopentasiloxane (D5) and 24.3 g (0.15 mol) of hexametyldisiloxane are added to the reaction mixture, and at a temperature of <50° C. again a methanol/water mixture [69.9 g (2.12 mol) methanol and 50.8 g (2.82 mol) water] is added dropwise. Following the first vacuum distillation at about 50° C. under a pressure <100 mbar, the reaction mixture is held under vacuum for a further hour. Following further addition of 16.9 g of methanol (0.52 mol), distillation took place again under a pressure <100 mbar at 120° C. Analysis by .sup.1H NMR gave a methoxy functionality of 6 wt %; the molar masses were found to be M.sub.w=4.440 g/mol, M.sub.n=1.769 g/mol, M.sub.w/M.sub.n=2.5. Using 83.6 g of xylene, the viscosity was adjusted, and the solids of the resin as well were adjusted to 85 wt %.

Resin 4

(77) In a method based on EP 1142929, a methoxy-functional methyl-phenyl-silicone resin was prepared. For this purpose, first of all, 562.5 g (2.66 mol) of phenyltrichlorosilane were slowly admixed with 167.4 g (5.21 mol) of methanol. Then 122.5 g (0.27 mol) of decamethylcyclopentasiloxane (D5) were added, and at 50° C. 48.0 g (2.60 mol) of water were added dropwise. This was followed by vacuum distillation under a pressure <100 mbar at 60° C. Following inertization with nitrogen and addition of a further 100.00 g (3.12 mol) of methanol, stirring was continued for 30 minutes more, and then a further vacuum distillation was carried out. Analysis by .sup.1H NMR gave a methoxy functionality of 15 wt %; the molar masses were found to be M.sub.w=1.656 g/mol, M.sub.n=966 g/mol, M.sub.w/M.sub.n=1.7.

Resin 5

(78) In a method based on EP 1142929, a methoxy-functional methyl-phenyl-silicone resin was prepared. For this purpose, 419.4 g (2.81 mol) of methyltrichlorosilane were slowly admixed with 129.4 g (4.03 mol) of methanol with stirring. Subsequently, 228.2 g (1.08 mol) of phenyltrichlorosilane were added dropwise, during which the reaction mixture rose in temperature to 35° C. Following the PTS addition, 249.9 g of a methanol/water mixture [186.4 g (5.82 mol) MeOH and 63.5 g (3.52 mol) H.sub.2O] were added, followed by stirring finally for 2 hours and, after the end of the addition, by vacuum distillation at 16 mbar. Analysis by .sup.1H NMR gave a methoxy functionality of 25 wt %; the molar masses were found to be M.sub.w=3.050 g/mol, M.sub.n=1.050 g/mol, M.sub.w/M.sub.n=2.7.

Resin 6

(79) In a method based on EP 0 157 318 B1, a methoxy-functional methyl-phenyl-silicone resin was prepared. 858.5 g of resin 3 were introduced with 9.4 g (0.15 mol) of ethylene glycol, 14.3 g of xylene and 41.0 g (0.31 mol) of trimethylolpropane, 0.1 g of butyl titanate was added, and the mixture was heated to reflux. Distillation was then carried out, before the increase in viscosity, until a clear resin was obtained. After cooling to 120° C., first half of 40.8 g of isobutanol were added, and the remaining amount of isobutanol was added after further cooling to 105° C. Lastly, stirring took place at 60° C. for an hour. The solids of the binder were adjusted to 80 wt % using xylene. Analysis by .sup.1H NMR gave a methoxy-functionality of 2 wt %; the molar masses were found to be M.sub.w=40 000 to 90 000 g/mol, M.sub.n=3260 to 3763 g/mol, M.sub.w/M.sub.n=12 to 24. The resulting resin was dissolved in xylene.

Resin 7

(80) In a method based on EP 1142929, an ethoxy-functional methyl-phenyl-silicone resin was prepared. For this purpose, first of all, 571.0 g (2.70 mol) of phenyltrichlorosilane were slowly admixed with 247.7 g (5.38 mol) of ethanol. Then 79.9 g (0.22 mol) of decamethylcyclopentasiloxane (D5) were added, and at 50° C. 60.5 g (3.36 mol) of water were added dropwise. This was followed by vacuum distillation under a pressure <100 mbar at 60° C. Following inertization with nitrogen and addition of a further 40.8 g (0.88 mol) of ethanol, stirring was continued for 30 minutes more, and then a further vacuum distillation was carried out. Analysis by .sup.1H NMR gave an ethoxy functionality of 14 wt %; the molar masses were found to be M.sub.w=1790 g/mol, M.sub.n=1160 g/mol, M.sub.w/M.sub.n=1.5.

Resin 8

(81) In a method based on EP 1142929, an ethoxy-functional phenyl-silicone resin was prepared by the hydrolysis and subsequent condensation of 646.1 g (3.05 mol) of phenyltrichlorosilane with an ethanol/water mixture [296.3 g (6.43 mol) EtOH/57.5 g H.sub.2O (3.19 mol)]. After the end of the addition of the ethanol/water mixture, the reaction mixture was distilled at 16 mbar. Analysis by .sup.1H NMR gave an ethoxy functionality of 25 wt %; the molar masses were found to be M.sub.w=940 g/mol, M.sub.n=740 g/mol, M.sub.w/M.sub.n=1.3.

Resin 9

(82) In a method based on EP 1142929, a methoxy-functional phenyl-silicone resin was prepared by the hydrolysis and subsequent condensation of 745.6 g (3.53 mol) of phenyltrichlorosilane with a methanol/water mixture [184.3 g (5.76 mol) MeOH/70.1 g H.sub.2O (3.89 mol)]. After the end of the addition of the methanol/water mixture, the reaction mixture was distilled at 16 mbar. Analysis by .sup.1H NMR gave a methoxy functionality of 17 wt %; the molar masses were found to be M.sub.w=1400 g/mol, M.sub.n=860 g/mol, M.sub.w/M.sub.n=1.6.

Resin 10

(83) In a method based on EP 1142929, a methoxy-functional methyl-phenyl-silicone resin was prepared. For this purpose, first of all, 576.5 g (2.73 mol) of phenyltrichlorosilane were slowly admixed with 172.4 g (5.38 mol) of methanol. Then 101.1 g (0.27 mol) of decamethylcyclopentasiloxane (D5) were added, and at 50° C. 49.2 g (2.73 mol) of water were added dropwise. This was followed by vacuum distillation under a pressure <100 mbar at 60° C. Following inertization with nitrogen and addition of a further 100.8 g (3.1 mol) of methanol, stirring was continued for 30 minutes more, and then a further vacuum distillation was carried out. Analysis by .sup.1H NMR gave a methoxy functionality of 17 wt %; the molar masses were found to be M.sub.w=1220 g/mol, M.sub.n=780 g/mol, M.sub.w/M.sub.n=1.6.

Example 2: Compositions/formulations

(84) quantity figures for the catalysts are based on the mass of the overall composition, and are expressed in wt %. Where a catalyst is added in dissolved form, the quantity figure is based on the amount of catalyst in the solution.

(85) The binders (resins) may optionally comprise a crosslinker. The quantity figures for the crosslinker are expressed in wt % based on the overall composition.

(86) Resin 3 was formulated using xylene as solvent. The concentration of resin 3 in xylene is 85 wt % based on the overall mass, and this corresponds to the solids content.

(87) In the case of resin 6, the solids was adjusted to 80 wt % following the addition of xylene.

(88) The various binders were introduced and mixed with the catalyst by stirring, using a spatula. The resultant compositions are listed in Table 1.

(89) TABLE-US-00002 TABLE 1 Compositions (the percentage figures are wt % based on the overall mixture, catalyst solvents where appropriate are disregarded); apart from Z1.1, Z4.13 and Z9.13, all of the compositions are inventive. Composition Catalyst Binder Crosslinker I Crosslinker II [%] Resin 1 [%] [%] [%] Z.1.1 TnBT 1.7 98.3 Z1.2 S23 1.2 98.8 Z1.3 S21 2.5 97.5 Z1.4 S21 2.0 98.0 Z1.5 S25 1.5 98.5 Z1.6 S25 1.0 99.0 Z1.7 S25 0.5 99.5 Z1.8 S27 0.5 99.5 Z1.9 S27 1.0 99.0 Z1.10 S14 1.0 (as 50 percent 99.0 solution in xylene) Z1.11 S17 1.0 99.0 Z1.12 S17 1.5 98.5 Z1.13 S31 1.5 98.5 Cat. [%] Resin 2 [%] Z2.1 S17 1.5 98.5 Z2.2 S31 2.0 98.0 Z2.3 S25 1.5 98.5 Z2.4 S27 1.0 99.0 Cat. [%] Resin 3 [%] PTMS [%] Z3.1 S23 1.2 69.16 29.64 Z3.2 S23 2.7 68.11 29.19 Z3.3 S21 2.5 48.75 48.75 Z3.4 S21 2.0 49.00 49.00 Z3.5 S25 1.5 49.25 49.25 Z3.6 S14 1.5 49.25 49.25 Z3.7 S14 1.0 (as 50 percent 49.50 49.50 solution in xylene) Z3.8 S17 2.0 49.00 49.00 Z3.9 S17 3.0 48.50 48.50 Z3.10 S31 2.0 49.00 49.00 Z3.11 S31 3.0 48.50 48.50 Z3.12 S26 3.0 48.50 48.50 Z3.13 S27 1.0 49.50 49.50 Z3.14 S27 1.5 49.25 49.25 Cat. [%] Resin 4 [%] PTMS [%] MTMS [%] Z4.1 S17 3.0 97.0 Z4.2 S31 3.0 97.0 Z4.3 S23 2.7 97.3 Z4.4 S21 2.5 97.5 Z4.5 S17 2.0 68.6 29.4 Z4.6 S17 3.0 67.9 29.1 Z4.7 S31 2.0 68.6 29.4 Z4.8 S31 3.0 67.9 29.1 Z4.9 S17 2.0 68.6 29.4 Z4.10 S17 3.0 67.9 29.1 Z4.11 S31 2.0 68.6 29.4 Z4.12 S31 3.0 67.9 29.1 Z4.13 TnBT 1.7 98.3 Cat. [%] Resin 5 [%] PTMS [%] Z5.1 S17 2.0 98.0 Z5.2 S31 2.0 98.0 Z5.3 S23 2.0 98.0 Z5.4 S21 2.0 98.0 Z5.5 S17 2.0 68.6 29.4 Z5.6 S31 2.0 68.6 29.4 Z5.7 S23 2.0 68.6 29.4 Z5.8 S21 2.0 68.6 29.4 Z5.9 S17 2.0 68.6 29.4 Z5.10 S31 2.0 68.6 29.4 Z5.11 S23 2.5 68.25 29.25 Z5.12 S21 2.5 68.25 29.25 Cat. [%] Resin 6 [%] PTMS [%] Z6.1 S17 1.2 49.4 49.4 Z6.2 S17 2.0 49.0 49.0 Z6.3 S31 1.6 49.2 49.2 Z6.4 S31 2.0 49.0 49.0 Z6.5 S23 2.7 48.65 48.65 Z6.6 S21 2.5 48.75 48.75 Cat. [%] Resin 7 [%] PTEOS [%] TEOS [%] Z7.1 S17 2.0 49.0 24.5 24.5 Z7.2 S17 2.5 48.75 24.37 24.37 Z7.3 S17 3.0 48.5 24.25 24.25 Z7.4 S31 2.0 49.0 24.5 24.5 Z7.5 S31 3.0 48.5 24.25 24.25 Propyltrieth- oxysilane Cat. [%] Resin 7 [%] [%] TEOS [%] Z7.6 S17 2.0 49.0 24.5 24.5 Z7.7 S17 3.0 48.5 24.25 24.25 Z7.8 S31 3.0 48.5 24.25 24.25 Cat. [%] Resin 8 [%] TEOS [%] Z8.1 S17 2.0 49.0 49.0 Z8.2 S17 3.0 48.5 48.5 Cat. [%] Resin 8 [%] PTEOS [%] TEOS [%] Z8.3 S17 2.0 49.0 24.5 24.5 Z8.4 S17 3.0 48.5 24.25 24.25 Cat. [%] Resin 9 [%] PTMS [%] MTMS [%] Z9.1 S17 2.0 68.6 29.4 Z9.2 S17 3.0 67.9 29.1 Z9.3 S31 2.0 68.6 29.4 Z9.4 S31 3.0 67.9 29.1 Z9.5 S17 2.0 68.6 29.4 Z9.6 S17 3.0 67.9 29.1 Z9.7 S31 2.0 68.6 29.4 Z9.8 S31 3.0 67.9 29.1 Cat. [%] Resin 9 [%] TEOS [%] Z9.9 S17 2.0 68.6 29.4 Z9.10 S17 3.0 67.9 29.1 Z9.11 S31 2.0 68.6 29.4 Z9.12 S31 3.0 67.9 29.1 Z9.13 TnBT 1.7 68.8 29.5 Amount [%] Resin 10 [%] PTMS [%] MTMS [%] Z10.1 S17 2.0 98.0 Z10.2 S17 3.0 97.0 Z10.3 S31 2.0 98.0 Z10.4 S31 3.0 97.0 Z10.5 S17 2.0 68.6 29.4 Z10.6 S17 3.0 67.9 29.1 Z10.7 S31 2.0 68.6 29.4 Z10.8 S31 3.0 67.9 29.1 Z10.9 S17 2.0 49.0 49.0 Z10.10 S17 3.0 48.5 48.5 Z10.11 S31 2.0 49.0 49.0 Z10.12 S31 3.0 48.5 48.5 Amount [%] Resin 6 [%] Resin 1 [%] Z11.1 S17 2.0 49.0 49.0 Z11.2 S31 2.0 49.0 49.0 Amount [%] Resin 7 [%] Resin 1 [%] Z12.1 S17 2.0 49.0 49.0 Z12.2 S17 3.0 48.5 48.5 Z12.3 S31 2.0 49.0 49.0 Z12.4 S31 3.0 48.5 48.5

Example 3: Use

(90) The drying times of certain compositions according to Table 1 were investigated in the form of coating materials, using the Drying Recorder (model BK3). The results are shown in Table 2.

(91) TABLE-US-00003 TABLE 2 Drying times of the inventive compositions according to Example 2 Composition Initial drying [h] Volume drying [h] Z1.1 1.0 1.2 Z1.2 <0.5 0.5 Z1.3 0.8 0.8 Z1.4 1.2 1.6 Z1.5 0.3 0.3 Z1.6 0.5 0.5 Z1.7 1.0 1.0 Z1.8 0.8 2.4 Z1.9 0.5 1.0 Z1.10 1.0 1.5 Z1.11 <0.5 <0.5 Z1.12 <0.5 <0.5 Z1.13 <0.5 <0.5 Z2.1 <0.5 0.8 Z2.2 <0.5 1.0 Z2.3 0.8 2.0 Z2.4 1.0 1.5 Z3.1 1.5 10.5 Z3.2 <0.5 1.6 Z3.3 1.2 2.4 Z3.4 1.6 3.0 Z3.5 0.8 2.0 Z3.6 0.8 1.6 Z3.7 1.0 1.5 Z3.8 0.8 1.5 Z3.9 0.5 0.8 Z3.10 0.5 1.0 Z3.11 <0.5 0.8 Z3.12 1.6 2.0 Z3.13 2.4 4.8 Z3.14 1.2 2.4 Z4.1 2.4 5.0 Z4.2 4.0 5.0 Z4.3 9.0 14.0 Z4.4 9.0 12.0 Z4.5 1.8 2.6 Z4.6 1.2 2.0 Z4.7 2.4 4.0 Z4.8 0.8 2.7 Z4.9 1.5 3.0 Z4.10 1.2 2.4 Z4.11 2.6 5.0 Z4.12 1.2 2.4 Z4.13 No drying No drying Z5.1 <0.5 1.0 Z5.2 <0.5 0.8 Z5.3 1.0 1.8 Z5.4 0.8 1.5 Z5.5 <0.5 0.8 Z5.6 0.5 1.0 Z5.7 1.0 2.5 Z5.8 0.8 1.5 Z5.9 <0.5 0.5 Z5.10 <0.5 <0.5 Z5.11 <0.5 1.0 Z5.12 <0.5 1.4 Z6.1 <0.5 1.2 Z6.2 0.8 1.5 Z6.3 0.2 1.2 Z6.4 0.5 1.5 Z6.5 1.5 3.5 Z6.6 0.8 3.5 Z7.1 <0.5 8.0 Z7.2 <0.5 4.0 Z7.3 <0.5 2.8 Z7.4 5.5 10.0 Z7.5 3.6 6.4 Z7.6 0.5 4.5 Z7.7 0.5 4.0 Z7.8 0.5 5.0 Z8.1 <0.5 0.5 Z8.2 <0.5 0.5 Z8.3 <0.5 4.0 Z8.4 <0.5 3.2 Z9.1 1.0 1.3 Z9.2 0.5 1.0 Z9.3 1.5 4.0 Z9.4 1.0 2.0 Z9.5 1.0 2.0 Z9.6 0.5 1.5 Z9.7 1.5 3.0 Z9.8 1.0 2.5 Z9.9 0.8 1.0 Z9.10 0.5 1.0 Z9.11 1.0 4.0 Z9.12 1.0 2.5 Z9.13 1.0 >24 Z10.1 4.0 5.0 Z10.2 2.5 4.0 Z10.3 5.5 9.5 Z10.4 5.0 6.5 Z10.5 2.0 3.2 Z10.6 1.2 2.0 Z10.7 3.0 5.0 Z10.8 1.2 2.8 Z10.9 1.2 4.5 Z10.10 1.2 2.5 Z10.11 1.6 3.2 Z10.12 1.2 2.0 Z11.1 <0.5 <0.5 Z11.2 <0.5 <0.5 Z12.1 2.3 3.8 Z12.2 1.6 2.0 Z12.3 4.0 10.0 Z12.4 1.6 2.9

(92) The results of Example 3 show that the compositions of the invention are suitable as coating materials.

(93) In the case of polysiloxanes containing aryl groups, the titanates lead either not at all or only very slowly to a curing via hydrolysis/condensation reactions.

(94) The drying times of the compositions of the invention are comparable to or better than those from the prior art.

(95) The surfaces of all cured compositions according to the invention are consistently hard.