POLYSILOXANE POLYMER

Abstract

The invention relates to the use of a polymer for improving the clean-ability of a surface coating or for reducing the dirt pick up of a surface coating, wherein the polymer is a a non-crosslinked polymer having a polymer main chain comprising i) polysiloxane segments comprising repeating units of the formula (I) wherein R 1 independent of each occurrence represents a hydrocarbyl group and n is an integer in the range of 6 to 150, and ii) non-polysiloxane segments having at least one functional group comprising at least one of hydroxyl group, acryloyl group, methacryloyl group, acetyl group, urethane group, and methyl ether group, wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.5%, calculated on the average number of silicon atoms per polysiloxane segment, and wherein at least one non-polysiloxane segment is located between two polysiloxane segments.

##STR00001##

Claims

1. A curable coating composition comprising: a binder, and an amount of a non-crosslinked polymer sufficient to achieve at least one of improved cleanability or reduced dirt pick up of a surface coating formed from the curable coating composition relative to a surface coating formed from a curable coating composition comprising the binder but not the polymer, the polymer having a polymer main chain comprising: i) polysiloxane segments comprising repeating units of the formula (I) ##STR00005## wherein R.sup.1 independent of each occurrence represents a hydrocarbyl group and n is an integer in the range of 6 to 150, and ii) non-polysiloxane segments having at least one functional group comprising at least one of hydroxyl group, acryloyl group, methacryloyl group, acetyl group, urethane group, and methyl ether group, wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.5%, calculated on the average number of silicon atoms per polysiloxane segment, and wherein at least one non-polysiloxane segment is located between two polysiloxane segments.

2. The curable coating composition according to claim 1, wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is less than 8.0%, calculated on the average number of silicon atoms per polysiloxane segment.

3. The curable coating composition according to claim 1, wherein R.sup.1 independent of each occurrence represents a C.sub.1 to C.sub.4 alkyl group or a phenyl group.

4. The curable coating composition according to claim 1, wherein n in formula (I) is an integer in the range of 10 to 120.

5. The curable coating composition according to claim 1, wherein the at least one functional group is linked to the non-polysiloxane segment via a group comprising at least one of an ester group or an ether group.

6. The curable coating composition according to claim 1, wherein the average number of functional groups per non-polysiloxane segment is in the range of 0.8 to 2.5.

7. The curable coating composition according to claim 1, wherein the at least one functional group comprises hydroxyl groups.

8. The curable coating composition according to claim 1, wherein the polymer has a weight average molecular weight in the range of 2000 g/mol to 100000 g/mol.

9. The curable coating composition according to claim 1, wherein terminal segments of the polymer are non-polysiloxane segments.

10. A curable coating composition comprising: a binder, and an amount of a non-crosslinked polymer sufficient to achieve at least one of improved cleanability or reduced dirt pick up of a surface coating formed from the curable coating composition relative to a surface coating formed from a curable coating composition comprising the binder but not the polymer, the polymer having a polymer main chain comprising: i) polysiloxane segments comprising repeating units of the formula (I) ##STR00006## wherein R.sup.1 independent of each occurrence represents a hydrocarbyl group and n is an integer in the range of 6 to 150, and ii) non-polysiloxane segments having at least one functional group comprising at least one of hydroxyl group, acryloyl group, methacryloyl group, acetyl group, urethane group, and methyl ether group, wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.5%, calculated on the average number of silicon atoms per polysiloxane segment, and wherein at least one non-polysiloxane segment is located between two polysiloxane segments, and wherein the polymer has been obtained by a process comprising: providing a polysiloxane having at least two SiH groups, wherein less than 9.5% of the silicon atoms of the polysiloxane have SiH groups, providing a non-polysiloxane compound having at least two ethylenically unsaturated groups per molecule, providing a non-polysiloxane compound having one ethylenically unsaturated group per molecule, wherein at least one of the non-polysiloxane compound having at least two ethylenically unsaturated groups per molecule or the non-polysiloxane compound having one ethylenically unsaturated group per molecule has at least one functional group per molecule comprising at least one of hydroxyl group, acryloyl group, methacryloyl group, acetyl group, urethane group, and methyl ether group, and covalently linking to the polysiloxane having at least two SiH groups, the non-polysiloxane compound having at least two ethylenically unsaturated groups per molecule, and the non-polysiloxane compound having one ethylenically unsaturated group per molecule.

11. The curable coating composition according to claim 1, wherein the binder has functional groups comprising at least one of hydroxyl group, acryloyl group, methacryloyl group, acetyl group, urethane group, and methyl ether group, and curable coating composition further comprises a crosslinking agent or crosslinking initiator for the functional groups of the binder.

12. The curable coating composition according to claim 11, wherein the polymer is included in the composition in an amount of from 0.10 to 10.00% by weight, based on the total weight of the composition.

13. A method for achieving at least one of improved cleanability or reduced dirt pick up of a surface coating formed from a surface coating composition, the method comprising including in the surface coating composition a non-crosslinked polymer having a polymer main chain comprising i) polysiloxane segments comprising repeating units of the formula (I) ##STR00007## wherein R.sup.1 independent of each occurrence represents a hydrocarbyl group and n is an integer in the range of 6 to 150, and ii) non-polysiloxane segments having at least one functional group comprising at least one of hydroxyl group, acryloyl group, methacryloyl group, acetyl group, urethane group, and methyl ether group, wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.5%, calculated on the average number of silicon atoms per polysiloxane segment, and wherein at least one non-polysiloxane segment is located between two polysiloxane segments.

Description

EXAMPLES

Preparation of Polymers

Comparative Example A

[0076] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D14 with Trimethylolpropane Diallylether and Ethylene Glycol Monoallylether (Molar Ratio 3.0:2.0:2.3)

[0077] 12.5% of the silicon atoms of the polysiloxane MH2D14 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 12.5%, calculated on the average number of silicon atoms per polysiloxane segment.

[0078] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 201.415 g of the methyl-hydrogen siloxane. The flask was heated to 75 C. and 0.550 g of a 0.2% solution of Karstedt catalyst in xylene were added. Subsequently, 23.300 g of trimethylolpropane diallylether were added via a dropping funnel during a period of 20 minutes, followed by a period of 30 minutes stirring at 100 C. Then 25.285 g ethylene glycol monoallylether were added via a dropping funnel during a period of 20 minutes, followed by stirring at 100 C. for 3 hours. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 2266 g/mol, Mw 5682 g/mol.

Comparative Example B

[0079] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D6 with Trimethylolpropane Diallylether and Ethylene Glycol Monoallylether (Molar Ratio 3.0:2.0:2.3)

[0080] 25.0% of the silicon atoms of the polysiloxane MH2D6 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 25.0%, calculated on the average number of silicon atoms per polysiloxane segment.

[0081] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 171.011 g of the methyl-hydrogen siloxane. The flask was heated to 75 C. and 0.550 g of a 0.2% solution of Karstedt catalyst in xylene were added. Subsequently, 37.881 g of trimethylolpropane diallylether were added via a dropping funnel during a period of 20 minutes, followed by a period of 3 hours stirring at 100 C. Then 41.108 g ethylene glycol monoallylether were added via a dropping funnel during a period of 20 minutes, followed by stirring at 100 C. for 3 hours. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 1827 g/mol, Mw 3563 g/mol

Example 1

[0082] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D79.3 with Trimethylolpropane Diallylether and Ethylene Glycol Monoallylether (Molar Ratio 3.0:2.0:2.3)

[0083] 2.46% of the silicon atoms of the polysiloxane MH2D79.3 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 2.46%, calculated on the average number of silicon atoms per polysiloxane segment.

[0084] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 238.427 g of the methyl-hydrogen siloxane. The flask was heated to 75 C. and 0.550 g of a 0.2% solution of Karstedt catalyst in xylene were added. Subsequently, 5.550 g of trimethylolpropane diallylether were added via a dropping funnel during a period of 20 minutes, followed by a period of 3 hours stirring at 100 C. Then 6.023 g ethylene glycol monoallylether were added via a dropping funnel during a period of 20 minutes, followed by stirring at 100 C. for 3 hours. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 2813 g/mol, Mw 22909 g/mol

Example 2

[0085] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D106.3 with Trimethylolpropane Diallylether and Ethylene Glycol Monoallylether (Molar Ratio 3.0:2.0:2.3)

[0086] 1.84% of the silicon atoms of the polysiloxane MH2D106.3 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 1.84%, calculated on the average number of silicon atoms per polysiloxane segment.

[0087] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 241.140 g of the methyl-hydrogen siloxane. The flask was heated to 75 C. and 0.550 g of a 0.2% solution of Karstedt catalyst in xylene were added. Subsequently, 4.249 g of trimethylolpropane diallylether were added via a dropping funnel during a period of 20 minutes, followed by a period of 3 hours stirring at 100 C. Then 4.661 g ethylene glycol monoallylether were added via a dropping funnel during a period of 20 minutes, followed by stirring at 100 C. for 3 hours. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 3710 g/mol, Mw 32053 g/mol

Preparation of Intermediate I1

[0088] Reaction of Trimethylolpropane Diallylether with Ethoxylated Trimethylolpropane Oxetane (Average of 3.3 Ethylene Oxide Groups)

[0089] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 137.32 g trimethylolpropane diallylether and 0.25 g trifluoromethane sulfonic acid. The mixture was heated to 80 C. At this temperature 362.68 g of ethoxylated trimethylolpropane oxetane (average of 3.3 ethylene oxide groups) were added during a period of 5 hours. Thereafter, the reaction was continued for further 3 hours. Subsequently, a basic mineral clay was added and the reaction mixture was stirred for 2 hours, followed by filtration. The reaction product was characterized by gel permeation chromatography: Mn 842 g/mol, Mw 2014 g/mol

Example 3

[0090] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D37 with the Intermediate 11 (Molar Ratio 2.4:3.4)

[0091] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0092] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 104.49 g of the methyl-hydrogen siloxane, 45.00 g of the intermediate I1, and 45.00 g of xylene. The flask was heated to 75 C. and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene were added. A temperature increased to 104 C. was observed. The reaction mixture was stirred at 100 C. for a period of 1 hour. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 3581 g/mol, Mw 21060 g/mol

Example 4

[0093] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D37 with the Intermediate 11 (Molar Ratio 2.9:3.9)

[0094] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0095] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 106.51 g of the methyl-hydrogen siloxane, 43.49 g of the intermediate I1, and 45.00 g of xylene. The flask was heated to 75 C. and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene were added. A temperature increased to 104 C. was observed. The reaction mixture was stirred at 100 C. for a period of 1 hour. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 3774 g/mol, Mw 23394 g/mol

Example 5

[0096] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D37 with the Intermediate 11 (Molar Ratio 3.2:4.2)

[0097] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0098] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 107.76 g of the methyl-hydrogen siloxane, 42.24 g of the intermediate I1, and 45.00 g of xylene. The flask was heated to 75 C. and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene were added. A temperature increased to 104 C. was observed. The reaction mixture was stirred at 100 C. for a period of 1 hour. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 4021 g/mol, Mw 24922 g/mol

Preparation of Intermediate I2

[0099] Reaction of Trimethylolpropane Diallylether with Epsilon Caprolactone and Trimethylolpropane Oxetane, Molar Ratio 1:3:1

[0100] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 143.47 g trimethylolpropane diallylether and 0.23 g trifluoromethane sulfonic acid. The mixture was heated to 80 C. At this temperature a mixture of 229.06 g epsilon caprolactone and 77.47 g trimethylolpropane oxetane was added during a period of 5 hours. Thereafter, the reaction was continued for further 90 minutes. Subsequently, a basic mineral clay was added and the reaction mixture was stirred for 2 hours, followed by filtration. The reaction product was characterized by gel permeation chromatography: Mn 1034 g/mol, Mw 1811 g/mol

Example 6

[0101] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D37 with the Intermediate 12 (Molar Ratio 2.4:3.4)

[0102] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0103] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 109.09 g of the methyl-hydrogen siloxane, 40.91 g of the intermediate I2, and 45.00 g of xylene. The flask was heated to 75 C. and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene were added. A temperature increased to 104 C. was observed. The reaction mixture was stirred at 100 C. for a period of 1 hour. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 4366 g/mol, Mw 27109 g/mol

Example 7

[0104] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D37 with the Intermediate 12 (Molar Ratio 2.9:3.9)

[0105] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0106] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 110.91 g of the methyl-hydrogen siloxane, 39.09 g of the intermediate I2, and 45.00 g of xylene. The flask was heated to 75 C. and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene were added. A temperature increased to 104 C. was observed. The reaction mixture was stirred at 100 C. for a period of 1 hour. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 4882 g/mol, Mw 29284 g/mol

Example 8

[0107] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D37 with the Intermediate 12 (Molar Ratio 3.2:4.2)

[0108] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0109] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 112.08 g of the methyl-hydrogen siloxane, 37.92 g of the intermediate I2, and 45.00 g of xylene. The flask was heated to 75 C. and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene were added. A temperature increased to 104 C. was observed. The reaction mixture was stirred at 100 C. for a period of 1 hour. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 4839 g/mol, Mw 31244 g/mol

Preparation of Intermediate I3

[0110] Reaction of Trimethylolpropane Diallylether with Ethoxylated Trimethylolpropane Oxetane (Average of 3.3 Ethylene Oxide Groups), Molar Ratio 1:1

[0111] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 215.46 g trimethylolpropane diallylether and 0.25 g trifluoromethane sulfonic acid. The mixture was heated to 80 C. At this temperature 284.54 g of ethoxylated trimethylolpropane oxetane (average of 3.3 ethylene oxide groups) were added during a period of 5 hours. Thereafter, the reaction was continued for further 6 hours. Subsequently, a basic mineral clay was added and the reaction mixture was stirred for 2 hours, followed by filtration. The reaction product was characterized by gel permeation chromatography: Mn 782 g/mol, Mw 1887 g/mol

Example 9

[0112] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D37 with the Intermediate 13 (Molar Ratio 2.4:3.4)

[0113] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0114] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 117.35 g of the methyl-hydrogen siloxane, 32.65 g of the intermediate I3, and 45.00 g of xylene. The flask was heated to 75 C. and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene were added. A temperature increased to 104 C. was observed. The reaction mixture was stirred at 100 C. for a period of 1 hour. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 4691 g/mol, Mw 27770 g/mol

Example 10

[0115] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D37 with the Intermediate I3 (Molar Ratio 2.9:3.9)

[0116] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0117] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 118.97 g of the methyl-hydrogen siloxane, 31.03 g of the intermediate I3, and 45.00 g of xylene. The flask was heated to 75 C. and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene were added. A temperature increased to 104 C. was observed. The reaction mixture was stirred at 100 C. for a period of 1 hour. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 4856 g/mol, Mw 29320 g/mol

Example 11

[0118] Reaction of a Methyl-Hydrogen Siloxane of Average Formula MH2D37 with the Intermediate 13 (Molar Ratio 3.4:4.2)

[0119] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0120] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 119.96 g of the methyl-hydrogen siloxane, 30.04 g of the intermediate I3, and 45.00 g of xylene. The flask was heated to 75 C. and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene were added. A temperature increased to 104 C. was observed. The reaction mixture was stirred at 100 C. for a period of 1 hour. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar for a period of 1 hour. The reaction product was characterized by gel permeation chromatography: Mn 4482 g/mol, Mw 31658 g/mol

Preparation of Intermediate I4

[0121] Reaction of a methyl-hydrogen siloxane of average formula MH2D37 with trimethylolpropane Diallylether and Allylglycol (Molar Ratio 3:2:2.3)

[0122] 5.12% of the silicon atoms of the polysiloxane MH2D37 have SiH groups. This corresponds to a reaction product wherein the number of links between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%, calculated on the average number of silicon atoms per polysiloxane segment.

[0123] In a flask equipped with stirrer, thermometer, reflux condenser and nitrogen purge were placed 91.31 g of the methyl-hydrogen siloxane. The flask was heated to 75 C. and 0.22 g of a 0.2% solution of Karstedt catalyst in xylene were added. During a period of 5 minutes 4.34 g of trimethylolpropane diallylether were via a dropping funnel. An initial temperature increased to 106 C. was observed. The reaction mixture was stirred at 100 C. for a period of 3 hours and a further hour at 110. Subsequently, 4.93 g of allylglycol were added via a dropping funnel during a period of 5 minutes, followed by 3 more hours of stirring at 100 C. Thereafter volatiles were removed by vacuum distillation at 130 C. and 15 mbar. The reaction product was characterized by gel permeation chromatography: Mn 2861 g/mol, Mw 22112 g/mol

Example 12

Reaction of Intermediate I4 with Methyl Methacrylate

[0124] In a flask equipped with stirrer, thermometer, reflux condenser, air inlet, and water separator were placed 83.22 g of intermediate I4 and 16.78 g of methyl methacrylate, 0.1 g of 4-methoxyphenol, and 0.1 g of 2,6-Di-tert-butyl-4-methylphenol. The mixture was heated to 105 C. and water was removed by azeotropic distillation. After removal of all water, the mixture was cooled to 50 C. and 0.50 g of zirconium acetylacetonate were added. The mixture was heated to reflux and methanol was distilled off for 12 hours. Subsequently, volatiles were evaporated by rotary evaporation (80 C., 45 mbar). NMR analysis indicated that about 90% of the hydroxyl groups had been converted to methacryloyl groups. The reaction product was further characterized by gel permeation chromatography: Mn 4043 g/mol, Mw 20136 g/mol.

[0125] Application Tests

[0126] Preparation of Solvent-Borne Clear Coat Composition

[0127] A clear coat composition was prepared from the raw materials summarized in Table 1:

TABLE-US-00001 Raw materials Parts by weight PART A Setalux 1184 SS-51 (acrylic polyol 76.4 from allnex) Methoxypropylacetate 6.2 Xylene 17.4 Polymer of the Examples above 2.0 PART B Desmodur N75 MPA/X (Aliphatic 10.0 polyisocyanate from Covestro)

[0128] The components of Part A were mixed to form a homogenous solution.

[0129] Immediately prior to application of the coating composition to a substrate, Part A and Part B were mixed to form a homogeneous solution.

[0130] To prepare clear coats, clear coat compositions were applied on glass plates using a 100 m spiral doctor blade. After a flash-off period of 20 minutes at room temperature, the applied coating was cured at 60 C. for a period of 16 hours.

[0131] After curing, the surface of the clear coats was subjected to the following tests.

[0132] Determination of the Contact Angle of Water

[0133] The contact angle of water was determined on the coated substrates prepared as described above using a Krss instrument (model easy drop having an integrated camera). The contact angle of water was measured in order to characterize the hydrophobicity of a surface. The measurements were performed at 23 C. and a relative humidity of 65%. The results were evaluated by using the software provided together with the Krss instrument. The higher the contact angle is, the more pronounced is the hydrophobicity and the easy-to-clean effect.

[0134] Determination of the Surface Energy and the Polar and Disperse Parts Thereof

[0135] For these measurements, five different test liquids with well-known surface tensions and polar and disperse parts were used. The test liquids were water, glycerol, ethylene glycol, 1-octanol and n-dodecane. The contact angle of the test liquids on the coated substrates was measured by the contact angle method as described above from drop volumes of 5 to 11 L. The surface energy was determined with the method of Owens-Wendt-Rabel and Kaelble. The lower the polar part of the surface energy, the more advanced is the desired easy-to-clean effect.

[0136] Edding Test as Anti-Marker Test

[0137] The film surface was inscribed with an Edding 400 permanent marker and a visual assessment was made of whether the Surface can be written on. An assessment was made of whether the ink spreads on the surface, or contracts. After the ink had dried, an attempt was made to remove it by wiping with a dry cloth. Evaluation: 1-5: [0138] 1=ink contracts, can be removed without residue using a paper cloth [0139] 5=ink spreads very well on the substrate, and is virtually impossible to remove

[0140] Carbon Black Slurry Test as Anti-Dirt Pick-Up Test

[0141] The carbon black W 200 slurry had the following composition: 57.6 g water, 26.3 g DISPERBYK-190 (40%) from BYK-Chemie GmbH, 1.0 g BYK-024 from BYK-Chemie GmbH, 0.1 g Acticide MBS (a biocide from Thor Chemie) and 15.0 g coloring carbon black FW 200 (obtainable from Evonik Industries). The aforesaid components were milled with a Dispermat CV (Teflon blades, 60 minutes, 10000 rpm (18 m/sec), 40 C.). The weight ratio of the mill base to the glass beads (1 mm) was 1:1.

[0142] The slurry was applied onto the surface of the clear coat with a brush and the plates were stored 1 hour at 100 C. Next, the pigment was washed off with water and a soft cloth, so that the loose pigment can be removed.

[0143] Evaluation: 1-5:

[0144] The residues remaining are assessed [0145] 1=no residues [0146] 5=major residues

[0147] Mineral Oil Run-Off Test as Hydrophoby/Oleophoby Test:

[0148] One drop of commercially customary mineral oil was placed on the film surface. The coated film surface was then inclined until the drop had run about 10 cm. After 5 minutes, the oil track or drop reformation was evaluated visually.

[0149] Evaluation: 1-5: [0150] 1=the oil track immediately reforms into individual drops [0151] 5=the oil track does not reform, but instead possibly spreads further

TABLE-US-00002 TABLE 2 below summarizes the test results with the clear coats Contact Disperse Surface Energy Angle Water Polar Part Part Total Edding Slurry Oil Additive [] [in mN/m] [in mN/m] [in mN/m] Test Test Repellency None 80 6.8 22.3 29.1 5 3-4 4 Com. Ex. A 94 2 23.4 25.4 2 2 1-2 Comp. Ex. B 86 4.5 23.3 27.8 4 2-3 1-2 Ex. 1 102 0.3 24.9 25.2 2 1-2 1 Ex. 2 98 0.9 25 25.9 1 1-2 1-2 Ex. 3 102 0.3 22.3 22.6 1 1-2 1-2 Ex. 4 102 0.2 22.7 22.9 1 2 1 Ex. 5 96 1.2 21.4 22.6 1 1-2 1 Ex. 6 100 0.9 19.1 20.0 1 1-2 1 Ex. 7 96 1.7 18.8 20.5 1 1-2 1 Ex. 8 99 1 18.9 19.9 1 1-2 1 Ex. 9 103 0.3 22.8 23.1 1 1-2 1 Ex. 10 98 0.8 22.5 23.3 1 1-2 1 Ex. 11 96 1.3 20.7 22.0 1-2 1-2 1

[0152] From the results in Table 2 it can be concluded that the polymers of the invention cause a higher water contact angle than the comparative examples on the clear coat surfaces. They also cause a lower polar part contribution of the total surface energy. This is an indication that the polysiloxanes of the invention hydrophobize the coating surface and equip it with easy-to-clean properties. This is reflected in the Soiling Tests on the coatings represented by the Edding Test, Carbon Black Slurry Test and Mineral Oil Run-Off Test.

[0153] The results show that by using the polymers of the invention as additive, dirt (as carbon black)-repelling and oil-repelling surfaces with improved anti-marker behavior (Edding test) are obtained whose performances are exceeding that of the comparative products.