POLYSILOXANES AS ANTI-ADHESIVE AND DIRT-REPELLANT ADDITIVES, METHOD FOR THE PRODUCTION AND USE THEREOF

Abstract

The invention relates to polysiloxanes which can be obtained by adding at least one monovinyl functional polysiloxane and at least one epoxy functional, monovinyl functional component to a Si—H functional polysiloxane. The invention also relates to the production of polysiloxanes, to compositions containing said polysiloxanes, to the use of the compositions in a coating method and to substrates coated with the composition and to the use of the polysiloxanes as additives for finishing surfaces of hardened compositions with anti-adhesive properties.

Claims

1. A polysiloxane obtained by the addition of at least one monovinyl-functional polysiloxane and at least one epoxy-functional, monovinyl-functional component onto an Si—H-functional polysiloxane, characterized in that the at least one monovinyl-functional polysiloxane possesses the formula (I): ##STR00017## in which Z is hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is a monovalent radical of the following formula: ##STR00018## in which p=0 or 1, q=0 to 30, and r=1 to 400, and, if p=1, q≧2, R.sup.a is a linear, halogenated or unhalogenated alkyl radical having 1 to 30 carbon atoms, a branched or cyclic, halogenated or unhalogenated alkyl radical having 3 to 30 carbon atoms, or an aryl radical having 6 to 30 carbon atoms, or an alkylaryl radical or an arylalkyl radical having 7 to 30 carbon atoms, or an alkoxyalkylene oxide-alkyl radical or alkoxypolyalkylene oxide-alkyl radical, all R.sup.b, R.sup.c, R.sup.d, and R.sup.e independently of one another are a linear, halogenated or unhalogenated alkyl radical having 1 to 30 carbon atoms, a branched or cyclic, halogenated or unhalogenated alkyl radical having 3 to 30 carbon atoms, or an aryl radical having 6 to 30 carbon atoms, or an alkylaryl radical or an arylalkyl radical having 7 to 30 carbon atoms, R.sup.d and R.sup.e additionally, independently of one another, may be R.sup.a[SiR.sup.bR.sup.cO].sub.r, in which R.sup.a, R.sup.b, R.sup.c, and r are as defined above and are selected independently thereof.

2. The polysiloxane as claimed in claim 1, characterized in that the Si—H-functional polysiloxane is catenated.

3. The polysiloxane as claimed in claim 1, characterized in that the at least one epoxy-functional, monovinyl-functional component possesses the formula (II): ##STR00019## in which Z is hydrogen or an alkyl group having 1 to 4 carbon atoms and Y is a monovalent radical of the following formula:
-L-Epoxy in which L is a linking group and Epoxy is an oxirane ring, and where the oxirane ring is bonded by one or both carbon atoms to the linking group L.

4. The polysiloxane as claimed in claim 1, characterized in that at least one monovinyl-functional component different from the monovinyl-functional polysiloxane and from the epoxy-functional, monovinyl-functional component had been reacted with the Si—H-functional polysiloxane, and this component possesses the formula (III): ##STR00020## in which Z is hydrogen or an alkyl group having 1 to 4 carbon atoms, and Q is a monovalent radical of the following formula:
-(L′).sub.v-R in which v=0 or 1, L′ is a linking group, and R is a radical —SiR.sup.x.sub.nR.sup.y.sub.3-n, in which n=1 to 3, R.sup.x independently at each occurrence is halogen, Oalkyl, or O—CO-alkyl, and R.sup.y is alkyl or is aryl having 6 to 10 carbon atoms; or R is a polymeric radical having ether, ester and/or urethane groups.

5. The polysiloxane as claimed in claim 1, characterized in that at least one monohydroxy-functional polymeric component which contains ether, ester and/or urethane groups had been reacted by condensation reaction with the Si—H-functional polysiloxane before addition reactions of monovinyl-functional components onto the Si—H-functional polysiloxane were carried out.

6. The polysiloxane as claimed in claim 1, characterized in that it possesses general formula (IV): ##STR00021## where Y is a monovalent radical of the following formula:
-L-Epoxy in which L is a linking group and Epoxy is an oxirane ring, and where the oxirane ring is bonded by one or both carbon atoms to the linking group L; Q is a monovalent radical of the following formula:
-(L′).sub.v-R in which v=0 or 1, L′ is a linking group, and R is a radical —SiR.sup.x.sub.nR.sup.y.sub.3-n, in which n=1 to 3, R.sup.x independently at each occurrence is halogen, Oalkyl, or O—CO-alkyl, and R.sup.y is alkyl or is aryl having 6 to 10 carbon atoms; or R is a polymeric radical having ether, ester and/or urethane groups; s=0 or 1; R.sup.1 independently at each occurrence is C.sub.1-C.sub.14 alkyl, C.sub.6-C.sub.10 aryl or C.sub.7-C.sub.12 aralkyl; R.sup.2 and R.sup.3 independently of one another are CH.sub.2CHZX, CH.sub.2CHZY or (CH.sub.2CHZ).sub.sQ, or are —(R.sup.4).sub.i—C.sub.1-C.sub.14 alkyl, —(R.sup.4).sub.i—C.sub.6-C.sub.14 aryl or —(R.sup.4).sub.i—C.sub.7-C.sub.14 aralkyl, in which i=0 or 1 and R.sup.4 is O, O—CO, O—CO—O or —OSO.sub.2—; A=0 to 20, B=2 to 300, C=0 to 20, and D=0 to 20; where if C=0, R.sup.2=X and/or R.sup.3=X, and where if D=0, R.sup.2=Y and/or R.sup.3=Y.

7. A process for preparing one or more polysiloxanes as defined in claim 1, characterized in that the Si—H-functional polysiloxane in an optional first stage is partially reacted with a monohydroxy-functional, polymeric component by condensation reaction, and in a further stage is reacted with the monovinyl-functional components by hydrosilylation reactions.

8. A composition comprising one or more of the polysiloxanes as defined in claim 1.

9. The composition as claimed in claim 8, characterized in that it is a coating material, a polymeric molding compound or a thermoplastic.

10. The composition as claimed in claim 8, characterized in that the composition comprises epoxy resins.

11. The composition as claimed in claim 8, characterized in that the one or more polysiloxanes are present in a total amount of 0.1 to 10 wt %, based on the total weight of the composition.

12. A method for coating a substrate selected from metal, glass, ceramic, and plastic materials, where a composition of the invention as defined in claim 8 is applied to the substrate, the coating is physically dried and/or cured by reactive self-crosslinking and/or cured by reactive external crosslinking.

13. A coated substrate obtained by the method as claimed in claim 12.

14. A method comprising adding the polysiloxanes as defined in claim 1 to a composition selected from the group of coating materials, polymeric molding compounds, and thermoplastics for equipping the surfaces of the cured compositions with antiadhesive and/or dirt-repellent properties.

15. The composition as claimed in claim 9, characterized in that the composition comprises epoxy resins.

Description

SYNTHESIS EXAMPLES

Gel Permeation Chromatography (GPC)

[0080] The gel permeation chromatography was carried out at 40° C. using an HPLC pump (Bischoff HPLC 2200) and a refractive index detector (Waters 419). The eluent used was tetrahydrofuran and the elution rate was 1 ml/min. Polystyrene standards were used for calibration. The number-average molecular weight M.sub.n, the weight-average molecular weight M.sub.w, the centrifuge-average molecular weight M.sub.c, and the polydispersity (=M.sub.w/M.sub.n) were determined using the NTeqGPC software.

Abbreviations

[0081] M=—O.sub.0.5Si(CH.sub.3).sub.3 [0082] M.sup.H=—O.sub.0.5SiH(CH.sub.3).sub.2 [0083] M.sup.Butyl=—O.sub.0.5Si(butyl)(CH.sub.3).sub.2 [0084] D==—O.sub.0.5Si(CH.sub.3).sub.2O.sub.0.5— [0085] D.sup.H=—O.sub.0.5SiH(CH.sub.3)O.sub.0.5— [0086] D.sup.R′=—O.sub.0.5SiR′(CH.sub.3)O.sub.0.5— [0087] D.sup.R″=—O.sub.0.5SiR″(CH.sub.3)O.sub.0.5— [0088] D.sup.R′″=—O.sub.0.5SiR′″(CH.sub.3)O.sub.0.5— [0089] M.sup.CH—CH2=—O.sub.0.5Si(CH═CH.sub.2)(CH.sub.3).sub.2

Synthesis of Monovinyl-Functional Polysiloxanes of the Following Formulae:

[0090]
M.sup.ButylD.sub.25M.sup.CH═CH2,M.sup.ButylD.sub.40M.sup.CH═CH2 and M.sup.ButylD.sub.66M.sup.CH═CH2

[0091] Monovinyl-terminated polydimethylsiloxanes possess an average molecular weight of 2000, 3000, 5000 and are prepared in analogy to example 1a (1.sup.st stage) of patent specification DE 10 2008 031 901 A1, with the difference that the terminal functionalization was carried out with chlorodimethylvinylsilane rather than chlorodimethylsilane.

Example 1

[0092] Reaction of a Methyl-Hydrogen-Polysiloxane Having the Mean Average Formula MD.sup.H.sub.8D.sub.91M with M.sup.ButylD.sub.25M.sup.CH═CH2 and Allyl Glycidyl Ether

[0093] A 250 ml 3-neck flask with stirrer, thermometer, and reflux condenser is charged at room temperature with 80.57 g of a methyl-hydrogen-polysiloxane having the mean average formula MD.sup.H.sub.8D.sub.91M and 37.47 g of a monovinyl-functional polysiloxane having the average formula M.sup.ButylD.sub.25M.sup.CH═CH2, and this initial charge is heated to 75° C. under a nitrogen atmosphere. When this temperature has been reached, 0.26 g of Karstedt catalyst at 0.2% in xylene is added. The quantity of heat released during the reaction raises the temperature to 103° C. After 30 minutes at 100° C., the remaining Si—H groups are determined by gas volumetry and the theoretical conversion of 20 mol % is found. For the 2.sup.nd reaction stage, 0.03 g of Karstedt catalyst at 0.2% in xylene is added, and then 11.96 of allyl glycidyl ether are metered in over the course of 10 minutes, the temperature rising to 106° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows complete conversion. In the subsequent distillation, under a reduced pressure of around 20 mbar at 130° C., all of the volatile constituents are distilled off in an hour. This gives a pale brown, clear, viscous product.

Average structure: MD.sup.R′.sub.xD.sup.R′.sub.yD.sub.91M

##STR00008##

[0094] GPC data found for the product are as follows:

[0095] M.sub.w: 18124 g/mol, M.sub.c: 33679 g/mol, M.sub.n: 3299 g/mol, polydispersity: 5.33

Example 2

[0096] Reaction of a Methyl-Hydrogen-Polysiloxane Having the Mean Average Formula MD.sup.H.sub.9D.sub.76M with M.sup.ButylD.sub.25M.sup.CH═CH2 and Allyl Glycidyl Ether

[0097] A 250 ml 3-neck flask with stirrer, thermometer, and reflux condenser is charged at room temperature with 73.49 g of a methyl-hydrogen-polysiloxane having the mean average formula MD.sup.H.sub.9D.sub.76M and 42.84 g of a monovinyl-functional polysiloxane having the average formula M.sup.ButylD.sub.25M.sup.CH═CH2, and this initial charge is heated to 75° C. under a nitrogen atmosphere. When this temperature has been reached, 0.26 g of Karstedt catalyst at 0.2% in xylene is added. The quantity of heat released during the reaction raises the temperature to 104° C. After 30 minutes at 100° C., the remaining Si—H groups are determined by gas volumetry and the theoretical conversion of 20 mol % is found. For the 2.sup.nd reaction stage, 0.03 g of Karstedt catalyst at 0.2% in xylene is added, and then 13.67 g of allyl glycidyl ether are metered in over the course of 10 minutes, the temperature rising to 106° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows complete conversion. In the subsequent distillation, under a reduced pressure of around 20 mbar at 130° C., all of the volatile constituents are distilled off in an hour. This gives a pale brown, clear, viscous product.

[0098] Average structure: MD.sup.R′.sub.xD.sup.R″.sub.yD.sub.mM

##STR00009##

[0099] GPC data found for the product are as follows:

[0100] M.sub.w: 19210 g/mol, M.sub.c: 37623 g/mol, M.sub.n: 3743 g/mol, polydispersity: 5.13

Example 3 (Comparative) (without Monovinyl-Functional Polysiloxane)

[0101] Reaction of a Methyl-Hydrogen-Polysiloxane Having the Mean Average Formula MD.sup.H.sub.9.5D.sub.153M with Allyl Glycidyl Ether

[0102] In a 250 ml 3-neck flask with stirrer, thermometer, and reflux condenser at room temperature 134.27 g of a methyl-hydrogen-polysiloxane having the mean average formula MD.sup.H.sub.9.5D.sub.153M are heated to 75° C. under a nitrogen atmosphere. When this temperature has been reached, 0.33 g of Karstedt catalyst at 0.2% in xylene is added, then 16.73 g of allyl glycidyl ether are metered in over the course of 10 minutes, the temperature rising to 108° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows complete conversion. In the subsequent distillation, under a reduced pressure of around 20 mbar at 130° C., all of the volatile constituents are distilled off in an hour. This gives a pale brown, clear, viscous product.

[0103] Average structure: MD.sub.153D.sup.R″.sub.9.5M where

##STR00010##

[0104] GPC data found for the product are as follows:

[0105] M.sub.w: 20683 g/mol, M.sub.c: 37697 g/mol, M.sub.n: 2571 g/mol, polydispersity: 8.04

Example 4 (Comparative) (without Monovinyl-Functional Polysiloxane)

[0106] Reaction of a Methyl-Hydrogen-Polysiloxane Having the Mean Average Formula MD.sup.H.sub.8D.sub.91M with Allyl Glycidyl Ether

[0107] In a 250 ml 3-neck flask with stirrer, thermometer, and reflux condenser at room temperature 127.62 g of a methyl-hydrogen-polysiloxane having the mean average formula MD.sup.H.sub.8D.sub.91M are heated to 80° C. under a nitrogen atmosphere. When this temperature has been reached, 0.33 g of Karstedt catalyst at 0.2% in xylene is added, then 22.38 g of allyl glycidyl ether are metered in over the course of 10 minutes, the temperature rising to 105° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows complete conversion. In the subsequent distillation, under a reduced pressure of around 20 mbar at 130° C., all of the volatile constituents are distilled off in an hour. This gives a pale brown, clear, viscous product.

[0108] Average structure: MD.sub.91D.sup.R″.sub.8M where

##STR00011##

[0109] GPC data found for the product are as follows:

[0110] M.sub.w: 13181 g/mol, M.sub.c: 23552 g/mol, M.sub.n: 2418 g/mol, polydispersity: 5.44

Example 5

[0111] Reaction of a Methyl-Hydrogen-Polysiloxane Having the Mean Average Formula MD.sup.H.sub.8D.sub.91M with M.sup.ButylD.sub.40M.sup.CH═CH2 and Allyl Glycidyl Ether

[0112] A 250 ml 3-neck flask with stirrer, thermometer, and reflux condenser is charged at room temperature with 88.79 g of a methyl-hydrogen-polysiloxane having the mean average formula MD.sup.H.sub.8D.sub.91M and 47.23 g of a monovinyl-functional polysiloxane having the average formula M.sup.ButylD.sub.40M.sup.CH═CH2, and this initial charge is heated to 75° C. under a nitrogen atmosphere. When this temperature has been reached, 0.30 g of Karstedt catalyst at 0.2% in xylene is added. The quantity of heat released during the reaction raises the temperature to 103° C. After 30 minutes at 100° C., the remaining Si—H groups are determined by gas volumetry and the theoretical conversion of 13.3 mol % is found. For the 2.sup.nd reaction stage, 0.03 g of Karstedt catalyst at 0.2% in xylene is added, and then 13.98 g of allyl glycidyl ether are metered in over the course of 10 minutes, the temperature rising to 106° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows complete conversion. In the subsequent distillation, under a reduced pressure of around 20 mbar at 130° C., all of the volatile constituents are distilled off in an hour. This gives a pale brown, clear, viscous product.

[0113] Average structure: MD.sup.R′.sub.xD.sup.R″.sub.yD.sub.91M

##STR00012##

[0114] GPC data found for the product are as follows:

[0115] M.sub.w: 17064 g/mol, M.sub.c: 31429 g/mol, M.sub.n: 3166 g/mol, polydispersity: 5.39

Example 6

[0116] Reaction of a Methyl-Hydrogen-Polysiloxane Having the Mean Average Formula MD.sup.H.sub.9D.sub.76M with M.sup.ButylD.sub.40M.sup.CH═CH2 and Allyl Glycidyl Ether

[0117] A 250 ml 3-neck flask with stirrer, thermometer, and reflux condenser is charged at room temperature with 68.53 g of a methyl-hydrogen-polysiloxane having the mean average formula MD.sup.H.sub.9D.sub.76M and 68.72 g of a monovinyl-functional polysiloxane having the average formula M.sup.ButylD.sub.40M.sup.CH═CH2, and this initial charge is heated to 75° C. under a nitrogen atmosphere. When this temperature has been reached, 0.30 g of Karstedt catalyst at 0.2% in xylene is added. The quantity of heat released during the reaction raises the temperature to 102° C. After 30 minutes at 100° C., the remaining Si—H groups are determined by gas volumetry and the theoretical conversion of 20 mol % is found. For the 2.sup.nd reaction stage, 0.03 g of Karstedt catalyst at 0.2% in xylene is added, and then 12.75 g of allyl glycidyl ether are metered in over the course of 10 minutes, the temperature rising to 106° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows complete conversion. In the subsequent distillation, under a reduced pressure of around 20 mbar at 130° C., all of the volatile constituents are distilled off in an hour. This gives a pale brown, clear, viscous product.

[0118] Average structure: MD.sup.R′.sub.xD.sup.R″.sub.yD.sub.76M

##STR00013##

[0119] GPC data found for the product are as follows:

[0120] M.sub.w: 20259 g/mol, M.sub.c: 39641 g/mol, M.sub.n: 4103 g/mol, polydispersity: 4.93

Example 7

[0121] Reaction of a Methyl-Hydrogen-Polysiloxane Having the Mean Average Formula MD.sup.H.sub.8D.sub.91M with M.sup.ButylD.sub.66M.sup.CH═CH2 and Allyl Glycidyl Ether

[0122] A 250 ml 3-neck flask with stirrer, thermometer, and reflux condenser is charged at room temperature with 91.73 g of a methyl-hydrogen-polysiloxane having the mean average formula MD.sup.H.sub.8D.sub.91M and 43.17 g of a monovinyl-functional polysiloxane having the average formula M.sup.ButylD.sub.66M.sup.CH═CH2 with 57.98 of xylene and this initial charge is heated to 75° C. under a nitrogen atmosphere. When this temperature has been reached, 0.30 g of Karstedt catalyst at 0.2% in xylene is added. The quantity of heat released during the reaction raises the temperature to 101° C. After 30 minutes at 100° C., the remaining Si—H groups are determined by gas volumetry and the theoretical conversion of 8 mol % is found. At 100° C. and 45 mbar, using a water separator, 50.1 g of xylene are distilled off over the course of 20 minutes. The reduced pressure is ended by introduction of nitrogen. For the 2.sup.nd reaction stage, 0.03 g of Karstedt catalyst at 0.2% in xylene is added, and then 15.1 g of allyl glycidyl ether are metered in over the course of 10 minutes, the temperature rising to 107° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows complete conversion. In the subsequent distillation, under a reduced pressure of around 20 mbar at 130° C., all of the volatile constituents are distilled off in an hour. This gives a pale brown, clear, viscous product.

[0123] Average structure: MD.sup.R′.sub.xD.sup.R″.sub.yD.sub.91M

##STR00014##

[0124] GPC data found for the product are as follows:

[0125] M.sub.w: 19450 g/mol, M.sub.n: 4287 g/mol, polydispersity: 4.53

Example 8

[0126] Reaction of a Methyl-Hydrogen-Polysiloxane Having the Mean Average Formula MD.sup.H.sub.24D.sub.76M with M.sup.ButylD.sub.40M.sup.CH═CH2, Allyl Polyether Having the Average Formula CH.sub.2═CH—CH.sub.2O(CH.sub.2—CH.sub.2O).sub.6—CH.sub.3, and Allyl Glycidyl Ether

[0127] A 250 ml 3-neck flask with stirrer, thermometer, and reflux condenser is charged at room temperature with 38.17 g of a methyl-hydrogen-polysiloxane having the mean average formula MD.sup.H.sub.24D.sub.76M and 55.39 g of a monovinyl-functional polysiloxane having the average formula M.sup.ButylD.sub.40M.sup.CH═CH2, and this initial charge is heated to 75° C. under a nitrogen atmosphere. When this temperature has been reached, 0.21 g of Karstedt catalyst at 0.2% in xylene is added. The quantity of heat released during the reaction raises the temperature to 100° C. After 30 minutes at 100° C., the remaining Si—H groups are determined by gas volumetry and the theoretical conversion of 20 mol % is found. For the 2.sup.nd reaction stage, 0.17 g of Karstedt catalyst at 0.2% in xylene and also 51.93 g of xylene are added, and then 27.6 g of allyl polyether having the average formula CH.sub.2═CH—CH.sub.2O(CH.sub.2—CH.sub.2O).sub.6—CH.sub.3 are metered in over the course of 10 minutes, the temperature rising to 101° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows further conversion of 55 mol %. For the 3.sup.rd reaction stage, 0.03 g of Karstedt catalyst at 0.2% in xylene and also 3.79 g of xylene are added and subsequently, over the course of 10 minutes, 8.84 g of allyl glycidyl ether are metered in, the temperature rising to 102° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows complete conversion. In the subsequent distillation, under a reduced pressure of around 20 mbar at 130° C., all of the volatile constituents are distilled off in an hour. This gives a pale brown, clear, viscous product.

[0128] Average structure: MD.sup.R′.sub.xD.sup.R″.sub.yD.sup.R′″.sub.zD.sub.76M

##STR00015##

[0129] GPC data found for the product are as follows:

[0130] M.sub.w: 28041 g/mol, M.sub.n: 3335 g/mol, polydispersity: 8.40

Example 9

[0131] Reaction of a Methyl-Hydrogen-Polysiloxane Having the Mean Average Formula MD.sup.H.sub.9D.sub.76M with M.sup.ButylD.sub.66M.sup.CH═CH2, Allyl Glycidyl Ether and Vinyltrimethoxysilane

[0132] A 250 ml 3-neck flask with stirrer, thermometer, and reflux condenser is charged at room temperature with 67.45 g of a methyl-hydrogen-polysiloxane having the mean average formula MD.sup.H.sub.9D.sub.76M and 67.62 g of a monovinyl-functional polysiloxane having the average formula M.sup.ButylD.sub.66M.sup.CH═CH2, and this initial charge is heated to 75° C. under a nitrogen atmosphere. When this temperature has been reached, 0.30 g of Karstedt catalyst at 0.2% in xylene is added. The quantity of heat released during the reaction raises the temperature to 102° C. After 30 minutes at 100° C., the remaining Si—H groups are determined by gas volumetry and the theoretical conversion of 20 mol % is found. For the 2.sup.nd reaction stage, 0.02 g of Karstedt catalyst at 0.2% in xylene is added, and then 4.56 g of allyl glycidyl ether are metered in over the course of 5 minutes. The temperature rises to 110° C. After 15 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows conversion of a further 40 mol %. For the 3.sup.rd reaction stage, 0.01 g of Karstedt catalyst at 0.2% in xylene are added and subsequently, over the course of 15 minutes, 10.37 g of vinyltrimethoxysilane are metered in, the temperature rising to 107° C. After 60 minutes of subsequent reaction at 100° C., gas-volumetric determination of the remaining Si—H groups shows complete conversion. In the subsequent distillation, under a reduced pressure of around 20 mbar at 130° C., all of the volatile constituents are distilled off in an hour. This gives a pale brown, clear, viscous product.

[0133] Average structure: MD.sup.R′.sub.xD.sup.R″.sub.yD.sup.R′″.sub.zD.sub.76M

##STR00016##

[0134] GPC data found for the product are as follows:

[0135] M.sub.w: 28041 g/mol, M.sub.c: 67596 g/mol, M.sub.n: 3335 g/mol, polydispersity: 8.40

Comparative Example A

[0136] Mono-SiH-functional polysiloxanes are prepared in accordance with the process described in patent specification DE 102008031901 (example 1a).

Synthesis of Monoamino-Functional Polysiloxane

[0137] A four-neck flask provided with stirrer, thermometer, dropping funnel, reflux condenser, and nitrogen inlet tube is charged with mono-SiH-functional polysiloxane (250 g, Mn≈2000 g/mol) and Karstedt catalyst (4.38 g, 0.2% solution in xylene), and the components are mixed thoroughly and heated to 100° C. Allylamine (9.29 g) is added dropwise over 30 minutes. The conversion of the mono-SiH-functional polysiloxane is monitored by gas-volumetric determination. Following complete conversion, the excess allylamine is removed by distillation. The amine number measured for the product is 24.1 mg KOH/g.

Synthesis of a Copolymer Containing Polysiloxane Groups

[0138] A four-neck flask provided with stirrer, thermometer, dropping funnel, reflux condenser, and nitrogen inlet tube is charged with the monoamino-functional polysiloxane from example 1 (254.7 g) and 1,6-hexanediglycidyl ether (169.6 g) and this initial charge is heated to 140° C. under nitrogen. After a reaction time of 2 hours, octylamine (75.6 g) is added slowly dropwise with stirring. The epoxide conversion is monitored by .sup.1H-NMR. Following quantitative conversion of the epoxide group, the reaction is discontinued.

[0139] The product obtained here possesses an epoxy-amine structure as polymer backbone and has polysiloxane side chains bonded to the polymer backbone.

[0140] GPC data found for the product are as follows:

[0141] M.sub.w: 9779 g/mol, M.sub.n: 3014 g/mol, polydispersity: 3.24

Comparative Example B

[0142] A four-neck flask provided with stirrer, thermometer, dropping funnel, reflux condenser, and nitrogen inlet tube is charged with 6.10 g of Silaplane FM-0721 (mono-methacryloyl-functional polysiloxane macromer having an average molecular weight of 5000; Chisso Corporation) and 100 g of PMA and these components are thoroughly mixed. Throughout the reaction, nitrogen is passed over the mixture. The temperature is raised to 135° C. and a mixture of 1.21 g of MAA, 25.3 g of IBMA, 15.4 g of HEMA, 17.4 g of STY and 0.89 g of Trigonox C is metered in over the course of 3 hours. After the end of metering, 0.15 g of Trigonox C is added immediately. After a further 30 minutes and 60 minutes, a further 0.15 g of Trigonox C is added each time. Thereafter the batch is held at 135° C. for an hour more.

[0143] The product obtained here possesses a poly(meth)acrylate backbone as polymer backbone and has hydroxyethyl groups along the poly(meth)acrylate backbone.

[0144] GPC data found for the product are as follows:

[0145] M.sub.w: 14500 g/mol, M.sub.n: 3746 g/mol, polydispersity: 3.87

Comparative Example C

[0146] A four-neck flask provided with stirrer, thermometer, dropping funnel, reflux condenser, and nitrogen inlet tube is charged with 7.21 g of Silaplane FM-0721 and 119 g of propylene glycol monomethyl ether acetate and these components are thoroughly mixed. Throughout the reaction, nitrogen is passed over the mixture. The temperature is raised to 135° C. and a mixture of 32.24 g of isobutyl methacrylate, 18.76 g of glycidyl methacrylate, 21.14 g of styrene and 1.08 g of tert-butyl peroxybenzoate is metered in over the course of 3 hours. After the end of metering, 0.18 g of tert-butyl peroxybenzoate is added immediately. After a further 30 minutes and 60 minutes, a further 0.18 g of Trigonox C is added each time. Thereafter the batch is held at 135° C. for an hour more.

[0147] The product obtained here possesses a poly(meth)acrylate backbone as polymer backbone and has glycidyl groups along the poly(meth)acrylate backbone.

[0148] GPC data found for the product are as follows:

[0149] M.sub.w: 16623 g/mol, M.sub.n: 5381 g/mol, polydispersity: 2.63

Comparative Example D

[0150] A four-neck flask provided with stirrer, thermometer, dropping funnel, reflux condenser, and nitrogen inlet tube is charged with 7.21 g of Silaplane FM-0721 and 119 g of propylene glycol monomethyl ether acetate and these components are thoroughly mixed. Throughout the reaction, nitrogen is passed over the mixture. The temperature is raised to 135° C. and a mixture of 41.62 g of isobutyl methacrylate, 9.38 g of glycidyl methacrylate, 21.14 g of styrene and 1.08 g of tert-butyl peroxybenzoate, Akzo Nobel is metered in over the course of 3 hours. After the end of metering, 0.18 g of tert-butyl peroxybenzoate is added immediately. After a further 30 minutes and 60 minutes, a further 0.18 g of tert-butyl peroxybenzoate is added each time. Thereafter the batch is held at 135° C. for an hour more.

[0151] The product obtained here possesses a poly(meth)acrylate backbone as polymer backbone and has glycidyl groups along the poly(meth)acrylate backbone, but fewer than in comparative example C.

[0152] GPC data found for the product are as follows:

[0153] M.sub.w: 12378 g/mol, M.sub.n: 4850 g/mol, polydispersity: 2.55

Use Examples and Test Methods

1. Determining the Hydrophobicity of the Formulations by Measurement of the Water Contact Angle

[0154] The coatings were cured at 40° C. for three days. The contact angle measurements relative to water were carried out after storage of the samples at room temperature for three days (measuring instrument: Krüss G2, Easy Drop).

2. Soiling Tests on the Formulations

[0155] The carbon black slurry test (“CB slurry test”), the carbon black handcream test (“CB cream test”), the carbon black mineral oil test (“CB oil test”) and the “marker test” were carried out.

[0156] The evaluation range extends from 1 to 5, with a figure of 1 denoting “no residues”, while a figure of 5 denotes “major residues”.

(a) Carbon Black Slurry Test (“CB Slurry Test”)

[0157] A carbon black slurry is prepared by mixing 2.0 g of Special Black 6 (Evonik), 100 g of water and 5 drops of liquid soap (Pril®). The carbon black slurry is applied to the coated metal panel using a small brush. This is followed by drying at 50° C. for 1 hour. The panels are then washed under running water, using a soft brush. Washing takes place, without using soap or relatively harsh scrubbing, until the coating has been cleaned as well as possible.

(b) Carbon Black Handcream Test (“CB Cream Test”):

[0158] A 1 weight percent preparation of carbon black powder (FW 200 from Evonik Degussa) in a handcream (Wuta camomile handcream from Herbacin Cosmetic GmbH) is prepared. This cream is rubbed with the finger onto the coated metal panels. The soiled panels are stored at room temperature overnight and then cleaned with dry paper (Tork paper hand towels from Svenska Cellulosa AB) or wet paper (soap), soaked with a 5% Pril® solution, in order to test the cleanability.

(c) Carbon Black Mineral Oil Test (“CB Oil Test”):

[0159] A 1 weight percent suspension of carbon black powder (FW 200 from Evonik Degussa) in mineral oil (Q8 Puccini 32P from Kuwait Petroleum International Lubricants) is prepared. This suspension is rubbed with the finger onto the coated metal panels. The soiled panels are stored at room temperature overnight and then cleaned with dry paper (Tork paper handtowels from Svenska Cellulosa AB) or wet paper, soaked with a 5% Pril® solution, in order to test the cleanability.

3. Marker Test

[0160] A permanent marker of type “Magic Ink Red” (available from Magic Ink Company, Japan) is used to write on the paint surface, and, after the ink has dried (1 minute), an attempt is made to wipe it off with a dry towel or with isopropanol-soaked paper. The evaluation range extends from 1 to 5, with a figure of 1 denoting “the ink can be removed without residue using a paper towel” and a figure of 5 denoting “virtually impossible to remove”.

4. Measuring the Leveling of the Formulations

[0161] The leveling was measured using the Wave-Scan Dual instrument from BYK-Gardner on the coated metal panels. The longwave (LW) and the shortwave (SW) were determined.

5. Determining the Slip Resistance

[0162] Determining the slip resistance or the reduction in slip resistance was carried out using the Altek 9505 AE slip meter in accordance with performance testing method APM-001 from BYK-Chemie GmbH. For this purpose, the coating material under test was applied to glass plates which measured 10×40 cm and had been cleaned in a dishwasher beforehand. The plate is clamped into an applicator unit and positioned in such a way that a 500 g weight can be placed centrally on the coating. The weight is pushed over the sample at a speed of 5 inch/min. The measurements are carried out against a standard sample (blank sample), which is used as a reference point for the evaluation. In the evaluation, an absolute value (COF=coefficient of friction) is reported.

Coating Material Systems

[0163] Performance testing of the polysiloxanes of the invention took place in five different coating materials.

Coating Material 1

Coating Material Based on a Solvent-Based Pigmented Epoxy Resin/Polyamide Hardener System (Conventional Epoxy System)

[0164] The procedure for producing the coating material is as follows. First of all a component A is prepared by mixing the materials listed as items 1 to 3 in table 1 until homogeneity, using a dissolver with a cog disk at 2000 revolutions per minute. The corresponding quantities are reported in parts by weight in table 1. The material of item 4 in table 1 is then added and mixing takes place at 3000 revolutions per minute until a perfect gel is formed. Thereafter the materials of items 5 to 7 in table 1 are added at 3000 revolutions per minute and stirring is continued for 15 minutes more. After that the materials of items 8 to 11 in table 1 are added at 2000 revolutions per minute and stirring is continued for 5 minutes more.

[0165] Component B is produced by stirring together the materials of items 12 to 14 in table 1 for 15 minutes at 2000 revolutions per minute.

[0166] In the next step, 2 wt % of additive (inventive polysiloxane or noninventive additive), based on the sum of components A and B, is added to the mixtures of components A and B, and stirring takes place for 5 minutes at 2000 revolutions per minute.

[0167] The coating material composition is applied in a wet film thickness of 150 μm to a glass plate. The glass plate is kept at room temperature (23° C.) overnight and then dried in an oven at 40° C. for 3 days.

[0168] After it has cooled, the coating film is subjected to the test methods set out above.

TABLE-US-00001 TABLE 1 Item Component A 1 Dowanol PM.sup.1 3.9 2 Xylene 4.7 3 Epikote 1001X75.sup.2 15.6 4 Bentone SD-2.sup.3 1.2 5 Disperbyk-142.sup.4 0.6 6 Ti-Pure R902.sup.5 25.0 7 Blanc Fixe N.sup.6 14.6 8 Epikote 1001X75.sup.2 23.4 9 Solvesso 100.sup.7 5.9 10 Dowanol PM.sup.1 2.4 11 Xylene 2.7 Total 100.0 Component B 12 Ancamide 220-X-70.sup.8 10.0 (95.5% crosslinker) 13 Ancamine K-54.sup.9 0.4 14 Xylene 2.0 Total 12.4 .sup.1Dowanol PM is a propylene glycol methyl ether from Dow Chemical Company .sup.2Epikote 1001X75 is a 75 wt % strength solution of an epoxy resin in xylene from Momentive .sup.3Bentone SD-2 is a rheological additive based on an organically modified bentonite clay from Elementis Specialties .sup.4Disperbyk-142 is a wetting and dispersing agent from Byk Chemie GmbH .sup.5Ti-Pure R902 is a titanium dioxide pigment from DuPont Titanium Technologies .sup.6Blanc Fixe N is a synthetic barium sulfate from Solvay Chemicals .sup.7Solvesso 100 is an aromatic solvent from ExxonMobil .sup.8Ancamide 220-X-70 is a hardener from Air Products .sup.9Ancamine K-54 is an epoxy accelerator from Air Products

Coating Material 2

[0169] Coating Material Based on a Solvent-Free Pigmented Epoxy Resin/Polyamide Epoxy Hardener System (Solvent-Free Epoxy System with High Viscosity)

[0170] The procedure for producing the coating material is as follows. First of all a component A is prepared by mixing the materials listed as items 1 to 5 in table 2 until homogeneity, using a dissolver with a cog disk at 2000 revolutions per minute. The corresponding quantities are reported in parts by weight in table 2. Thereafter the material of items 6 to 7 in table 2 is added and mixed at 3000 revolutions per minute. After that the materials of item 8 in table 2 are added at 3000 revolutions per minute and stirring is continued for 10 minutes more.

[0171] In the next step, 2 wt % of additive (inventive polysiloxane or noninventive additive), based on the sum of components A and B, is added to the mixtures of components A and B, and stirring takes place for 5 minutes at 2000 revolutions per minute.

[0172] The coating material composition is applied in a wet film thickness of 150 μm to a glass plate. The glass plate is kept at room temperature (23° C.) overnight and then dried in an oven at 40° C. for 3 days.

[0173] After it has cooled, the coating film is subjected to the test methods set out above.

TABLE-US-00002 TABLE 2 Item Component A 1 Epikote 828.sup.1 41.00 2 Ruetasolv DI.sup.2 5.00 3 Disperbyk 2152.sup.3 0.80 4 BYK A 530.sup.4 0.80 5 BYK-310.sup.5 0.10 6 Blanc Fixe micro.sup.6 25.00 7 Ti-Pure R960.sup.7 23.00 8 Ruetasolv DI 4.30 Total 100.0 Component B 9 Epikure 3155.sup.8 28.70 Total 28.70 .sup.1Epikote 828 is an epoxy resin from Shell International Chemical Corporation .sup.2Ruetasolv DI “Ruetasolv DI” is diisopropylnaphthalene from Rutgers Kureha .sup.3Disperbyk 2152 is a wetting and dispersing agent from Byk Chemie GmbH .sup.4BYK A 530 is a defoamer from Byk Chemie GmbH .sup.5BYK-310 is a surface additive from Byk Chemie GmbH .sup.6Blanc Fixe micro is a synthetic barium sulfate from Sachtleben Chemie .sup.7Ti-Pure R902 is a titanium dioxide pigment from DuPont Titanium Technologies .sup.8Epikure 3155 is a hardener from Momentive

Coating Material 3

[0174] Coating Material Based on a Solvent-Free Pigmented Epoxy Resin/Polyamino Amide Hardener System (Solvent-Free Epoxy System with Low Viscosity)

[0175] The procedure for producing the coating material is as follows. First of all a component A is prepared by mixing the materials listed as items 1 to 4 in table 3 until homogeneity, using a dissolver with a cog disk at 2000 revolutions per minute. The corresponding quantities are reported in parts by weight in table 3. Thereafter the materials of items 5 to 6 in table 3 are added at 3000 revolutions per minute and stirring is continued for 15 minutes more. After that the materials of item 7 in table 3 are added at 2000 revolutions per minute and stirring is continued for 5 minutes more.

[0176] In the next step, 2 wt % of additive (inventive polysiloxane or noninventive additive), based on the sum of components A and B, is added to the mixtures of components A and B, and stirring takes place for 5 minutes at 2000 revolutions per minute.

[0177] The coating material composition is applied in a wet film thickness of 150 μm to a glass plate. The glass plate is kept at room temperature (23° C.) overnight and then dried in an oven at 40° C. for 3 days.

[0178] After it has cooled, the coating film is subjected to the test methods set out below.

TABLE-US-00003 TABLE 3 Item Component A 1 Araldite GY793 BD.sup.1 41.00 2 Disperbyk 142.sup.2 1.00 3 BYK A 530.sup.3 0.80 4 BYK 310.sup.4 0.20 5 Blancfixe micro.sup.5 30.00 6 Ti-Pure R960.sup.6 22.00 7 Benzyl alcohol.sup.7 5.00 Total 100.0 Component B 8 Aradur 44 BD.sup.8 17.00 Total 17.00 .sup.1Araldite GY793 BD is an epoxy resin from Huntsman .sup.2Disperbyk 142 is a wetting and dispersing agent from Byk Chemie GmbH .sup.3BYK A 530 is a defoamer from Byk Chemie GmbH .sup.5BYK-310 is a surface additive from Byk Chemie GmbH .sup.6Blanc Fixe micro is a synthetic barium sulfate from Sachtleben Chemie .sup.7Ti-Pure R902 is a titanium dioxide pigment from DuPont Titanium Technologies .sup.8Aradur 44 BD is a hardener from Huntsman

Coating Material 4

[0179] Coating Material Based on a High-Solids Pigmented Epoxy Resin/Polyamide Hardener System (Epoxy System with High Solids Fraction and High Viscosity)

[0180] The procedure for producing the coating material is as follows. First of all a component A is prepared by mixing the materials listed as items 1 to 4 in table 4 until homogeneity, using a dissolver with a cog disk at 2000 revolutions per minute. The corresponding quantities are reported in parts by weight in table 4. Thereafter the materials of items 5 to 6 in table 4 are added at 3000 revolutions per minute and stirring is continued for 15 minutes more. After that the materials of items 7 to 9 in table 4 are added at 2000 revolutions per minute and stirring is continued for 5 minutes more.

[0181] In the next step, 2 wt % of additive (inventive polysiloxane or noninventive additive), based on the sum of components A and B, is added to the mixtures of components A and B, and stirring takes place for 5 minutes at 2000 revolutions per minute.

[0182] The coating material composition is applied in a wet film thickness of 150 μm to a glass plate. The glass plate is kept at room temperature (23° C.) overnight and then dried in an oven at 40° C. for 3 days.

[0183] After it has cooled, the coating film is subjected to the test methods set out above.

TABLE-US-00004 TABLE 4 Item Component A 1 Epikote 874X90.sup.1 38.20 2 BYK-A530.sup.2 0.80 3 BYK-310.sup.3 0.10 4 Disperbyk-2152.sup.4 0.80 5 Ti-Pure R960.sup.5 25.40 6 Blanc Fixe micro.sup.6 25.70 7 Epikote 834X80.sup.7 4.60 8 MEK.sup.8 2.00 9 Dowanol PM.sup.9 1.40 Total 100.0 Component B 8 Epikure 3155.sup.10 19.74 Total 19.74 .sup.1Epikote 874X90 is an epoxy resin from Momentive .sup.2BYK A 530 is a defoamer from Byk Chemie GmbH .sup.3BYK 310 is a surface additive from Byk Chemie GmbH .sup.4Disperbyk 2152 is a wetting and dispersing agent from Byk Chemie GmbH .sup.5Blanc Fixe micro is a synthetic barium sulfate from Sachtleben Chemie .sup.6Ti-Pure R902 is a titanium dioxide pigment from DuPont Titanium Technologies .sup.7Epikote 834X80 is an epoxy resin from Momentive .sup.8MEK is methyl ethyl ketone .sup.9Dowanol PM is propylene glycol monomethyl ether from Dow .sup.10Epikure 3155 is a hardener from Momentive

Coating Material 5

[0184] Coating Material Based on a High-Solids Pigmented Epoxy Resin/Polyamide Hardener System (Epoxy System with High Solids Fraction and Low Viscosity)

[0185] The procedure for producing the coating material is as follows. First of all a component A is prepared by mixing the materials listed as items 1 to 4 in table 5 until homogeneity, using a dissolver with a cog disk at 2000 revolutions per minute. The corresponding quantities are reported in parts by weight in table 5. Thereafter the materials of items 5 to 6 in table 5 are added at 3000 revolutions per minute and stirring is continued for 15 minutes more. After that the materials of items 7 to 9 in table 5 are added at 2000 revolutions per minute and stirring is continued for 5 minutes more. Subsequently, item 11 is used for dilution at 2000 revolutions per minute, and stirring is continued for 5 minutes more.

[0186] In the next step, 2 wt % of additive (inventive polysiloxane or noninventive additive), based on the sum of components A and B, is added to the mixtures of components A and B, and stirring takes place for 5 minutes at 2000 revolutions per minute.

[0187] The coating material composition is applied in a wet film thickness of 150 μm to a glass plate. The glass plate is kept at room temperature (23° C.) overnight and then dried in an oven at 40° C. for 3 days.

[0188] After it has cooled, the coating film is subjected to the test methods set out above.

TABLE-US-00005 TABLE 5 Item Component A 1 Epikote 874X90.sup.1 38.20 2 BYK-A530.sup.2 0.80 3 BYK-310.sup.3 0.10 4 Disperbyk-2152.sup.4 0.80 5 Ti-Pure R960.sup.5 25.40 6 Blanc Fixe micro.sup.6 25.70 7 Epikote 834X80.sup.7 4.60 8 MEK.sup.8 2.00 9 Dowanol PM.sup.9 1.40 Total 100.0 Component B 10 Epikure 3155.sup.10 19.74 Total 19.74 Component C 11 Dowanol PM.sup.9 8.00 Total 8.00

Test Results

Coating Material 1

[0189]

TABLE-US-00006 TABLE 6a CB Marker slurry CB cream test test Additive test Soap Towel Towel no additive 3 5 5 5 Comparative example A 1 1 2 1 Comparative example B 5 3 4 5 Comparative example C 5 1 4 5 Comparative example D 5 5 5 5 BYK 307* (comparative) 1 5 5 4 Example 3 (comparative) 1 1 2 1 Example 4 (comparative) 1 1 2 1 Example 1 1 1 1 1 Example 2 1 1 1 1 Example 5 1 1 1 1 Example 6 1 1 1 1 Example 7 1 1 1 1 *polyether-modified polysiloxane from Byk-Chemie GmbH

[0190] The results of table 6a show that by using the polysiloxanes of the invention as additive, dirt-repelling and oil-repelling surfaces are obtained whose quality is at least comparable with, if not, in certain tests, actually exceeding that of, the comparative products. Of particular surprise was that the polysiloxanes of the invention in fact have better properties than the additive of comparative example A, despite the latter, on the basis of its epoxy-amine backbone, being chemically even closer to the epoxy resin-based coating material composition of coating material 1.

TABLE-US-00007 TABLE 6b Leveling Marker Water contact (Lw/Sw) COF test angle (°) no additive 24.5/25.4  0.55 5 79 Example 3 (comparative) 3.9/18.0 0.05 1 99 Example 4 (comparative) 3.9/17.4 0.06 1 96 Example 1 3.6/17.1 0.05 1 101 Example 5 3.4/17.2 0.05 1 102 Example 6 3.4/17.2 0.05 1 100

[0191] From the results in table 6b it can be seen that the polysiloxanes of the invention exhibit not only better leveling but also a higher water contact angle than the additives of noninventive comparative examples 3 and 4.

Coating Material 2

[0192]

TABLE-US-00008 TABLE 7 Water CB CB cream contact slurry test Leveling Marker angle test Towel Soap (Lw/Sw) COF test (°) no 3 5 5 27.9/28.4 0.17 5 86 additive Example 3 1 1 1 32.7/27.9 0.06 1 99 (compar- ative) Example 4 1 1 1 25.3/28.4 0.07 2 98 (compar- ative) Example 1 1 1 1 27.3/28.1 0.04 1 103 Example 5 1 1 1 17.6/28.4 0.04 1 99 Example 6 1 1 1 17.6/27.3 0.05 1 98

[0193] In coating material 2 as well, the polysiloxanes of the invention possess a significantly greater leveling-promoting effect in the longwave range for approximately the same water contact angle, or they possess a higher water contact angle for similar leveling.

Coating Material 3

[0194]

TABLE-US-00009 TABLE 8 Water CB CB cream contact slurry test Leveling Marker angle test Towel Soap (Lw/Sw) COF test (°) no 1 3 5 15.1/30.7  0.19 5 95 additive Example 3 4 1 1 8.5/23.0 0.04 1 99 (compar- ative) Example 4 1 1 1 7.3/23.5 0.04 1 93 (compar- ative) Example 1 1 1 1 8.0/23.1 0.04 1 97 Example 5 1 1 1 9.5/25.7 0.04 1 97 Example 6 2 1 1 9.4/25.5 0.05 1 100

Coating Material 4

[0195]

TABLE-US-00010 TABLE 9 Water CB CB cream contact slurry test Leveling Marker angle test Towel Soap (Lw/Sw) COF test (°) no 1 5 5  6.4/12.7 0.14 5 82 additive Example 3 1 5 5 6.9/8.9 0.08 2 89 (compar- ative) Example 4 1 5 5 8.6/9.8 0.08 3 88 (compar- ative) Example 1 1 5 3 7.7/9.1 0.08 2 90 Example 5 1 4 3  7.5/10.0 0.09 1 99 Example 6 1 4 3 7.8/9.9 0.10 2 93

Coating Material 5

[0196]

TABLE-US-00011 TABLE 10 Water CB CB cream contact slurry test Leveling Marker angle test Towel Soap (Lw/Sw) COF test (°) no 4 5 5 7.1/7.6 0.15 5 78 additive Example 3 1 3 2 6.7/7.9 0.06 2 92 (compar- ative) Example 4 1 5 3 5.7/7.6 0.07 1 88 (compar- ative) Example 1 1 3 1 5.4/7.3 0.07 1 93 Example 5 1 2 1 6.2/8.3 0.09 1 93 Example 6 1 2 1 6.5/9.0 0.08 1 98

[0197] The results in the table show that the polysiloxanes of the invention hydrophobize the paint surface and equip it with “easy-to-clean” properties.