Polysiloxane-based fouling control coating systems

Abstract

The present application discloses novel multilayer polysiloxane-based fouling control coating systems having included therein active constituents like biocides and/or enzymes. Further, the polysiloxane-based layers may individually have included as a part thereof hydrophilic oligomer/polymer moieties, and/or said may further comprising one or more hydrophilic-modified polysiloxane oils.

Claims

1. A fouling control coating system comprising: a substrate having a surface; a cured first coat, the cured first coat comprising one or more layers of a first polysiloxane-based binder matrix and one or more biocides being pyrithione complexes present in an amount of 1 to 20% by dry weight, wherein the first polysiloxane-based binder matrix constitutes at least 40% by dry weight of the cured first coat, and wherein 50 to 90% by weight of the first polysiloxane-based binder matrix is represented by polysiloxane parts; and a cured second coat on top of the cured first coat such that the cured first coat is between the cured second coat and the substrate the cured second coat comprising one or more layers of a second polysiloxane-based binder matrix, wherein the second polysiloxane-based binder matrix constitutes at least 40% by dry weight of the cured second coat, and wherein more than 50% by weight of the second polysiloxane-based binder matrix is represented by polysiloxane parts; wherein, the cured first coat further comprises 0.01 to 20% by dry weight of one or more polysiloxane oils modified with hydrophilic groups being poly(ethylene glycol) groups, wherein said one or more polysiloxane oils modified with hydrophilic groups do not react with any of the first polysiloxane-based binder matrix or the second polysiloxane-based binder matrix, and the second cured coat is free of hydrophilic-modified polysiloxane oils.

2. The fouling control coating system according to claim 1, wherein the cured second coat does not contain biocide.

3. The fouling control coating system according to claim 1, wherein the first polysiloxane-based binder matrix is a polydimethylsiloxane-based binder matrix.

4. The fouling control coating system according to claim 1, wherein the second polysiloxane-based binder matrix is a polydimethylsiloxane-based binder matrix.

5. The fouling control coating system according to claim 1, wherein: the first polysiloxane-based binder matrix is a polydimethylsiloxane-based binder matrix, the first polysiloxane-based binder matrix constitutes 50-90% by dry weight of the cured first coat, and the one or more biocides constitute 2-20% by dry weight of said cured first coat; the second polysiloxane-based binder matrix is a polydimethylsiloxane-based binder matrix, the second polysiloxane-based binder matrix constitutes 50-90% by dry weight of the cured second coat, and the cured second coat contains biocide; and the one or more polysiloxane oils modified with hydrophilic groups are polydimethylsiloxane oils modified with hydrophilic groups being poly(ethylene glycol) groups.

6. The fouling control coating system according to claim 1, wherein the polysiloxane oils modified with hydrophilic groups are present in the first cured coat in an amount of 1 to 10% by dry weight.

7. A method of establishing the fouling control coating system according to claim 1 on the surface of the substrate, comprising the sequential steps of: a) applying one or more first layers of a first polysiloxane-based coating composition onto the surface of the substrate and allowing the first layer(s) to cure, thereby forming the cured first coat; and b) applying one or more second layers of a second polysiloxane-based coating composition onto said cured first coat, and allowing the second layer(s) to cure, thereby forming the cured second coat.

8. The method of claim 7, wherein the surface is at least a part of the outermost surface of a marine structure.

Description

EXAMPLES

(1) Preparation Method for the Model Paints

(2) Part (i): binder, solvents, pigments, biocides (if needed) and additives are mixed on a Diaf dissolver equipped with an impeller disc (e.g. 70 mm diameter impeller disc in a 1 L can for 15 minutes at 2000 rpm).

(3) Part (ii): ethyl silicate, solvents, catalyst, and 2,4-pentanedione are mixed on a Diaf dissolver equipped with an impeller disc (e.g. 70 mm diameter impeller disc in a 1 L can for 2 minutes at 500 rpm).

(4) Before the application, part (i) and part (ii) are mixed together with the hydrophilic-modified polysiloxane oils and/or the reactive hydrophilic modified polysiloxane binder according to the compositions provided in the examples, and if present, enzymes are added in a solution/suspension in water, whereafter the mix is then stirred to obtain homogeneity.

(5) Test Methods

(6) Viscosity

(7) In the present application with claims, viscosity is measured at 25° C. in accordance with ISO 2555:1989.

(8) Water Contact Angle Measurements

(9) Establishment of the equilibrium water contact angle of the cured surface is done using sessile drop contact angles, measured by a contact goniometer (Dataphyics OCA) with Milli-Q water as test liquid. The substrate is placed in a temperature controlled chamber, and static contact angles measured by dispersing a drop of 20 μl onto the substrate. Water contact angles are established automatically using the Dataphysixs OCA software. The water contact angle is considered stable when two consecutive measurements at least five minutes apart are not considered significantly different from each other. If this does not happen, the water contact angle after 60 minutes is reported.

(10) Raft Test

(11) Preparation of Panels

(12) An acrylic panel (150×200 mm), sandblasted on one side to facilitate adhesion of the coating, is coated with 100 μm (DFT) of a commercial epoxy (HEMPEL Light Primer 45551) applied by air spraying. After 6-24 hrs of drying at room temperature a tie coat is applied by doctor blade of 300 μm clearance. After 16-30 hrs of drying the first layer is applied by doctor blade with a clearance as specified in the examples. After 16-30 hrs of drying the second coat is applied by doctor blade with a clearance so that the wet film thickness of the layer becomes as specified in the corresponding examples. The panels are dried for at least 72 hrs before immersion on the raft.

(13) Testing

(14) Panels are tested at two different locations; Spain and Singapore.

(15) Test site in Spain: Located in Vilanova in north-eastern Spain. At this test site the panels are immersed into sea water with salinity in the range of 37-38 parts per thousand at an average temperature of 17-18° C.

(16) Test site in Singapore: At this test site the panels are immersed into sea water with salinity in the range of 29-31 parts per thousand at a temperature in the range of 29-31° C.

(17) Panels are inspected ever 4-12 weeks and evaluated according to the following scale:

(18) TABLE-US-00001 Level Description Excellent Only slime Good Algae + Animals < 10% Fair 10% < Algae + Animals < 25% Poor Algae + Animals > 25%

EXAMPLES

(19) The following model paints can be prepared for testing for antifouling performance. All entries in model paints table are in weight unless otherwise stated. In the calculation of the final polysiloxane matrix, all the hydrolysable groups are presumed completely hydrolysed and reacted into a matrix through a condensation reaction with the polysiloxane binder. Therefore, the ethyl silicate contributes with 41% of its weight to the calculations of the final polysiloxane matrix and vinyltrimethoxysilane contributes with 54% of its weight correspondingly. When calculating the polysiloxane content of the binder matrix, the constituents are included in the calculations as the starting materials, however with the above-mentioned corrections for ethyl silicate and vinyltrimethoxysilane.

(20) Materials

(21) RF-5000, ex. Shin-Etsu—Japan, silanol-terminated polydimethylsiloxane

(22) Xylene from local supplier

(23) Aerosil R972, ex. Evonik industries

(24) Silikat TES 40 WN, ex. Wacker chemie—Germany, ethyl silicate

(25) Neostann U-12, ex. Nitto, Kasai—Japan, Dibutyltin dilaurate

(26) Acetylaceton, ex. Wacker Chemie—Germany, 2, 4-pentanedione

(27) Byk331, ex. Byk—Germany, non-reactive polyether modified polydimethylsiloxane oil

(28) Bayferrox 130M, ex. Lancess—Germany, Iron oxide

(29) Copper Omadine, ex. Arch Chemicals Inc.—Ireland, Copper Pyrithione

(30) DC190, ex. Dow Corning—USA, Polyether modified polysiloxane

(31) Tego glide 435, ex. Evonik Industries—Germany, non-reactive polyether modified polydimethylsiloxane oil DC5103, ex. Dow Corning—USA, polyether modified polysiloxane (siloxylated polyether)

(32) DC 550, ex. Dow Corning—USA, polyphenylmethyldimethylsiloxane

(33) DC 57, ex. Dow Corning—USA, polyether modified polydimethyl siloxane.

(34) SIV9280.0, ex. Gelest—USA, Vinyltris(methylethylketoximino)silane.

(35) Fumed silica

(36) Polyamide wax

(37) Sachtleben R320, ex. Sachtleben—Germany, Micronized rutile titanium dioxide.

(38) Zinc omadine, ex. Arch Chemicals Inc.—Ireland, Zinc Pyrithione

(39) Econea, ex. JanssenPMP—Belgium, Tralopyril

(40) Cellulase, (22178) ex. Sigma Aldrich Cellulase from Aspergillus Niger

(41) Savinase 16L type EX, ex. Novozymes—Denmark, solution of protease (subtilisin). copolymer

(42) KF6015, ex. Shin-Etsu—Japan, polyether-modified silicone fluid.

(43) Dynasylan VTMO, ex. Evonik Industries—Germany, vinyltrimethoxysilane

(44) Platinum-divinyltetramethyldisiloxane complex in xylene—2.1-2.4% platinum concentration, CAS No. 68478-92-2

(45) Polydimethylsiloxane, hydride terminated—MW.sub.n=1100, eq. weight=550 g/eq

(46) Methylhydrosiloxane-dimethylsiloxane copolymer, hydride terminated—MWn=2300, eq.

(47) weight=200 g/eq

(48) Polyethylene glycol di allyl ether—MW.sub.n=300 g/mol, Eq. weight=150 g/eq

(49) Polyethylene glycol mono allyl ether (hydroxyl terminated)—MW.sub.n=350 g/mol, eq. weight=350 g/eq

(50) Polyethylene glycol mono allyl ether (hydroxyl terminated)—MW.sub.n=500 g/mol, eq. weight=500 g/eq

(51) Branched Hydrophilic Modified Polsiloxane (HMP3):

(52) A branched, curable poly(ethylene glycol) modified polysiloxane is prepared by mixing 25.0 g polydimethylsiloxane-methylhydrosiloxane, hydride terminated dissolved in 50.0 g water free toluene, with 0.14 g platinum-divinyltetramethyldisiloxane complex in xylene solution. The solution is heated to 80° C. To this solution, 4.0 g of vinyltrimethoxysilane is added drop-wise and allowed to react for ½h at 80° C. After the completion of the reaction, 68.5 g polyethylene glycol mono allyl ether [A350] is added drop-wise, and allowed to react for 3 h at 80° C. The content of PEG-modified PDMS binder in HMP3 is 66.1% w/w. The amount of PEG in the HMP3 binder is 70.3% w/w.

(53) Linear hydrophilic modified polysiloxane (HMP4):

(54) A linear, curable poly(ethylene glycol) modified polysiloxane is prepared by mixing 100.0 g of hydride terminated polydimethylsiloxane dissolved in 75.0 g water free toluene, with 0.17 g of platinum-divinyltetramethyldisiloxane complex in xylene solution. The solution is heated to 80° C. under stirring. To this solution 1.7 g polyethylene glycol di allyl ether [AA300] is added drop-wise, and allowed to react for 2 h at 80° C. After the completion of the reaction 5.4 g of vinyltrimethoxysilane is added drop-wise at 80° C. and allowed to react for 1 h at 80° C. The content of PEG-modified PDMS binder in HMP4 is 58.8% w/w. The amount of PEG in the HMP4 binder is 5.0% w/w.

(55) Branched Hydrophilic Modified Polysiloxane (HMP5):

(56) A branched, curable poly(ethylene glycol) modified polysiloxane is prepared by mixing 25.0 g polydimethylsiloxane-methylhydrosiloxane, hydride terminated dissolved in 50.0 g water free toluene, with 0.14 g platinum-divinyltetramethyldisiloxane complex in xylene solution. The solution is heated to 80° C. To this solution, 4.0 g of vinyltrimethoxysilane is added drop-wise and allowed to react for ½h at 80° C. After the completion of the reaction, 90.0 g polyethylene glycol mono allyl ether [A500] is added drop-wise, and allowed to react for 3 h at 80° C. The content of PEG-modified PDMS binder in HMP5 is 64.4% w/w. The amount of PEG in the HMP5 binder is 75.6% w/w.

(57) The reactive hydrophilic modified polysiloxanes (MHP3, MHP4, HMP5) are stored in a closed container under dry nitrogen to avoid contact with moisture prior to the formulation.

Example 1

(58) Base 1

(59) TABLE-US-00002 Part i RF-5000 silanol-terminated 69.1 g polysiloxane Xylene 24.6 g Aerosil 1.2 g Polyamide wax 0.8 g Bayferrox 130M 4.3 g sum 100.0 g
Base 2

(60) TABLE-US-00003 Part i RF-5000 silanol-terminated 64.3 g polysiloxane Xylene 23.0 g Aerosil 1.1 g Polyamide wax 0.6 g Bayferrox 130M 4.0 g Copper Omadine 7.0 g sum 100.0 g
Base 3

(61) TABLE-US-00004 Part i RF-5000 silanol-terminated 60.6 g polysiloxane Xylene 21.6 g Aerosil 1.0 g Polyamide wax 0.6 g Bayferrox 130M 3.7 g Copper Omadine 12.4 g sum 99.9 g
Base 4

(62) TABLE-US-00005 Part i RF-5000 silanol-terminated 55.1 g polysiloxane Xylene 16.1 g Aerosil 0.59 g Sachtleben R320 28.5 g sum 100.0 g
Base 5

(63) TABLE-US-00006 Part i RF-5000 silanol-terminated 64.3 g polysiloxane Xylene 23.0 g Aerosil 1.1 g Polyamide wax 0.6 g Bayferrox 130M 4.0 g Zinc Omadine 7.0 g sum 100.0 g
Base 6

(64) TABLE-US-00007 Part i RF-5000 silanol-terminated 64.3 g polysiloxane Xylene 23.0 g Aerosil 1.1 g Polyamide wax 0.6 g Bayferrox 130M 4.0 g Econea 7.0 g sum 100.0 g
One-Component Paint 1*

(65) TABLE-US-00008 Part i RF-5000 silanol-terminated 40.8 g polysiloxane Xylene 20.2 g Filler 14.4 Polyamide wax 0.3 g Sachtleben R320 (pigment) 14.2 g SIV9380.0 5.4 Copper Omadine 4.8 g sum 100.1 g

(66) This composition may be used as a one-component composition without the need of a curing agent.

(67) Curing Agent 1

(68) TABLE-US-00009 Part ii Silikat TES 40WN 31.9 g Xylene 46.3 g Acetylaceton 16.4 g Neostann U-12 5.5 g sum 100.1 g

Example 1.A

(69) TABLE-US-00010 Water contact Antifouling 1.sup.st layer 2.sup.nd layer angle of the performance Gap-size/ Gap-size/ 2.sup.nd layer Performance in Curing approx. Curing approx. Measured after Spain after 8 Base agent DFT Base agent Additive DFT 60 minutes weeks A1 92.5 g Base 2 7.5 g 400 μm/ 88.5 g 7.7 g 3.8 g 400 μm/ 17° Excellent (CuPT.sub.2) C.A. 1 150 μm Base 1 C.A. 1 Byk331 150 μm A2 92.5 g Base 2 7.5 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ 17° Excellent (CuPT.sub.2) C.A. 1 150 μm Base 1 C.A. 1 Byk331 100 μm A3 92.5 g Base 2 7.5 g 400 μm/ 88.5 g 7.7 g 3.8 g 250 μm/ 17° Excellent (CuPT.sub.2) C.A. 1 150 μm Base 1 C.A. 1 Byk331  50 μm RefA4   92 g Base 1   8 g 400 μm/ 88.5 g 7.7 g 3.8 g 400 μm/ 17° Poor C.A. 1 150 μm Base 1 C.A. 1 Byk331 150 μm A5 92.9 g Base 3 7.1 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ 17° Excellent (CuPT.sub.2) C.A. 1 150 μm Base 1 C.A. 1 Byk331 100 μm Ref A6 92.9 g Base   7.1 g 400 μm/   92 g 8.0 g 300 μm/ 83° Fair 3(CuPT.sub.2) C.A. 1 150 μm Base 1 C.A. 1 100 μm Ref A7   92 g Base 1   8 g 400 μm/   92 g 8.0 g 300 μm/ 83° Poor C.A. 1 150 μm Base 1 C.A. 1 100 μm Ref A8 92.5 g Base 2 7.5 g 400 μm/ Intersleek 900 300 μm/ 65° Poor (CuPT.sub.2) C.A. 1 150 μm 100 μm

Example 1.B

(70) TABLE-US-00011 Water contact Antifouling 1.sup.st layer 2.sup.nd layer angle of the performance Measured Gap-size/ 2.sup.nd layer Performance in Curing after 60 Curing approx. Measured after Spain after 10 Base agent minutes Base agent Additive DFT 60 minutes weeks B1 92.5 g Base 2 7.5 g 400 μm/ 88.7 g 7.7 g 3.6 g 300 μm/ <10° Good (CuPT.sub.2) C.A. 1 150 μm Base 1 C.A. 1 Tego 100 μm Glide 435 B2   92 g Base 1   8 g 400 μm/ 88.7 g 7.7 g 3.6 g 300 μm/ <10° Poor C.A. 1 150 μm Base 1 C.A. 1 Tego 100 μm Glide 435 B3 92.5 g Base 2 7.5 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ <10° Fair (CuPT.sub.2) C.A. 1 150 μm Base 1 C.A. 1 DC5103 100 μm RefB4   92 g Base 1   8 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ <10° Poor C.A. 1 150 μm Base 1 C.A. 1 DC5103 100 μm Ref B5 92.5 g Base 2 7.5 g 400 μm/ Intersleek 900 300 μm/  65° Poor (CuPT.sub.2) C.A. 1 150 μm 100 μm

Example 1.C

(71) TABLE-US-00012 Water contact 1.sup.st layer 2.sup.nd layer angle of the Antifouling Gap-size/ Gap-size/ 2.sup.nd layer performance Curing approx. Curing approx. Measured after after 54 weeks Base agent Additive DFT Base agent DFT 60 minutes in Spain C1 87.9 g 7.1 g   5 g 400 μm/ 7.5 g 7.6 g 3.5 g 400 μm/ 15° Good Base 2 C.A. 1 Byk331 150 μm Base 1 C.A. 1 DC550 150 μm (CuPT.sub.2)   2 g DC57 Ref  7.5 g 7.6 g 3.5 g 400 μm/ 7.5 g 7.6 g 3.5 g 400 μm/ 15° Poor C2 Base 1 C.A. 1 DC550 150 μm Base 1 C.A. 1 DC550 150 μm 2 g DC57   2 g DC57

Example 1.D

(72) TABLE-US-00013 Water contact angle of the 1.sup.st layer 2.sup.nd layer 2.sup.nd layer Antifouling Gap-size/ Gap-size/ Measured performance Curing approx. Curing approx. after 60 after 49 weeks Base agent Additive DFT Base agent Additive Biocide DFT minutes in Spain D1 One-component 400 μm/ 87.9 g 7.1 g 5 g Tego 400 μm/ <10° Fair paint 1 100 g 150 μm Base 4 C.A 1 435 150 μm (ZnPT.sub.2) Ref 7.5 g 7.6 g 3.5 g 400 μm/  15° Poor D2 Base 1 C.A. 1 DC550 150 μm   2 g DC57

Example 1.E

(73) TABLE-US-00014 Water contact Antifouling 1.sup.st layer 2.sup.nd layer angle of the performance Gap-size/ Gap-size/ 2.sup.nd layer Performance in Curing approx. Curing approx. Measured after Spain after 10 Base agent DFT Base agent Additive DFT 60 minutes weeks E1 92.5 g 7.5 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/  17° Excellent Base 6 C.A. 1 150 μm Base 1 C.A. 1 Byk331 100 μm (Econea) E2 92.5 g 7.5 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ <10° Excellent Base 6 C.A. 1 150 μm Base 1 C.A. 1 Tego 100 μm (Econea) glide 435 E3 88.9 g 7.4 g 3.7 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ <10° Excellent Base 6 C.A. 1 Tego 150 μm Base 1 C.A. 1 Tego 100 μm (Econea) glide 435 glide 435 E4 88.9 g 7.4 g 3.7 g 400 μm/ 70.8 g 7.7 g 3.8 g 300 μm/ <10° Excellent Base 6 C.A. 1 Tego 150 μm Base 1 C.A. 1 Tego 100 μm (Econea) glide 435 8.5 g glide 435 Base 6 E5 92.5 g 7.5 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ <10° Excellent Base 5 C.A. 1 150 μm Base 1 C.A. 1 Tego 100 μm (ZnPT.sub.2) glide 435 E6 46.3 g 7.5 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ <10° Good Base 5 C.A. 1 150 μm Base 1 C.A. 1 Tego 100 μm (ZnPT.sub.2) glide 435 46.2 g Base 6 (Econea) Ref E7 88.5 g 7.7 g 3.8 g 300 μm/  17° Poor Base 1 C.A. 1 Byk331 100 μm Ref E8 88.5 g 7.7 g 3.8 g 300 μm/ <10° Fair Base 1 C.A. 1 Tego 100 μm glide 435 Ref E9 92.5 g 7.5 g 400 μm/ Intersleek 900 300 μm/  65° Poor Base 5 C.A. 1 150 μm 100 μm (ZnPT.sub.2)

Example 1.F

(74) TABLE-US-00015 Antifouling 1.sup.st layer 2.sup.nd layer performance Gap-size/ Gap-size/ Weight % of Performance in Curing approx. Curing Modified approx. PEG in outer Spain after 10 Base agent DFT Base agent binder DFT layer (solids) weeks F1 92.5 g 7.5 g 400 μm/ 66.8 g 5.8 g 27.4 g 300 μm/ 18.3 Fair Base 5 C.A. 1 150 μm Base 1 C.A. 1 HMP3 100 μm (ZnPT.sub.2) F1 88.9 g 7.4 g 3.7 g 400 μm/ 66.8 g 5.8 g 27.4 g 300 μm/ 18.3 N/A Base 6 C.A. 1 Tego 150 μm Base 1 C.A. 1 HMP3 100 μm (econea) glide 435 Ref F3 66.8 g 5.8 g 27.4 g 300 μm/ 18.3 Poor Base 1 C.A. 1 HMP3 100 μm F4 92.5 g 7.5 g 400 μm/ 66.3 g 5.8 g 28.0 g 300 μm/ 19.7 Excellent Base 5 C.A. 1 150 μm Base 1 C.A. 1 HMP5 100 μm (ZnPT.sub.2) Ref F5 66.3 g 5.8 g 28.0 g 300 μm/ 19.7 Poor Base 1 C.A. 1 HMP5 100 μm F6 92.5 g 7.5 g 400 μm/ 64.6 g 5.6 g 29.8 g 300 μm/ 1.3 Poor Base 5 C.A. 1 150 μm Base 1 C.A. 1 HMP4 100 μm (ZnPT.sub.2) Ref F7 64.6 g 5.6 g 29.8 g 300 μm/ 1.3 poor Base 1 C.A. 1 HMP4 100 μm Ref F8 92.5 g 7.5 g 400 μm/ Intersleek 900 300 μm/ Poor Base 5 C.A. 1 150 μm 100 μm (ZnPT.sub.2)

Example 1.G

(75) TABLE-US-00016 Water contact Antifouling angle of the performance 1.sup.st layer 2.sup.nd layer 2.sup.nd layer Weight % Antifouling Gap-size/ Gap-size/ Measured of PEG in performance Curing approx. Curing approx. after 60 outer layer after 10 weeks Base agent Enzyme DFT Base agent DFT minutes (solids) in Spain G1 89.2 g 7.8 g   3 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ <10° Fair Base 1 C.A.1 Savinase 150 μm Base 1 C.A. 1 Tego 100 μm glide 435 G2 83.7 g 7.3 g   9 g 200 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ <10° Fair Base 1 C.A.1 Savinase  50 μm Base 1 C.A. 1 Tego 100 μm glide 435 G3 85.8 7.5 g   3 g 400 μm/ 88.5 g 7.7 g 3.8 g 300 μm/ <10° Excellent Base 1 C.A. 1 savinase 150 μm Base 1 C.A. 1 Tego 100 μm  3.7 g glide 435 Tego glide 435 Ref 88.5 g 7.7 g  3.8 g 400 μm/ <10° Fair G4 Base 1 C.A. 1 Tego 150 μm glide 435 G5 89.2 g 7.8 g   3 g 400 μm/ 92.0 g 8.0 g 300 μm/  83° Poor Base 1 C.A.1 Savinase 150 μm Base 1 C.A. 1 100 μm G6 85.8 7.5   3 g 400 μm/ 92.0 g 8.0 g 300 μm/  83° Excellent Base 1 C.A.1 savinase 150 μm Base 1 C.A. 1 100 μm  3.7 g Tego glide 435 Ref 92.0 g 8.0 g 300 μm/  83° Poor G7 Base 1 C.A. 1 100 μm G8 89.2 g 7.8 g   3 g 400 μm/ 88.5 g 7.7 g  3.8 g 300 μm/ <10° Fair Base 1 C.A.1 Endolase 150 μm Base 1 C.A. 1 Tego 100 μm glide 435 G9 89.2 g 7.8 g   3 g 400 μm/ 66.8 g 5.8 g 27.4 g 300 μm/ 18.3 Fair Base 1 C.A.1 Savinase 150 μm Base 1 C.A. 1 HMP3 100 μm Ref 66.8 g 5.8 g 27.4 g 300 μm/ 18.3 Poor G10 Base 1 C.A. 1 HMP3 100 μm G11 89.2 g 7.8 g   3 g 400 μm/ 64.6 g 5.6 g 29.8 g 300 μm/ 1.3 Poor Base 1 C.A.1 Savinase 150 μm Base 1 C.A. 1 HMP4 100 μm Ref 64.6 g 5.6 g 29.8 g 300 μm/ 1.3 Poor G12 Base 1 C.A. 1 HMP4 100 μm G13 86.5 g 7.5 g   3 g 400 μm/ 88.5 g 7.7 g  3.8 g 300 μm/ <10° Fair Base 1 C.A. 1 Savinase 150 μm Base 1 C.A. 1 Tego 100 μm   3 g glide 435 endolase Ref 89.2 g 7.8 g   3 g 400 μm/ Intersleek 900 300 μm/  65° Poor G14 Base 1 C.A.1 Savinase 150 μm 100 μm

Example 1.H

(76) TABLE-US-00017 Water contact 1.sup.st layer 2.sup.nd layer angle of the Gap-size/ Gap-size/ 2.sup.nd layer Curing approx. Curing approx. Measured after Antifouling Base agent Enzyme DFT Base agent DFT 60 minutes performance H1 88.9 g 7.4 g 3.7 g 400 μm/ 92.0 g 8.0 g 300 μm/ Excellent Base 5 C.A. 1 Tego 150 μm Base 1 C.A. 1 100 μm  (ZnPT.sub.2) glide 435 H2 88.9 g 7.4 g 3.7 g 400 μm/ 92.0 g 8.0 g 200 μm/ Excellent Base 5 C.A. 1 Tego 150 μm Base 1 C.A. 1  50 μm  (ZnPT.sub.2) glide 435 H3 88.9 g 7.4 g 3.7 g 400 μm/ 92.0 g 8.0 g 300 μm/ Good Base 5 C.A. 1 Byk 331 150 μm Base 1 C.A. 1 100 μm  (ZnPT.sub.2) Ref 92.0 g 8.0 g 300 μm/ Poor H4 Base 1 C.A. 1 100 μm H5 66.8 g 5.8 g 27.4 g  400 μm/ 92.0 g 8.0 g 300 μm/ Fair Base 5 C.A. 1 HMP3 150 μm Base 1 C.A. 1 100 μm  (ZnPT.sub.2) H6 66.8 g 5.8 g 27.4 g  400 μm/ 92.0 g 8.0 g 300 μm/ Fair Base 1 C.A. 1 HMP3 150 μm Base 1 C.A. 1 100 μm    3 g Savinase H7 85.8 7.5   3 g 400 μm/ 92.0 g 8.0 g 300 μm/ Good Base 1 C.A. 1 savinase 150 μm Base 1 C.A. 1 100 μm  3.7 g Tego glide 435 Ref 92.5 g 7.5 g 400 μm/ Intersleek 900 300 μm/ 65° Poor H8 Base 5 C.A. 1 150 μm 100 μm (ZnPT.sub.2) AX1 89.2 g 7.8 g 3 g 400 μm/ Intersleek 900 300 μm/ 65° Good Base 1 C.A.1 Savinase 150 μm 100 μm Ref 92.0 g 8.0 g Intersleek 900 300 μm/ 65° Poor AX2 Base 1 C.A. 1 100 μm