Optically Clear Biofouling Resistant Compositions and Methods for Marine Instruments

• US 20100278771A1
• Filed: 02/26/2010
• Published: 11/04/2010
• Est. Priority Date: 02/26/2009
• Status: Active Grant

• Current Assignee: Mid-Mountain Materials, Inc., Severn Marine Technologies, LLC
• Original Assignee: Mid-Mountain Materials, Inc., Severn Marine Technologies, LLC
• Inventors: Knapp, John, Lobe, Henry, Das, Amulya K., Moffat, Gary
• Granted Patent: US 9,562,163 B2
• Time in Patent Office: Days
• US Class Current: 424/78.09
• CPC Class Codes: A01N 55/00 Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing organo-phosphorus compounds A01N57/00
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: C09D 5/14 Paints containing biocides, e.g. fungicides, insecticides or pesticides C09D5/16 takes precedence
• CPC Class Codes: C09D 5/1625 organic
• CPC Class Codes: C09D 5/1675 Polyorganosiloxane-containing compositions
• CPC Class Codes: C09D 5/1693 as part of a multilayer system

Abstract

An optically clear biofouling resistant coating compositions specially formulated for very high light transmission and more particularly coating compositions which can be applied to marine instruments and sensors. The compositions provide a biofouling resistant coating on the surface of the marine instruments and sensors which prevents underwater organisms from adhering and growing on the surfaces of the structures over a long period of time.

Claims

1. An optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors comprising curably reactive organopolysiloxane having at least one terminal reactive functional group and silicon bonded organic groups, an organopolysiloxane cross linking agent, optionally a filler and/or a reinforcing silica, optionally an adhesion promoter, and optionally a metal catalyst;

wherein said terminal reactive group is a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an amido group, a halogen, or a vinyl group; and

said silicon bonded organic group is a methyl group, an ethyl group, a vinyl group, a haloalkyl group, or a phenyl group.

2. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, wherein the curably reactive organopolysiloxane is a hydroxyl, alkoxy, aryloxy, amino, amido, halogen, or vinyl group terminated polydimethylsiloxane.

3. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, wherein the filler comprises nanoparticles of amorphous fumed silica untreated or treated with silanes.

4. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 3, wherein said amorphous fumed silica is treated with trimethylchlorosilane, hexamethyldisilazane, or low molecular weight organoalkoxysilane, organochlorosilane, organosilazane.

5. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, wherein the filler is a resin filler comprising short chain silicone polymers that are soluble in the biofouling resistant organosiloxane-based coating composition.

6. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, wherein the catalyst is catalytic amount of a platinum group metal catalyst.

7. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, further comprising optically clear ingredients such as diluents, extenders, stabilizers, surfactants, and processing aids such as cyclic or linear polydiorganosiloxanes.

8. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 7, wherein the diluents include silicon short chain linear siloxanes, cyclic siloxanes, and organic solvents.

9. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, comprising about 40-70 wt % dimethyl, methylhydrogen siloxane;

15-40% dimethyl siloxane, dimethylvinyl-terminated;

10-30 wt % dimethylvinylated and trimethylated silica;

1.0-5.0 tetramethyl tetravinyl cyclotetrasiloxane;

less than 1 wt % ethylbenzene, 0.5 wt % xylene, and a catalytic amount of platinum.

10. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, comprising about 60-90 wt % vinylpolydimenthylsiloxane;

10-30% vinyl containing resin (ployalkylalkenylsiloxane);

0.0001 benzene;

0.0001 toluene and a catalytic amount of platinum.

11. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, comprising about than 60-80 wt % dimethylsiloxane, hydroxy-terminated;

7.0-13.0 wt % amorphous fumed silica;

1.0-5.0 wt % ethyltriacetoxysilane;

1.0-5.0 wt % methyltriacetoxysilane.

12. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 11, further comprising at least one of tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, or other alkoxysilanes.

13. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, wherein the adhesion promoter is at least one silane coupling agent selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)-aminopropyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, a condensation reaction product between 3-glycidoxypropyltrialkoxysilane and a silanol-endcapped dimethyloligosiloxane, a condensation reaction product between 3-glycidoxypropyltrialkoxysilane and a silanol-endcapped methylvinyloligosiloxane, condensation reaction product between 3-glycidoxypropyltrialkoxysilane and a silanol-endcapped dimethylsiloxane-methylvinylsiloxane copolymer.

14. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, wherein the adhesion promoter comprises a mixture of organic and inorganic compounds.

15. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 14, wherein the adhesion promoter comprises greater than 60.0 wt % Octamethyltrisiloxane, 5.0-10.0 wt % 1-methoxyisopropyl orthosilicate, 5.0-10.0 tetrapropyl orthosilicate, and 3.0-7.0 tetrabutyl titanate.

16. The optically clear biofouling resistant organosiloxane-based coating composition for marine instrument housings and sensors of claim 1, wherein the composition further comprises at least one organic compound having antibiofoulant properties selected from compounds consisting of algaecides, herbicides, bactericides, pesticides, capsaicin and zosteric acid.

17. A method of forming optically clear biofouling resistant coating on marine instrument housings and sensors, comprising coating a surface thereof with a biofouling resistant composition comprising a curably reactive organopolysiloxane having at least one terminal reactive functional group and silicon bonded organic groups, an organopolysiloxane cross linking agent, optionally a filler and/or a reinforcing silica, optionally an adhesion promoter, and optionally a metal catalyst;

wherein said terminal reactive group is a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an amido group, a halogen, or a vinyl group; and

said silicon bonded organic group is a methyl group, an ethyl group, a vinyl group, a haloalkyl group, or a phenyl group;

said coating composition having a refractive index of at least 1.30.

18. The method of claim 17, wherein the curably reactive organopolysiloxane of the biofouling resistant composition is a hydroxyl, alkoxy, aryloxy, amino, amido, halogen, or vinyl group terminated polydimethylsiloxane.

19. The method of claim 17, wherein the filler comprises nanoparticles of amorphous fumed silica untreated or treated with silanes.

20. The method of claim 19, wherein said amorphous fumed silica is treated with trimethylchlorosilane, hexamethyldisilazane, or low molecular weight organoalkoxysilane, organochlorosilane, organosilazane.

21. The method of claim 17, wherein said filler is a resin filler comprising short chain silicone polymers that are soluble in the biofouling resistant organosiloxane-based coating composition.

22. The method of claim 17, wherein said biofouling resistant composition further comprises optically clear ingredients such as diluents, extenders, stabilizers, surfactants, and processing aids such as cyclic or linear polydiorganosiloxanes.

23. The method of claim 22, wherein said diluents include silicon short chain linear siloxanes, cyclic siloxanes, and organic solvents.

24. The method of claim 17, wherein said biofouling resistant composition comprises about 40-70 wt % dimethyl, methylhydrogen siloxane;

15-40% dimethyl siloxane, dimethylvinyl-terminated;

10-30 wt % dimethylvinylated and trimethylated silica;

1.0-5.0 tetramethyl tetravinyl cyclotetrasiloxane;

less than 1 wt % ethylbenzene, 0.5 wt % xylene, and a catalytic amount of platinum.

25. The method of claim 17, wherein said biofouling resistant composition comprises about 60-90 wt % vinylpolydimenthylsiloxane;

10-30% vinyl containing resin (ployalkylalkenylsiloxane);

0.0001 benzene;

0.0001 toluene and a catalytic amount of platinum.

26. The method of claim 17, wherein said biofouling resistant composition comprises about 60-80 wt % dimethylsiloxane, hydroxy-terminated;

7.0-13.0 wt % amorphous fumed silica;

1.0-5.0 wt % ethyltriacetoxysilane;

1.0-5.0Wt % methyltriacetoxysilane.

27. The method of claim 26, wherein said biofouling resistant composition further comprises at least one of tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, or other alkoxysilanes.

28. The method of claim 17, wherein said adhesion promoter is at least one silane coupling agent selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)-aminopropyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, a condensation reaction product between 3-glycidoxypropyltrialkoxysilane and a silanol-endcapped dimethyloligosiloxane, a condensation reaction product between 3-glycidoxypropyltrialkoxysilane and a silanol-endcapped methylvinyloligosiloxane, condensation reaction product between 3-glycidoxypropyltrialkoxysilane and a silanol-endcapped dimethylsiloxane-methylvinylsiloxane copolymer.

29. The method of claim 17, wherein said adhesion promoter comprises a mixture of organic and inorganic compounds.

30. The method of claim 29, wherein said adhesion promoter comprises about 60.0-85.0 wt % Octamethyltrisiloxane, 5.0-10.0 wt % 1-methoxyisopropyl orthosilicate, 5.0-10.0 tetrapropyl orthosilicate, and 3.0-7.0 tetrabutyl titanate.

31. The method of claim 17, wherein said biofouling resistant coating composition further comprises at least one organic compound having antibiofoulant properties selected from compounds consisting of algaecides, herbicides, bactericides, pesticides, capsaicin and zosteric acid.

32. The method of claim 17, wherein the sensor elements is made of stainless steel, glass, epoxy, polyurethane, titanium, ceramics polyvinylchlorides (PVC), polycarbonates (PC), polyurethanes (PU), polypropylenes (PP), polyethylenes (PE), polyesters, polymethylmethacrylate (PMMA), hydroxyethylmethacrylate, N-vinyl pyrrolidones, fluorinated polymers such as polytetrafluoroethylene, polyamides, polystyrenes, copolymers or mixtures of the above polymers.

33. The method of claim 17, wherein the housing element is made of aluminum, titanium, stainless steel, copper nickel, glass, polyurethane, poly vinyl chloride, ceramic, poly acetyl, fiberglass reinforced plastic, carbon fiber reinforced plastic, other thermo plastics, other thermo sets.

34. The method of claim 17, wherein the marine instrument is an acoustic sensor, optical sensors electrode or electromagnetic sensors strain gauge devices.

35. A method of preventing or reducing biofouling on marine instrument housings and sensors comprising using mechanical wipers on surfaces coated with an optically clear biofouling resistant coating composition comprising a curably reactive organopolysiloxane having at least one terminal reactive functional group and silicon bonded organic groups, an organopolysiloxane cross linking agent, optionally a filler and/or a reinforcing silica, optionally an adhesion promoter, and optionally a metal catalyst;

wherein said terminal reactive group is a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an amido group, a halogen, or a vinyl group; and

said silicon bonded organic group is a methyl group, an ethyl group, a vinyl group, a haloalkyl group, or a phenyl group.

36. A method of forming durable optically clear biofouling resistant coating on marine instrument housings and sensors, comprising first coating a surface thereof with an optically clear tie coat, and then coating said surface with a biofouling resistant composition comprising a curably reactive organopolysiloxane having at least one terminal reactive functional group and silicon bonded organic groups, an organopolysiloxane cross linking agent, optionally a filler and/or a reinforcing silica, optionally an adhesion promoter, and optionally a metal catalyst;

wherein said terminal reactive group is a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an amido group, a halogen, or a vinyl group; and

said silicon bonded organic group is a methyl group, an ethyl group, a vinyl group, a haloalkyl group, or a phenyl group.

37. The method of claim 36, wherein the tie coat is a primer capable of forming an intimate covalent bond matrix with the instrument housing and/or sensor surface.

38. The method of claim 36, wherein the tie coat is a polyamine/polyamide blend epoxy resin comprising about 65-70 Wt % Bisphenol a-epichlorohydrin polymer;

30-35 wt % Alkyl(c12-14) glycidyl ether;

diluent n-Butyl glycidyl ether; and

C18-unsaturated fatty acids, dimers, and reaction products with polyethylenepolyamines.

39. The method of claim 36, wherein the tie coat is an epoxy resin comprising about 25-50%;

polyoxypropylenediamine;

reaction products of isophorone diamine with phenol/formaldehyde 10-25%;

Isophoronediamine 10-25%;

Reaction products of benzene-1,3-dimethanamine with hydroxybenzene and formaldehyde 10-25%;

Hydroxybenzene 5-12% and m-Xylene diamine 5-12%.

40. The method of claim 36, wherein the tie coat is an epoxy resin comprising Bisphenol-A type epoxy resin 50-70%;

Benzyl alcohol 10-20%

Bisphenol-F type epoxy resin 10-20%;

Ethylene glycol monobutyl ether 0.1-0.3%.

41. The method of claim 36, wherein the tie coat is a polyurethane adhesive.

42. The method of claim 36, where in the surface to be coated is corona treated.

43. A method of forming durable optically clear biofouling resistant coating on marine instrument housings having one or more sections in O-ring sealable engagement comprising the steps of:

a) putting a clear plastic tape over the O-ring sealable engagement;

b) coating the clear plastic tape with the biofouling resistant coating composition of the present invention;

c) forming at least one hole on the tape in order to equalize the pressure across the tape.