Nontoxic antifouling systems

• US 5,449,553 A
• Filed: 03/28/1994
• Issued: 09/12/1995
• Est. Priority Date: 03/06/1992
• Status: Expired due to Term

• Current Assignee: the united states of america as represented by the secretary of the navy
• Original Assignee: the united states of america as represented by the secretary of the navy
• Inventors: Griffith, James R.
• Primary Examiner(s): NAKARANI, DHIRAJLAL S
• Application Number:
  US08/219,224
• Time in Patent Office: 533 Days
• Field of Search: 428/332, 428/334, 428/335, 428/336, 428/447, 428/448, 428/446, 428/450, 428/451, 428/452
• US Class Current: 428/332
• CPC Class Codes: B08B 17/04 by using removable coverings
• CPC Class Codes: B08B 7/04 by a combination of operations
• CPC Class Codes: C09D 5/1693 as part of a multilayer system
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/263 Coating layer not in excess of 5 mils thick or equivalent
• CPC Class Codes: Y10T 428/264 Up to 3 mils
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31667 Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Abstract

A nontoxic antifouling system is provided at ambient conditions on a subste which has a solid release layer bonded to a solid bonding layer which in turn is bonded to said substrate. The release layer has excellent release property and is bonded to the bonding layer. The bonding layer contains a component which is believed to react with the same or a similar component in the release layer to enhance the desired bond therebetween. The bonding layer is tougher than the release layer but its release property is inferior to that of the release layer.

Claims

1. An article comprising a substrate, a silicone rubber bonding layer of about 15 microns or more in thickness which is a reaction product comprising an organopolysiloxane containing terminal silicon-bonded hydroxyl groups and a polymerizable vinyl aromatic compound bonded to said substrate;

and a silicone rubber release layer of about 20 microns or more in thickness which is a reaction product comprising an organopolysiloxane containing terminal silicon-bonded hydroxyl groups bonded to said bonding layer, said release layer is characterized by quasi mechanical toughness that is imparted to said release layer by said bonding layer which said release layer does not have in absence of said bonding layer, said release layer is damaged when an attempt is made to separate it from said bonding layer, said release layer has better release properties than polytrafluoroethylene, and the bond between said bonding layer and said release layer cannot be broken manually by a finger nail.

2. The article of claim 1 wherein the vinyl aromatic compound is styrene.

3. The article of claim 2 wherein said bonding layer is a reaction product comprising 25-60 weight percent of the organopolysiloxane and 40-70 weight percent of vinyl aromatic compound, based on the weight of said bonding layer;

and said release layer is a reaction product comprising 90-99 weight percent of the organopolysiloxane, 0.1-5 weight percent alkyl silicate, and 0.1-5 weight percent curing agent, based on the weight of said release layer.

4. The article of claim 3 wherein the organopolysiloxane of said release layer contains organic groups and terminal silicon-bonded hydroxyl groups and has viscosity in the range of about 1,000 to 50,000 cps at 25°

C.;

organic groups in the organopolysiloxane of said release layer are selected from the group consisting of monovalent hydrocarbon radicals and halogenated aryl radicals, the organic groups are attached to the organopolysiloxane by means of carbon-silicon bonds;

the alkyl silicate of said release layer is selected from the group consisting of (a) monomeric organosilicates defined by the formula;

##STR5## where R and R'"'"' are individually selected from the group consisting of alkyl groups and halogen-substituted alkyl groups, and R'"'"' additionally is selected from the group consisting of aryl, aralkyl, alkaryl, alkoxy, aryloxy groups, and halogenated derivatives thereof, and (b) partial hydrolysis products of the monomeric organosilicates;

the organopolysiloxane of said bonding layer has viscosity in the range of 1,000 to 20,000 cps at 25°

C. in which the organo groups are free of alkenyl radicals and are selected from the group consisting of monovalent hydrocarbon radicals, halogenated monovalent hydrocarbon radicals and cyanoalkyl radicals;

the organopolysiloxane of said bonding layer having at least one polymeric organic side chain grafted thereto;

the vinyl aromatic compound is polymerized with at least one polyfunctional monomer;

said bonding layer contains cross-linked particulate matter generated in situ.

5. The article of claim 4 wherein the organopolysiloxane in said release and said bonding layers is defined by the formula:

##STR6## where the R groups are individually selected from the group consisting of monovalent hydrocarbon radicals containing 1 to 6 carbon atoms;

the R'"'"' groups are individually selected from the group consisting of monovalent hydrocarbon radicals containing 1 to 6 carbon atoms, halogenated hydrocarbon radicals containing 1 to 6 carbon atoms, and cyanoalkyl radicals containing 1 to 6 carbon atoms;

the Z groups are hydrolyzable by ambient moisture or are condensable and are individually selected from the group consisting of hydroxyl, halogen, amino, amido, aminoxy, oximo, aryloxy, acyloxy, alkoxy, and phosphate groups;

n is a number from 1 to 3; and

x is a number from 1 to 20,000.

6. Article of claim 5 wherein said bonding layer is bonded on one side to said substrate and on the opposite side to said release layer;

said bonding layer is also prepared in the presence of 0.1-20 wt % of a curing agent, based on the weight of said bonding layer;

said curing agent is selected from the group consisting of polyalkoxysilanes of the formula (R"O)_z SiR"'"'"'_4-z, polyalkoxysiloxanes in which the silicon atoms are linked through Si--O--Si linkages and the remaining valences of the silicon atom are satisfied by R"O and R"'"'"' groups, metallic salts, and mixtures thereof, where R" and R"'"'"' are individually selected from the group consisting of monovalent hydrocarbon radicals of 1-8 carbon atoms and z is 3 or 4.

7. The article of claim 6 wherein said substrate is selected from the group consisting of metal, wood, plastic, concrete, and mixtures thereof;

Zs in the organopolysiloxane are hydroxyl groups;

maximum thickness of said bonding layer is about 250 microns; and

maximum thickness of said release layer is about 1000 microns.

8. The article of claim 1 wherein the vinyl aromatic compound is polymerized with a monofunctional monomer selected from the group consisting of polymerizable straight-chain hydrocarbons of 2-6 carbon atoms, halogenated straight-chain hydrocarbons of 2-6 carbon atoms, vinyl esters of 2-6 carbon atoms, unsaturated acids of 2-6 carbon atoms, N-vinyl compounds and vinylsilicone compounds.

9. The article of claim 1 wherein said bonding layer is a reaction product comprising hydroxyl-terminated polydimethylsiloxane, styrene and butyl acrylate.

10. The article of claim 1 wherein said bonding layer is a reaction product of hydroxyl-terminated polydimethylsiloxane, styreno and a monofunctional monomer selected from the group consisting of polymerizable straight-chain hydrocarbons of 2-6 carbon atoms, halogenated straight-chain hydrocarbons of 2-6 carbon atoms, vinyl esters of 2-6 carbon atoms, unsaturated acids of 2-6 carbon atoms, and N-vinyl compounds.

11. The article of claim 10 wherein said bonding layer is a reaction product comprising a polyfunctional monomer in amount of 005-5% based on the weight of the monofunctional monomer.

12. The article of claim 1 wherein said vinyl aromatic compound is selected from the group consisting of styrene, vinylpyridine and vinylnaphthalene.

13. An article comprising a substrate, a silicone rubber bonding layer bonded to said substrate, and a silicone rubber release layer bonded to said bonding layer;

said bonding layer is a reaction product comprising an organopolysiloxane, a monofunctional monomer selected from the group consisting of vinyl aromatic compounds, a polyfunctional monomer selected from the group consisting of monomers having functionality of at least two, a free radical initiator selected from the group consisting of organic peroxide initiators, and a curing agent;

said release layer is a reaction product comprising an organopolysiloxane containing terminal silicon-bonded hydroxyl groups.

14. The article of claim 13 wherein said bonding layer is prepared from, based in the weight of the following bonding components:

(a) 10-80 weight percent of the organopolysiloxane containing terminal silicon-bonded hydroxyl groups,

(b) 30-80 weight percent of the monofunctional monomer and the polyfunctional monomer wherein amount of the polyfunctional monomer is 0.05-5 weight percent, based on the weight of the monofunctional monomer;

(c) 0.05-3 weight percent of the initiator, and

(d) 0.1-20 weight percent of the curing agent.

15. The article of claim 13 wherein said bonding layer is prepared from, based on the weight of the following bonding layer components:

(a) 25-60 weight percent of the organopolysiloxane,

(b) 40-70 weight percent of the monofunctional monomer and the polyfunctional monomer wherein amount of the polyfunctional monomer is 0.1-1 weight percent, based on the weight of the monofunctional monomer,

(c) 0.05-3 weight percent of the initiator, and

(d) 0.1-20 weight percent of the curing agent.

16. The article of claim 15 wherein said release layer is prepared from, based on the weight of the following release layer components:

(1) 90-99 weight percent of the organopolysiloxane,

(2) 0.1-5 weight percent alkyl silicate, and

(3) 0.1-5 weight percent curing agent.

17. The article of claim 16 wherein the monofunctional monomer is styrene;

wherein the polyfunctional monomer is selected from the group consisting of polyol esters of acrylic acid and methacrylic acid; and

wherein the vinyl aromatic compound is polymerized with a monofuctional monomer selected from the group consisting of polymerizable straight-chain hydrocarbons of 2-6 carbon atoms, halogenated straight-chain hydrocarbons of 2-6 carbon atoms, vinyl esters of 2-6 carbon atoms, unsaturated acids of 2-6 carbon atoms, N-vinyl compounds and vinylsilicone compounds.

18. The article of claim 13 wherein said vinyl aromatic compound is selected from the group consisting of styrene, vinylpyridine and vinylnaphthalene.

20. The article of claim 17 wherein said vinyl aromatic compound is selected from the group consisting of styrene, vinylpyridine and vinylnaphthalene.

19. An article comprising a substrate, a silicone rubber bonding layer of about 15 microns or more in thickness which is a reaction product comprising an organopolysiloxane and a polymerizable vinyl aromatic compound bonded to said substrate;

and a silicone rubber release layer of about 20 microns or more in thickness which is a reaction product comprising an organopolysiloxane bonded to said bonding layer, the organopolysiloxane in said bonding layer and in said release layer contains terminal silicon-bonded hydroxyl groups, said release layer has better release properties than polytrafluoroethylene, said release layer is characterized by quasi mechanical toughness that is imparted to said release layer by said bonding layer which said release layer does not have in absence of said bonding layer, said release layer is damaged when an attempt is made to separate it from said bonding layer, and the bond between said bonding layer and said release layer cannot be broken manually by a finger nail.

21. An article comprising a substrate, a silicone rubber bonding layer of about 15 microns or more in thickness which is a reaction product comprising an organopolysiloxane containing terminal silicon-bonded hydroxyl groups and styrene bonded to said substrate;

and a silicone rubber release layer of about 20 microns or more in thickness which is a reaction product comprising an organopolysiloxane containing terminal silicon-bonded hydroxyl groups bonded to said bonding layer, said release layer is characterized by quasi mechanical toughness that is imparted to said release layer by said bonding layer which said release layer does not have in absence of said bonding layer, said release layer is damaged when an attempt is made to separate it from said bonding layer, said release layer has better release properties than polytrafluoroethylene, and the bond between said bonding layer and said release layer cannot be broken manually by a finger nail.