Anti-fouling coating composition, process for applying same and coating thereby obtained

Claim 2

An anti-fouling, film-forming composition comprising: (a) a hydrophilic component selected from the group consisting of a polyvinyl ester in which the acid group of the ester is selected from the group consisting of acetic, propionic and butyric acid groups, said polyvinyl ester having an average molecular weight in the range of 8,000 to 35,000, and a copolymer of vinyl chloride and said vinyl ester having at least 25 molar percent of said vinyl ester and a molecular weight in the range of 8,000 to 35,000; (b) a hydrophobic component having no more than 35 carbon atoms therein and having 1-3 urethane groups per molecule; (c) a solvent component having one or more compounds selected from the group consisting of a hydroxyl-containing compound having the formula R"(OH) n' wherein R" represents an aliphatic, arylaliphatic or cycloaliphatic hydrocarbon group having 2-10 carbon atoms and n' is an integer having a value of 1-3, R" may also have 1 carbon atom when n' is 1, a monoether or monoester of an alkylene glycol having no more than 10 carbon atoms, an aromatic hydrocarbon having a kauri butanol value of 73-105, and a ketone having no more than 10 carbon atoms; and (d) an organic tin polymer derived by the reaction of a COOH-containing polymer with R 3 SnOH or (R 3 Sn) 2 O wherein R is a lower alkyl, cycloalkyl or aryl radical.

Claim 3

The composition of claim 1, in which said hydrophilic component is said polyvinyl ester.

Claim 4

The composition of claim 1, in which said hydrophilic component is a polyvinylacetate.

Claim 5

The composition of claim 1, in which said hydrophilic component is a copolymer of said vinyl ester and vinyl chloride having at least 50 molar percent vinyl ester.

Claim 6

The composition of claim 4 in which said vinyl ester is vinyl acetate.

Claim 7

The composition of claim 1, in which said hydrophilic component is a copolymer of said vinyl ester and vinyl chloride having at least 75 molar percent vinyl ester.

Claim 8

The composition of claim 6, in which said vinyl ester is vinyl acetate.

Claim 9

The composition of claim 1, in which said vinyl ester is vinyl acetate.

Claim 10

The composition of claim 1, in which said hydrophobic component has an average of 2 urethane groups per molecule.

Claim 11

The composition of claim 9, in which said hydrophobic component is the reaction product of a diisocyanate and a monohydric compound selected from the group consisting of monohydric alcohols and a monoalkylether of a glycol.

Claim 12

The composition of claim 10, in which said reaction product is derived from a diisocyanate selected from the group consisting of hexamethylene diisocyanate, tolylene diisocyanate and phenylene diisocyanate and from a monohydric compound selected from the group consisting of ethanol, propanol, butanol, and the monoethyl and monopropyl ethers of ethylene and propylene glycols.

Claim 13

The composition of claim 11, in which said monohydric compound is selected from the group consisting of ethanol and the monoethyl ether of ethylene glycol.

Claim 14

The composition of claim 1, in which said COOH-containing polymer is derived from an alkyd resin having an acid number of at least 20.

Claim 15

The composition of claim 1, in which said COOH-containing polymer is a polymer of acrylic acid or an alpha-alkyl acrylic acid in which said alpha-alkyl group has no more than 4 carbon atoms.

Claim 16

The composition of claim 14, in which said polymer is a polymer of methacrylic acid.

Claim 17

The composition of claim 1, in which on the basis of solids content there is 19-38 percent by weight of the hydrophilic component, 6-12 percent by weight of the hydrophobic component, and 50-75 percent by weight of the said organic tin polymer.

Claim 18

The composition of claim 16, in which there is 18-30 percent by weight of the hydrophilic component, 6-8 percent by weight of the hydrophobic component and 65-75 percent by weight of the said tin polymer.

Claim 19

The composition of claim 16, in which said hydrophobic component is the reaction product of a diisocyanate and a monohydric compound selected from the group consisting of monohydric alcohols and monoalkylethers of glycols.

Claim 20

The composition of claim 16, in which said reaction product is from a diisocyanate selected from the group consisting of hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, decylene diisocyanate and phenylene diisocyanate and said monohydric compound is selected from the group consisting of ethanol, propanol, butanol, and the monoethyl and monopropyl ethers of ethylene glycol, propylene glycol and diethylene glycol.

Claim 21

The composition of claim 19, in which said monohydric compound is selected from the group consisting of ethanol and the monoethyl ether of ethylene glycol.

Claim 22

The composition of claim 20, in which said organic tin polymer is derived by the reaction of a tin compound selected from the group consisting of the hydroxide or oxide of tri-n-butyltin, tri-n-propyltin and tri-n-phenyltin with a polymeric acid selected from the group consisting of polymethyacrylic, polyacrylic and poly(vinylbenzoic) acids.

Claim 23

The composition of claim 1, in which said hydrophilic component comprises 10.45-16.72 percent by weight of polyvinylacetate; said hydrophobic component comprises 3.7-6 percent by weight of the reaction product of toluene diisocyanate and ethyl alcohol; 39.6-49.5 percent by weight of said organic tin polymer and the balance making up 100 percent by weight comprises one or more solvents selected from the group consisting of ethyl alcohol, methylethyl ketone, n-butylmonoether of ethylene glycol, toluene and ethyl acetate.

Claim 24

The composition of claim 22, in which said tin polymer is derived from an alkyd resin having an acid number of at least 20.

Claim 25

The composition of claim 22, in which said tin polymer is derived from a polymer of acrylic acid or an alpha-alkyl acrylic acid in which said alpha-alkyl group has no more than 4 carbon atoms.

Claim 26

The composition of claims 1, 2, 5, 9, 13 or 18 in which said hydrophobic component has no more than 20 carbon atoms therein.

Claim 27

An anti-fouling coating deposited on a surface of an object to be submerged in sea water comprising 50-75 percent by weight based on said coating of an organic tin polymer derived by the reaction of a carboxylic acid-containing polymer with R 3 SnOH or (R 3 Sn) 2 O wherein R is a lower alkyl, cycloalkyl or aryl radical; 19-38 percent by weight of a hydrophilic component selected from the group consisting of a polyvinyl ester in which the acid group of the ester is selected from the group consisting of acetic, propionic and butyric acid groups, said polyvinyl ester having an average molecular weight in the range of 8,000 to 35,000, and a copolymer of vinyl chloride and said vinyl ester having at least 25 molar percent of said vinyl ester and a molecular weight in the range of 8,000 to 35,000; and a hydrophobic component having no more than 35 carbon atoms therein and having 1-3 urethane groups per molecule.

Claim 28

An anti-fouling coating deposited on a surface of an object to be submerged in sea water comprising 50-75 percent by weight based on said coating of an organic tin polymer derived by the reaction of a carboxylic acid-containing polymer with R 3 SnOH or (R 3 Sn) 2 O wherein R is a lower alkyl, cycloalkyl or aryl radical; 19-38 percent by weight of a hydrophilic component selected from the group consisting of a polyvinyl ester in which the acid group of the ester is selected from the group consisting of acetic, propionic and butyric acid groups, said polyvinyl ester having an average molecular weight in the range of 8,000 to 35,000, and a copolymer of vinyl chloride and said vinyl ester having at least 25 molar percent of said vinyl ester and a molecular weight in the range of 8,000 to 35,000; and a hydrophobic component having no more than 35 carbon atoms therein and having 1-3 urethane groups per molecule.

Claim 29

The anti-fouling coating of claim 26, in which said carboxylic acid-containing polymer is an alkyd resin having an acid number of at least 20; said hydrophilic component is polyvinylacetate; and said hydrophobic component is the reaction product of a diisocyanate selected from the group consisting of hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, decylene diisocyanate and phenylene diisocyanate with a monohydric compound selected from the group consisting of ethanol, propanol, butanol and the monoethyl and monopropyl ethers of ethylene and propylene glycols.

Claim 30

The anti-fouling coating of claim 26, in which said carboxylic acid-containing polymer is a polymer of acrylic acid or an alpha-alkylacrylic acid in which said alpha-alkyl group has no more than 4 carbon atoms therein; said hydrophilic component is polyvinylacetate; and said hydrophobic component is the reaction product of a diisocyanate selected from the group consisting of hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, decylene diisocyanate and phenylene diisocyanate with a monohydric compound selected from the group consisting of ethanol, propanol, butanol and the monoethyl and monopropyl ethers of ethylene and propylene glycols.

Claim 31

The coating of claim 28 in which said acrylic acid is methacrylic acid.

Claim 32

The coating of claim 26, in which said hydrophobic component has no more than 20 carbon atoms therein.

Claim 33

The process of protecting a surface of an object from fouling by exposure to sea water comprising the steps of applying to said surface a film-forming composition comprising: (a) 10-22 percent by weight of a hydrophilic component selected from the group consisting of a polyvinyl ester in which the acid group of the ester is selected from the group consisting of acetic, propionic and butyric acid groups, said polyvinyl ester having an average molecular weight in the range of 8,000 to 35,000, and a copolymer of vinyl chloride and said vinyl ester having at least 25 molar percent of said vinyl ester and a molecular weight in the range of 8,000 to 35,000; (b) 2.5-7.5 percent by weight of a hydrophobic component having no more than 35 carbon atoms therein and having 1-3 urethane groups per molecule; (c) 30-50 percent by weight of an organic tin polymer derived by the reaction of a COOH-containing polymer with R 3 SnOH or (R 3 Sn) 2 O wherein R is a lower alkyl, cycloalkyl or aryl radical; and (d) 20-40 percent by weight of a solvent component having one or more compounds selected from the group consisting of a hydroxyl-containing compound having the formula R"(OH) n' wherein R" represents an aliphatic, arylaliphatic or cycloaliphatic hydrocarbon group having 2-10 carbon atoms, except that R" may also have one carbon atom when n' is 1, and n' is an integer having a value of 1-3, a monoether or monoester of an alkylene glycol having no more than 10 carbon atoms, an aromatic hydrocarbon having a kauri butanol value of 73-105, and a ketone having no more than 10 carbon atoms. and allowing said coating to dry to a hard film before the resultant coated surface is exposed to sea water.

Claim 34

The process of protecting a surface of an object from fouling by exposure to sea water comprising the steps of applying to said surface a film-forming composition comprising: (a) 10-22 percent by weight of a hydrophilic component selected from the group consisting of a polyvinyl ester in which the acid group of the ester is selected from the group consisting of acetic, propionic and butyric acid groups, said polyvinyl ester having an average molecular weight in the range of 8,000 to 35,000, and a copolymer of vinyl chloride and said vinyl ester having at least 25 molar percent of said vinyl ester and a molecular weight in the range of 8,000 to 35,000; (b) 2.5-7.5 percent by weight of a hydrophobic component having no more than 35 carbon atoms therein and having 1-3 urethane groups per molecule; (c) 30-50 percent by weight of an organic tin polymer derived by the reaction of a COOH-containing polymer with R 3 SnOH or (R 3 Sn) 2 O wherein R is a lower alkyl, cycloalkyl or aryl radical; and (d) 20-40 percent by weight of a solvent component having one or more compounds selected from the group consisting of a hydroxyl-containing compound having the formula R"(OH) n' wherein R" represents an aliphatic, arylaliphatic or cycloaliphatic hydrocarbon group having 2-10 carbon atoms, except that R" may also have one carbon atom when n' is 1, and n' is an integer having a value of 1-3, a monoether or monoester of an alkylene glycol having no more than 10 carbon atoms, an aromatic hydrocarbon having a kauri butanol value of 73-105, and a ketone having no more than 10 carbon atoms. and allowing said coating to dry to a hard film before the resultant coated surface is exposed to sea water.

Claim 35

The process of claim 31, in which said hydrophobic component has no more than 20 carbon atoms therein.

Claim 36

The process of claim 31 in which said hydrophilic component comprises 10.5-16 percent by weight of said composition.

Claim 37

The process of claim 33 in which said hydrophobic component comprises 3.5-6 percent by weight of said composition.

Claim 38

The process of claim 34 in which said tin polymer component comprises 40-50 percent by weight of said composition.

Claim 39

The process of claim 35 in which said solvent comprises 30-38 percent by weight of said composition.

Claim 40

The process of claim 36, in which said hydrophobic component has no more than 20 carbon atoms therein.