Non-toxic coating composition, methods of use thereof and articles protected from attachment of biofouling organisms

A method for protecting a surface exposed to an aqueous environment from fouling organisms present in said aqueous environment, said method comprising applying to said surface a composition comprising

• (i) a compound of formula (II)
• wherein
• Ra denotes C4-C20-alkyl, C5-C20-cycloalkyl or -heterocycloalkyl or C5-C20-alkoxy, C6-C12-aryl, C5-C1o-heteroaryl or C7-C11-aralkyl;
• Rb denotes an m+w·n-valent aliphatic C1-C8 radical, a cycloaliphatic or heterocycloaliphatic C3-C15 radical, an araliphatic C7-C20 radical, an alkoxy- or acyloxy-containing aliphatic C3-C15 radical;
• A and B independently of one another denote —O—, —S— or —NH—;
• Y denotes hydroxy, C1-C10-alkoxy, C2-C6-acyloxy, amino, mercapto or —O-Z-O—;
• Z denotes C1-C6-alkylene;
• w denotes the valency of the radical Y and
• m and n independently of one another denote integers from 1 to 8, with the proviso that the sum of m+n is not more than 12, and
• (ii) a film forming agent.

A marine paint composition comprising a) one or more compounds of formula (II)

• wherein
• Ra denotes C4-C20-alkyl, C5-C20-cycloalkyl or -heterocycloalkyl or C5-C20-alkoxy, C6-C12-aryl, C5-C10-heteroaryl or C7-C11-aralkyl;
• Rb denotes an m+w·n-valent aliphatic C1-C8 radical, a cycloaliphatic or heterocycloaliphatic C3-C15 radical, an araliphatic C7-C20 radical, an alkoxy- or acyloxy-containing aliphatic C3-C15 radical;
• A and B independently of one another denote —O—, —S— or —NH—;
• Y denotes hydroxy, C1-C10-alkoxy, C2-C6-acyloxy, amino, mercapto or —O-Z-O—;
• Z denotes C1-C6-alkylene;
• w denotes the valency of the radical Y and
• m and n independently of one another denote integers from 1 to 8, with the proviso that the sum of m +n is not more than 12, and
• (ii) a film forming agent
• b) a film forming agent,
• c) optionally, one or more typical additives, and
• d) optionally, menthol and/or isopulegol,
• wherein the total amount of components a) and, if present, d) is effective for inhibiting or preventing fouling organisms, when the marine paint is applied to a substrate and the substrate is thereafter exposed to sea water.

A paint or coating composition comprising

• (i) menthol and/or isopulegol and
• (ii) a compound selected from the group consisting of
• a) menthyl esters of a natural occuring hydroxycarboxylic acid having 2 to 6 carbon atoms, which are in turn optionally esterified by C1-C4 carboxylic acids on the hydroxy group;
• b) compounds of formula (I):
• wherein
• R1 represents a C2-C6-alkylene radical having at least 1, but not more than 3, hydroxy group(s) and
• either R2 and R3 independently of one another represent C1-C10-alkyl which is optionally substituted by 1 to 3 radicals from the group comprising hydroxy, amino and halogen, or C5-C7-cycloalkyl, or C6-C12-aryl, with the proviso that the total amount of the carbon atoms of R2 and R3 is not less than 3, or
• R2 and R3 together represent an alkylene radical which, together with the carbon atom which carries the radicals R2 and R3, forms a 5-7-membered ring, it being possible for this alkylene radical, for its part, to be substituted by C1-C6-alkyl groups;
• d) compounds of formula (III):
• wherein
• R═H and k is a whole number from 1 to 4, or R═CH3 and k is a whole number from 0 to 4;
• e) compounds of formula (IV):
• wherein
• R′ is H or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, hydroxyalkyl, alkynyl, acyloxyalkyl, alkoxyalkyl, aminoalkyl, acylaminoalkyl, carboxyalkyl radical or an alkylcarboxyalkyl radical of the formula —CpH2pCOOR′″, wherein —CpH2p is a straight or branched chain alkylene group in which p is an integer from 1 to 6 and R′″ is C1-C8-alkyl, each of said radicals containing up to 25 carbon atoms, and
• R″ is hydroxy or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, hydroxyalkyl, alkynyl, acyloxyalkyl, alkoxyalkyl, aminoalkyl, acylaminoalkyl, carboxyalkyl radical or an alkylcarboxyalkyl radical of the formula —CpH2pCOOR′″, wherein —CpH2p is a straight or branched chain alkylene group in which p is an integer from 1 to 6 and R′″ is C1-C8-alkyl, each of said radicals containing up to 25 carbon atoms;
• with the proviso that when R′ is hydrogen R″ may also be an aryl radical of up to 10 carbon atoms selected from benzyl and substituted phenyl wherein the substituents are selected from C1-C4 alkyl, hydroxy and C1-C4-alkoxy, nitro and halogen;
• f) compounds of formula (V):
• wherein
• R# is C1-C5-alkyl, C1-C8-hydroxyalkyl or alkylcarboxyalkyl with up to 6 carbon atoms,
• RX is hydrogen or C1-C5-alkyl;
• and
• RY and RZ independently are C1-C5-alkyl, with the provisos that
• RX, RY and RZ together provide a total of at least 5 carbon atoms, preferably 5-10 carbon atoms, and
• when RX is hydrogen, RY is C2-C5-alkyl and RZ is C3-C5-alkyl and at least one of RY and RZ is branched, preferably in alpha or beta position relative to the carbon atom marked (*) in the formula (V);
• and
• (iii) a film forming agent.

A method for protecting a surface exposed to an aqueous environment from fouling organisms present in said aqueous environment, which comprises applying to said surface a coating including menthol and/or isopulegol and at least one compound listed under a) to f)

• a) menthyl esters of a natural occuring hydroxycarboxylic acid having 2 to 6 carbon atoms, which are in turn optionally esterified by C1-C4 carboxylic acids on the hydroxy group;
• b) compounds of formula (I):
• wherein
• R1 represents a C2-C6-alkylene radical having at least 1, but not more than 3, hydroxy group(s) and
• either R2 and R3 independently of one another represent C1-C10-alkyl which is optionally substituted by 1 to 3 radicals from the group comprising hydroxy, amino and halogen, or C5-C7-cycloalkyl, or C6-C12-aryl, with the proviso that the total amount of the carbon atoms of R2 and R3 is not less than 3, or
• R2 and R3 together represent an alkylene radical which, together with the carbon atom which carries the radicals R2 and R3, forms a 5-7-membered ring, it being possible for this alkylene radical, for its part, to be substituted by C1-C6-alkyl groups;
• d) compounds of formula (III):
• wherein
• R═H and k is a whole number from 1 to 4, or R═CH3 and k is a whole number from 0 to 4;
• e) compounds of formula (IV):
• wherein
• R′ is H or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, hydroxyalkyl, alkynyl, acyloxyalkyl, alkoxyalkyl, aminoalkyl, acylaminoalkyl, carboxyalkyl radical or an alkylcarboxyalkyl radical of the formula —CpH2pCOOR , wherein —CpH2p is a straight or branched chain alkylene group in which p is an integer from 1 to 6 and R′″ is C1-C8-alkyl, each of said radicals containing up to 25 carbon atoms, and
• R′″ is hydroxy or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, hydroxyalkyl, alkynyl, acyloxyalkyl, alkoxyalkyl, aminoalkyl, acylaminoalkyl, carboxyalkyl radical or an alkylcarboxyalkyl radical of the formula —CpH2pCOOR′″, wherein —CpH2p is a straight or branched chain alkylene group in which p is an integer from 1 to 6 and R′″ is C1-C8-alkyl, each of said radicals containing up to 25 carbon atoms;
• with the proviso that when R′ is hydrogen R″ may also be an aryl radical of up to 10 carbon atoms selected from benzyl and substituted phenyl wherein the substituents are selected from C1-C4 alkyl, hydroxy and C1-C4-alkoxy, nitro and halogen;
• f) compounds of formula (V):
• wherein
• R# is C1-C5-alkyl, C1-C8-hydroxyalkyl or alkylcarboxyalkyl with up to 6 carbon atoms,
• RX is hydrogen or C1-C5-alkyl;
• and
• RY and RZ independently are C1-C5-alkyl, with the provisos that
• RX, RY and RZ together provide a total of at least 5 carbon atoms, preferably 5-10 carbon atoms, and
• when RX is hydrogen, RY is C2-C5-alkyl and RZ is C3-C5-alkyl and at least one of RY and RZ is branched, preferably in alpha or beta position relative to the carbon atom marked (*) in the formula (V).

A method for protecting a surface exposed to an aqueous environment from fouling organisms present in said aqueous environment, comprising applying to said surface a composition comprising:

• a) menthyl esters of a natural occuring hydroxycarboxylic acid having 2 to 6 carbon atoms, which are in turn optionally esterified by C1-C4 carboxylic acids on the hydroxy group;
• b) compounds of formula (I):
• wherein
• R1 represents a C2-C6-alkylene radical having at least 1, but not more than 3, hydroxy group(s) and
• either R2 and R3 independently of one another represent C1-C10-alkyl which is optionally substituted by 1 to 3 radicals from the group comprising hydroxy, amino and halogen, or C5-C7-cycloalkyl, or C6-C12-aryl, with the proviso that the total amount of the carbon atoms of R2 and R3 is not less than 3, or
• R2 and R3 together represent an alkylene radical which, together with the carbon atom which carries the radicals R2 and R3, forms a 5-7-membered ring, it being possible for this alkylene radical, for its part, to be substituted by C1-C6-alkyl groups;
• d) compounds of formula (III):
• wherein
• R═H and k is a whole number from 1 to 4, or R═CH3 and k is a whole number from 0 to 4;
• e) compounds of formula (IV):
• wherein
• R′ is H or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, hydroxyalkyl, alkynyl, acyloxyalkyl, alkoxyalkyl, aminoalkyl, acylaminoalkyl, carboxyalkyl radical or an alkylcarboxyalkyl radical of the formula —CpH2pCOOR′″, wherein —CpH2p, is a straight or branched chain alkylene group in which p is an integer from 1 to 6 and R′″ is C1-C8-alkyl, each of said radicals containing up to 25 carbon atoms, and
• R″ is hydroxy or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, hydroxyalkyl, alkynyl, acyloxyalkyl, alkoxyalkyl, aminoalkyl, acylaminoalkyl, carboxyalkyl radical or an alkylcarboxyalkyl radical of the formula —CpH2pCOOR′″, wherein —CpH2p is a straight or branched chain alkylene group in which p is an integer from 1 to 6 and R′″ is C1-C8-alkyl, each of said radicals containing up to 25 carbon atoms;
• with the proviso that when R′ is hydrogen R″ may also be an aryl radical of up to 10 carbon atoms selected from benzyl and substituted phenyl wherein the substituents are selected from C1-C4 alkyl, hydroxy and C1-C4-alkoxy, nitro and halogen;
• f) compounds of formula (V):
• wherein
• R# is C1-C5-alkyl, C1-C8-hydroxyalkyl or alkylcarboxyalkyl with up to 6 carbon atoms,
• RX is hydrogen or C1-C5-alkyl;
• and
• RY and RZ independently are C1-C5-alkyl, with the provisos that
• RX, RY and RZ together provide a total of at least 5 carbon atoms, preferably 5-10 carbon atoms, and
• when RX is hydrogen, RY is C2-C5-alkyl and RZ is C3-C5-alkyl and at least one of RY and RZ is branched, preferably in alpha or beta position relative to the carbon atom marked (*) in the formula (V).

A marine paint composition comprising

• a. one or more compounds selected from the group consisting of the compounds listed under a) to f)
• a) menthyl esters of a natural occuring hydroxycarboxylic acid having 2 to 6 carbon atoms, which are in turn optionally esterified by C1-C4 carboxylic acids on the hydroxy group;
• b) compounds of formula (I):
• wherein
• R1 represents a C2-C6-alkylene radical having at least 1, but not more than 3, hydroxy group(s) and
• either R2 and R3 independently of one another represent C1-C10-alkyl which is optionally substituted by 1 to 3 radicals from the group comprising hydroxy, amino and halogen, or C5-C7-cycloalkyl, or C6-C12-aryl, with the proviso that the total amount of the carbon atoms of R2 and R3 is not less than 3, or
• R2 and R3 together represent an alkylene radical which, together with the carbon atom which carries the radicals R2 and R3, forms a 5-7-membered ring, it being possible for this alkylene radical, for its part, to be substituted by C1-C6-alkyl groups;
• d) compounds of formula (III):
• wherein
• R═H and k is a whole number from 1 to 4, or R═CH3 and k is a whole number from 0 to 4;
• e) compounds of formula (IV):
• wherein
• R′ is H or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, hydroxyalkyl, alkynyl, acyloxyalkyl, alkoxyalkyl, aminoalkyl, acylaminoalkyl, carboxyalkyl radical or an alkylcarboxyalkyl radical of the formula —CpH2pCOOR′″, wherein —CpH2p is a straight or branched chain alkylene group in which p is an integer from 1 to 6 and R′″ is C1-C8-alkyl, each of said radicals containing up to 25 carbon atoms, and
• R″ is hydroxy or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, hydroxyalkyl, alkynyl, acyloxyalkyl, alkoxyalkyl, aminoalkyl, acylaminoalkyl, carboxyalkyl radical or an alkylcarboxyalkyl radical of the formula —CpH2pCOOR′″, wherein —CpH2p is a straight or branched chain alkylene group in which p is an integer from 1 to 6 and R is C1-C8-alkyl, each of said radicals containing up to 25 carbon atoms;
• with the proviso that when R′ is hydrogen R″ may also be an aryl radical of up to 10 carbon atoms selected from benzyl and substituted phenyl wherein the substituents are selected from C1-C4 alkyl, hydroxy and C1-C4-alkoxy, nitro and halogen;
• f) compounds of formula (V):
• wherein
• R# is C1-C5-alkyl, C1-C8-hydroxyalkyl or alkylcarboxyalkyl with up to 6 carbon atoms,
• RX is hydrogen or C1-C5-alkyl;
• and
• RY and RZ independently are C1-C5-alkyl, with the provisos that
• RX, RY and RZ together provide a total of at least 5 carbon atoms, preferably 5-10 carbon atoms, and
• when RX is hydrogen, RY is C2-C5-alkyl and RZ is C3-C5-alkyl and at least one of RY and RZ is branched, preferably in alpha or beta position relative to the carbon atom marked (*) in the formula (V),
• b. a film forming agent,
• c. optionally, one or more typical additives, and
• d. optionally, menthol and/or isopulegol,
• wherein the total amount of components a) and, if present, d) is effective for inhibiting or preventing fouling organisms, when the marine paint is applied to a substrate and the substrate is thereafter exposed to sea water.