Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
  • C09D5/1668—Vinyl-type polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic

Definitions

• the present invention relates to an antifouling coating composition
• an antifouling coating composition comprising a trialkylsilyl (meth)acrylate polymer, tralopyril, a metal carboxylate and optionally a carboxylic acid, as well as to a method of preparing the composition.
• the composition has excellent long term storage stability.
• the invention also relates to paint comprising the composition and to a paint container containing the composition. Additionally the invention relates to an article comprising a coating on at least a part of a surface thereof and to a method of coating an article to prevent fouling thereon comprising coating at least a part of a surface of the article with the composition.
• antifouling paints are used. These paints generally comprise polymers which form a film (sometimes referred to as film-forming binder), antifouling agents which deter or control the fouling, pigments and solvents. In many cases the paint also comprises one or more further compounds such as extenders, dehydrating agents and thixotropic agents.
• Tralopyril is an antifouling agent having a broad-spectrum activity against hard- shelled and soft bodied animal organisms. It is therefore an attractive antifouling agent to incorporate into paint and especially paint designed for application to surfaces of submerged vessels such as ships.
• tralopyril in paints, however, is that when it is combined with silyl (meth)acrylate polymer, the paint tends to thicken or even gel during storage and particularly during storage for >1 month, e.g. 6 months.
• paints comprising silyl (meth)acrylate polymer and tralopyril tend to increase in viscosity during storage indicating that reactions are happening in the paint and it is not entirely stable. This is obviously a practical problem.
• the viscosity of paint determines how it can be applied (e.g. whether it can be sprayed) and also impacts on the surface finish.
• the paint is typically applied to very large surface areas and is most often applied by airless spraying. The viscosity of the paint must therefore be in a range that enables application by state of the art equipment. A paint cannot be thinned and sprayed if it has gelled.
• EP-A-3078715 recognises the stability problem encountered in paints comprising silyl (meth)acrylates and tralopyril. It confirms that such paints have a tendency to thicken during storage. EP-A-3078715 goes on to disclose that the problem can be overcome by the addition of a stabiliser selected from carbodiimides and/or silanes.
• JP2016089167 discloses that paints comprising hydrolysable resin comprising a triorganosilyl group but lacking cuprous oxide or a copper compound are also unstable. JP2016089167 goes on to describe that this problem can be overcome by a composition comprising a specific copolymer of triisopropylsilyl methacrylate and methoxyethyl (meth) acrylate and tralopyril, but lacking any copper compound.
• an antifouling coating composition comprising:
• metal carboxylate is an alkali metal carboxylate, an alkaline earth metal carboxylate or a transition metal carboxylate, and is derived from a carboxylic acid having 5 to 50 carbon atoms; and (iv) optionally a carboxylic acid;
• weight ratio of said carboxylic acid to said metal carboxylate is 0:100 to 45:55.
• the present invention provides a method for preparing a composition as hereinbefore described, comprising mixing:
• metal carboxylate is an alkali metal carboxylate, an alkaline earth metal carboxylate or a transition metal carboxylate, and is derived from a carboxylic acid having 5 to 50 carbon atoms;
• the present invention provides a paint comprising a composition as hereinbefore described.
• the present invention provides a paint container containing a composition as hereinbefore described.
• the present invention provides an article comprising (e.g. covered with or coated with) a coating on at least a part of a surface thereof, wherein said coating comprises the composition as hereinbefore described.
• the present invention provides a method of coating an article to prevent fouling thereon, wherein said method comprises:
• the present invention provides the use of a composition as hereinbefore described for coating at least a part of a surface of an article to prevent fouling thereon.
• anti-antifouling coating composition refers to a composition that, when applied to a surface, prevents or minimises growth of marine organisms on a surface.
• the term "paint” refers to a composition comprising the antifouling coating composition as herein described and optionally solvent which is ready for use, e.g. for spraying.
• the antifouling coating composition may itself be a paint or the antifouling coating composition may be a concentrate to which solvent is added to produce a paint.
• trialkylsilyl (meth)acrylate polymer refers to a polymer comprising repeat units derived from trialkylsilyl (meth)acrylate monomers.
• a trialkylsilyl (meth)acrylate polymer will comprise at least 5 wt%, more preferably at least 20 wt% and still more preferably at least 40 wt% repeat units derived from trialkylsilyl (meth)acrylate monomers, i.e. trialkylsilyl acrylate and/or trialkylsilyl methacrylate monomers.
• alkyl refers to saturated, straight chained, branched or cyclic groups. Alkyl groups may be substituted or unsubstituted.
• cycloalkyl refers to a saturated or partially saturated mono- or bicyclic alkyl ring system containing 3 to 10 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted.
• alkylene refers to a bivalent alkyl group.
• aryl refers to a group comprising at least one aromatic ring.
• the term aryl encompasses heteroaryl as well as fused ring systems wherein one or more aromatic ring is fused to a cycloalkyl ring.
• Aryl groups may be substituted or unsubstituted.
• An example of an aryl group is phenyl, i.e. C 6 H 5 . Phenyl groups may be substituted or unsubstituted.
• substituted refers to a group wherein one or more, for example up to 6, more especially 1 , 2, 3, 4, 5 or 6, of the hydrogen atoms in the group are replaced independently of each other by the corresponding number of the described substituents.
• optionally substituted as used herein means substituted or unsubstituted.
• metal carboxylate refers to a metal salt of a carboxylic acid.
• Metal carboxylates comprise at least one carboxylate (-COO " ) which is bound or complexed with a metal cation, e.g. M + , M 2+ .
• carboxylic acid refers to a compound comprising 1 to 3 -COOH groups.
• Preferred carboxylic acids comprise one -COOH group, i.e. preferred carboxylic acids are monocarboxylic acids.
• resin acid refers to a mixture of carboxylic acids present in resins.
• rosin refers to rosin and rosin derivatives.
• molecular weight refers to weight average molecular weight (Mw), unless otherwise specified.
• PDI polymer dispersity index refers to the ratio Mw/Mn, wherein Mn refers to number average molecular weight.
• volatile organic compound refers to a compound having a boiling point of 250 °C or less at a standard atmospheric pressure of 101 .3 kPa.
• anti-antifouling agent refers to a compound or mixture of compounds that prevents the settlement of marine organisms on a surface, and/or prevents the growth of marine organisms on a surface and/or encourages the dislodgement of marine organisms from a surface.
• the term “extender” is used interchangeably with “filler” and refers to a compound which increases the volume or bulk of a coating composition.
• the present invention relates to an antifouling coating composition
• an antifouling coating composition comprising:
• metal carboxylate is an alkali metal carboxylate, an alkaline earth metal carboxylate or a transition metal carboxylate, and is derived from a carboxylic acid having 5 to 50 carbon atoms;
• composition further comprises one or more of: (v) additional antifouling agent; (vi) a binder; (vii) a pigment and/or extender; (viii) a dehydrating agent; (ix) an additive; and (x) a solvent.
• the combination of a trialkylsilyl (meth)acrylate polymer, tralopyril and a particular mixture of metal carboxylate and carboxylic acid advantageously provides a composition which has long term storage stability as well as excellent application properties.
• the antifouling coating composition can be stored for an extended period of time (e.g. at least 1 month at ambient temperature) and still have a viscosity of less than 2000 cP which enables it to be applied to a surface, e.g. by spraying.
• the antifouling coating compositions of the present invention preferably comprise a carboxylic acid and a metal carboxylate in a weight ratio of 0:100 to 30:70, more preferably 0:100 to 20:80 and still more preferably 0:100 to 10:90.
• the weight ratio of carboxylic acid to metal carboxylate is 0:100.
• the weight ratio of carboxylic acid to metal carboxylate is 0.5:99.5 to 45:55, more preferably 0.5:99.5 to 30:70 and still more preferably 0.5:99.5 to 20:80.
• the carboxylic acid and metal carboxylate ratio is preferably 0:100 to 20:80, more preferably 0:100 to 5:95 and still more preferably 0:100 to 2:98. These ratios provide the greatest storage stability long term. If a relatively low amount of tralopyril is present (e.g. 0.5-3 wt% based on the total weight of the composition) the carboxylic acid and metal carboxylate ratio is preferably 0:100 to 45:55, more preferably 0:100 to 30:70 and still more preferably 0:100 to 20:80.
• the above-mentioned carboxylic acid to metal carboxylate ratios are based on the amount by weight of carboxylic acid and metal carboxylate added to the antifouling paint during its preparation.
• the ratios do not include any carboxylic acid which may be generated in situ in a composition or any carboxylic acid present in the added metal carboxylate.
• Preferably the ratios do not include any metal carboxylate which is generated in situ, e.g. as a side reaction, in a composition.
• the metal carboxylate present in the antifouling coating composition of the present invention is an alkali metal carboxylate (e.g. potassium carboxylate), an alkaline earth metal carboxylate (e.g. magnesium carboxylate, calcium carboxylate) or a transition metal carboxylate (e.g. zinc carboxylate, copper carboxylate).
• the metal carboxylate is a transition metal carboxylate.
• the metal carboxylate is a zinc carboxylate.
• the metal carboxylate present in the antifouling coating composition of the present invention is derived from a carboxylic acid having 2 to 50 carbon atoms, more preferably 5 to 40 carbon atoms and still more preferably 10 to 20 carbon atoms.
• the metal carboxylate is not derived from a carboxylic acid present within a polymer.
• the metal carboxylate present in the antifouling coating composition of the present invention is preferably derived from a carboxylic acid selected from a resin acid, a derivative of resin acid, C 6- 2o cyclic carboxylic acid, C 5- io acyclic aliphatic carboxylic acid and C 7 - 2 o aromatic carboxylic acid and mixtures thereof.
• resin acids include gum rosin, wood rosin, tall oil rosin, abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, palustric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, communic acid, mercusic acid, secodehydroabietic acid; and sandarac resin containing sandaracopimaric acid, dihydroagathalic acid, dihydroagatholic acid, methyl pinifolic acid, communic acid and dihydroagathic acid.
• Resin derivatives include hydrogenated rosin, disproportionated rosin, dihydroabietic acid and tetrahydroabietic acid.
• Representative examples of C 5- io acyclic carboxylic acids include VersaticTM acids, neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4- dimethyl-2-isopropylpentanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, 2,2- dimethyloctanoic acid, 2,2-diethylhexanoic acid, pivalic acid, 2,2-dimethylpropionic acid, trimethylacetic acid, neopentanoic acid, 2-ethylhexanoic acid, isononanoic acid and 3,5,5-trimethylhexanoic acid.
• C 6- 2o cyclic carboxylic acids include naphthenic acid, 1 ,4-dimethyl-5-(3-methyl-2-butenyl)-3-cyclohexen-1 - ylcarboxylic acid, 1 ,3-dimethyl-2-(3-methyl-2-butenyl)-3-cyclohexen-1 yl-carboxylic acid, 1 ,2,3-trimethyl-5-(1 -methyl-2-propenyl)-3-cyclohexen-1 -yl-carboxylic acid, 1 ,4,5- trimethyl-2-(2-methyl-2-propenyl)-3-cyclohexen-1 -yl-carboxylic acid, 1 ,4,5-trimethyl-2- (2-methyl-1 -propenyl)-3-cyclohexen-1 -yl-carboxylic acid, 1 ,5,6-trimethyl-3-(2-methyl-1 - propenyl)-4-cyclohexen-1 -yl-carboxylic acid
• the metal carboxylate present in the antifouling coating composition of the present invention is derived from abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, palustric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, communic acid and mixtures thereof.
• the metal carboxylate present in the antifouling coating composition of the present invention is derived from gum rosin, wood rosin, tall oil rosin and especially gum rosin. These rosins comprise mixtures of the afore-mentioned resin acids.
• the metal carboxylate present therein is derived from C5-20 carboxylic acids, neodecanoic acid, naphthenic acid, 1 -methyl-3-(4-methyl-3-pentenyl)-3-cyclohexen-1 -yl-carboxylic acid, 1 - methyl-4-(4-methyl-3-pentenyl)-4-cyclohexen-1 -yl-carboxylic acid, 1 ,4,5-trimethyl-2-(2- methyl-1 -propenyl)-3-cyclohexen-1 -yl-carboxylic acid and 1 ,5,6-trimethyl-3-(2-methyl-1 - propenyl)-4-cyclohexen-1 -yl-carboxylic acid.
• the metal carboxylate present in the antifouling coating composition of the present invention is preferably a zinc salt of one of the afore-mentioned carboxylic acids.
• the metal carboxylate is a zinc salt of a carboxylic acid selected from resin acids, derivatives of resin acids, C 6- 2o cyclic carboxylic acids, C 5- io aliphatic carboxylic acids and C7-20 aromatic carboxylic acids and mixtures thereof.
• the metal carboxylate present in the antifouling coating composition of the present invention is a zinc salt of gum rosin, gum rosin derivative, abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, palustric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, communic acid; and sandarac resin containing sandaracopimaric acid, dihydroagathalic acid, dihydroagatholic acid, methyl pinifolic acid, communic acid and dihydroagathic acid.
• the metal carboxylate present in the antifouling coating composition of the present invention is a rosin zinc salt, a zinc salt of a rosin derivative or mixtures thereof and especially preferably gum rosin zinc salt, a zinc salt of a gum rosin derivative or mixtures thereof.
• the total amount of metal carboxylate present in the compositions of the invention is 0.5-25 wt%, more preferably 1.0-20 wt% and still more preferably 1 .5- 15 wt%, based on the total weight of the composition.
• Suitable metal carboxylates may be prepared by techniques well known in the art. Alternatively suitable metal carboxylates may be purchased commercially.
• the antifouling coating compositions of the present invention optionally comprise a carboxylic acid.
• a carboxylic acid is present.
• a carboxylic acid is substantially absent and is preferably absent.
• metal carboxylate and carboxylic acid which has been found to provide long term storage stability in coating compositions comprising trialkylsilyl (meth)acrylate and tralopyril.
• the carboxylic acid preferably comprises 2 to 50 carbon atoms, more preferably 5 to 40 carbon atoms and still more preferably 10 to 20 carbon atoms.
• the carboxylic acid optionally present in the antifouling coating composition of the present invention is preferably a resin acid, a derivative of a resin acid, C 6- 2o cyclic carboxylic acid, C 5- io acyclic aliphatic carboxylic acid and C7-20 aromatic carboxylic acid) and mixtures thereof.
• resin acids include gum rosin, wood rosin, tall oil rosin, abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, levopimaric acid, palustric acid, sandaracopimaric acid, communic acid and mercusic acid, secodehydroabietic acid; sandarac resin containing sandaracopimaric acid, dihydroagathalic acid, dihydroagatholic acid, methyl pinifolic acid, communic acid and dihydroagathic acid.
• resin acid derivatives include hydrogenated rosin, disproportionated rosin, dihydroabietic acid and tetrahydroabietic acid.
• C 5- io acyclic aliphatic carboxylic acids include VersaticTM acids, neodecanoic acid, 2,2,3,5- tetramethylhexanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2,5-dimethyl-2- ethylhexanoic acid, 2,2-dimethyloctanoic acid, 2,2-diethylhexanoic acid, pivalic acid, 2,2-dimethylpropionic acid, trimethylacetic acid, neopentanoic acid, 2-ethylhexanoic acid, isononanoic acid and 3,5,5-trimethylhexanoic acid.
• C 6 -2o cyclic carboxylic acids include naphthenic acid, 1 ,4-dimethyl-5-(3-methyl-2- butenyl)-3-cyclohexen-1 -yl-carboxylic acid, 1 ,3-dimethyl-2-(3-methyl-2-butenyl)-3- cyclohexen-1 -yl-carboxylic acid, 1 ,2,3-trimethyl-5-(1 -methyl-2-propenyl)-3-cyclohexen- 1 -yl-carboxylic acid, 1 , 4, 5-trimethyl-2-(2-methyl-2-propenyl)-3-cyclohexen-1 -yl- carboxylic acid, 1 , 4, 5-trimethyl-2-(2-methyl-1 -propenyl)-3-cyclohexen-1 -yl-carboxylic acid, 1 ,5, 6-trimethyl-3-(2-methyl-1 -propenyl)-4-cyclohexen-1 -yl-carboxy
• Suitable carboxylic acids may be purchased commercially.
• the total amount of carboxylic acid present in the compositions of the invention is 0-5 wt%, more preferably 0-2.5 wt% and still more preferably 0.1 -1 .5 wt%, based on the total weight of the composition. More preferably less than 5 wt% and still more preferably less than 2 wt% of carboxylic acid is present in the compositions of the present invention.
• a relatively high amount of tralopyril e.g.
• the amount of carboxylic acid is preferably 0-2.5 wt%, more preferably 0-1 .5 wt% and still more preferably 0.1 -0.5 wt%. These ratios provide the greatest storage stability long term. If a relatively low amount of tralopyril (e.g. 0.5-3 wt% based on the total weight of the composition) the amount of carboxylic acid is preferably 0-5 wt%, more preferably 0.1 - 2.5 wt% and still more preferably 0.1 -2.0 wt%.
• the trialkylsilyl (meth)acrylate polymer present in the antifouling coating composition of the present invention is preferably a copolymer.
• the trialkylsilyl (meth)acrylate polymer present in the antifouling coating composition comprises a residue of at least one trialkylsilyl (meth)acrylate monomer and preferably a residue of at least one trialkylsilyl (meth)acrylate monomer of formula (I):
• R 1 is H or CH 3 ;
• R 2 are each independently selected from linear or branched Ci -4 alkyl groups
• R 3 are each independently selected from the group consisting of linear or branched Ci_
• each R 4 is independently a linear or branched Ci -4 alkyl group
• Z is a Ci-C 4 alkylene
• n is an integer from 0 to 1 ;
• n is an integer from 0 to 5.
• Representative examples of R 2 and R 4 groups include methyl, ethyl, n-propyl, i- propyl, n-butyl, i-butyl and t-butyl.
• Z include -CH 2 -, -CH 2 CH 2 -, -(CH 2 )3- and -(CH 2 ) 4 -.
• Branched C 3-4 alkylene groups are also envisaged, e.g. -CH 2 CH(CH 3 )CH 2 -.
• m is 0.
• n 0.
• R 3 are each independently selected from linear or branched Ci -20 alkyl groups. Still more preferably R 3 are each independently selected from linear or branched Ci -8 alkyl groups and still more preferably from C 2-6 alkyl groups.
• trialkylsilyl (meth)acrylate monomers e.g. as defined by the general formula (I) include:
• (meth)acrylates such as triisopropylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-sec-butylsilyl (meth)acrylate, butyldiisopropylsilyl (meth)acrylate, t-butyldimethylsilyl (meth)acrylate, thexyldimethylsilyl (meth)acrylate, triisopropylsiloxycarbonylmethyl (meth)acrylate, triisopropylsiloxycarbonylethyl (meth)acrylate, t-butyldimethylsiloxycarbonylmethyl (meth)acrylate, nonamethyltetrasiloxy (meth)acrylate, bis(trimethylsiloxy)methylsilyl (meth)acrylate and tris(trimethylsiloxy)silyl (meth)acrylate.
• Preferred monomers are trialkylsilyl (meth)acrylates wherein one or more of the alkyl group(s) is branched.
• Particularly preferred monomers include triisopropylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, and thexyldimethylsilyl (meth)acrylate.
• Triisopropylsilyl acrylate and triisopropylsilyl methacrylate are particularly preferred.
• the trialkylsilyl (meth)acrylate polymer present in the antifouling coating composition of the present invention preferably comprises 1 -3 different monomers of formula (I) and more preferably 1 or 2 different monomers of formula (I).
• the trialkylsilyl (meth)acrylate polymer present in the antifouling coating composition of the present invention further comprises a residue of one or more (meth)acrylate monomers.
• Preferred meth(acrylate) monomers present in the trialkylsilyl (meth)acrylate polymer are those of formulae (lla)-(llc):
• R 5 is hydrogen or methyl
• R 6 is a cyclic ether and X is a C1-C4 alkylene
• R 7 is hydrogen or methyl
• R 8 is a C 3 -Ci 8 substituent with at least one oxygen or nitrogen atom, preferably at least one oxygen atom;
• R 9 is hydrogen or methyl
• R 10 is a CrC 8 hydrocarbyl
• R 5 is hydrogen or methyl
• R 6 is a cyclic ether (such as oxolane, oxane, dioxolane, dioxane optionally alkyl substituted)
• X is a C1-4 alkylene, preferably a Ci -2 alkylene.
• the cyclic ether may contain a single oxygen atom in the ring or 2 or 3 oxygen atoms in the ring.
• the cyclic ether may contain a ring comprising 2 to 8 carbon atoms, such as 3 to 5 carbon atoms. The whole ring might comprise 4 to 8 atoms, such as 5 or 6 atoms.
• the cyclic ether ring may be substituted such as by one or more, such as one, C1-6 alkyl group. That substituent group might be at any position on the ring including the position that binds to the X group.
• Suitable monomers of formula (I la) include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isopropylideneglycerol methacrylate, glycerolformal methacrylate and cyclic trimethylolpropane formal acrylate.
• Formula (I la) most preferably represents tetrahydrofurfuryl acrylate having the structure below:
• R 7 is hydrogen or methyl
• R 8 is a C 3- 18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom.
• R 8 is of formula -(CH 2 CH 2 0) m -R 11 where R 11 is a Ci-io hydrocarbyl substituent, preferably a CMO alkyl or a C 6- io aryl substituent, and m is an integer in the range of 1 to 6, preferably 1 to 3.
• R 8 is of formula -(CH 2 CH 2 0) m -R 11 where R 11 is an alkyl substituent, preferably methyl or ethyl, and m is an integer in the range of 1 to 3, preferably 1 or 2.
• Preferred monomers of formula (lib) include one or more of 2-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-(2- ethoxyethoxy)ethyl methacrylate and 2-(2-ethoxyethoxy)ethyl acrylate.
• trialkylsilyl (meth)acrylate polymers present in the antifouling coating composition of the present invention it is generally not preferred to have monomers of both formula (lla) and (lib) present.
• R 9 is hydrogen or methyl
• R 10 is a Ci-8 hydrocarbyl substituent, preferably a Ci -8 alkyl substituent, most preferably methyl, ethyl, n-butyl or 2-ethylhexyl.
• Preferred monomers of formula (lie) include methyl methacrylate and n-butyl acrylate.
• Preferred trialkylsilyl (meth)acrylate polymers present in the antifouling coating composition of the invention comprise at least one monomer of formula (lie).
• the trialkylsilyl (meth)acrylate polymer present in the antifouling coating composition of the present invention may optionally comprise other polymerizable monomers.
• alkyl esters of acrylic acid and methacrylic acid such as 3,5,5-trimethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, isotridecyl (meth)acrylate, octadecyl (meth)acrylate
• cyclic alkyl esters of acrylic acid and methacrylic acid such as cyclohexyl (meth)acrylate, 4-t- butylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, isobornyl (meth)acrylate
• aryl esters of acrylic acid and methacrylic acid such
• Preferred trialkylsilyl (meth)acrylate polymers present in the antifouling coating composition of the present invention have a weight average molecular weight (Mw) of 5000 to 80000, more preferably 10000 to 70000 and still more preferably 20000 to 60000.
• Preferred trialkylsilyl (meth)acrylate polymers present in the antifouling coating composition of the present invention have a number average molecular weight (Mn) of 3000 to 20000, more preferably 5000 to 15000 and still more preferably 7000 to 12000.
• Preferred trialkylsilyl (meth)acrylate polymers present in the antifouling coating composition of the present invention have a Tg of 10 °C to 80 °C, more preferably 15 °C to 70 °C and still more preferably 20 °C to 60 °C.
• the antifouling coating composition may comprise one or more (e.g. 1 , 2, 3, 4 or 5) trialkylsilyl (meth)acrylate polymers as hereinbefore described.
• Preferred antifouling coating compositions of the present invention comprise 1 , 2, 3 or 4 trialkylsilyl (meth)acrylate polymers and still more preferably 1 or 2 trialkylsilyl (meth)acrylate polymers.
• the amount of monomers of formula (I) is preferably 5 to 80 wt%, more preferably 20 to 70 wt% and still more preferably 40 to 65 wt% based on the total weight of monomers.
• the total amount of monomers of formula (I la) and (lib) is preferably 1 to 40 wt%, more preferably 2 to 30 wt% and still more preferably 5 to 25 wt% based on the total weight of monomers.
• the amount of monomers of formula (lie) is preferably 1 to 50 wt%, more preferably 2 to 45 wt% and still more preferably 5 to 40 wt% based on the total weight of monomers.
• the amount of other monomers is preferably 0 to 20 wt%, more preferably 0 to 15 wt% and still more preferably 0 to 10 wt% based on the total weight of monomers.
• the total amount of trialkylsilyl (meth)acrylate polymer present in the compositions of the invention is 1 -50 wt%, more preferably 2-40 wt% and still more preferably 5-35 wt%, based on the total weight of the composition.
• Suitable trialkylsilyl (meth)acrylate polymers may be prepared using polymerization techniques known in the art.
• the trialkylsilyl (meth)acrylate polymer may, for example, be obtained by polymerizing a monomer mixture in the presence of a polymerization initiator by any of various methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization. Controlled polymerization techniques may, for example, be employed.
• the polymer is preferably diluted with an organic solvent to give a polymer solution having an appropriate viscosity.
• Suitable polymerization initiators include azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2'- azobis(isobutyronitrile) and 1 ,1 '-azobis(cyanocyclohexane) and peroxides such as t- butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxydiethylacetate, t- butyl peroxyisobutyrate, di-t-butyl peroxide, t-butyl peroxybenozate, and t-butyl peroxyisopropylcarbonate, t-amyl peroxypivalate, t-amyl peroxy-2- ethylhexan
• suitable organic solvent examples include aromatic hydrocarbons such as xylene, toluene, mesitylene; ketones such as methyl isobutyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone; esters such as butyl acetate, amyl acetate, ethylene glycol methyl ether acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, alcohols such as n-butanol, 2-butanol, benzyl alcohol; ether alcohols such as butoxyethanol, 1 -methoxy-2-propanol; aliphatic hydrocarbons such as white spirit; and optionally a mixture of two or more solvents. These compounds are used alone or as a mixture of two or more thereof.
• trialkylsilyl (meth)acrylate polymers may be purchased commercially.
• the antifouling coating composition of the present invention comprises tralopyril or a salt thereof.
• This is an organic antifouling agent that is capable of preventing or removing marine fouling from a surface.
• the organic biocide, tralopyril is sold by Janssen as Econea®.
• Tralopyril is 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1 H- pyrrole-3-carbonitrile and has the structure shown below:
• Tralopyril exhibits a broad spectrum of activity against various marine organisms including barnacles, mussels and tube worms. Salts thereof may also be used.
• the term tralopyril is used below to discuss this biocide. The teaching equally applies to salts thereof.
• Antifouling coating compositions of the present invention comprise tralopyril in an amount to ensure biocidal activity. Preferred amounts are 0.5 to 10 wt% (dry solids), preferably 1 to 7 wt%, preferably 2 to 6 wt%.
• tralopyril exhibits greater biocidal efficacy towards marine organisms compared to metal biocides, meaning that the amount of metal biocide can be reduced or eliminated. In turn, unwanted effects such as discoloration due to the precipitation of copper salts is avoided or reduced.
• a disadvantage of using tralopyril is that it causes instability in trialkylsilyl (meth)acrylate containing compositions. This problem is, however, overcome in the antifouling coating compositions herein which comprises a particular combination of metal carboxylate and optionally a carboxylic acid.
• the antifouling coating composition comprises one or more additional antifouling agents.
• antifouling agent biologically active compounds, antifoulant, biocide, toxicant are used in the industry to describe known compounds that act to prevent marine fouling on a surface.
• the further antifouling agent present in the compositions of the invention is preferably a marine antifouling agent.
• the antifouling agent may be inorganic, organometallic or organic. Suitable antifouling agents are commercially available.
• inorganic antifouling agents include copper and copper compounds such as copper oxides, e.g. copper(l) oxide and copper(ll) oxide; copper alloys, e.g. copper-nickel alloys; copper salts, e.g. copper(l) thiocyanate and copper sulphide.
• copper oxides e.g. copper(l) oxide and copper(ll) oxide
• copper alloys e.g. copper-nickel alloys
• copper salts e.g. copper(l) thiocyanate and copper sulphide.
• organometallic antifouling agents include zinc pyrithione; organocopper compounds such as copper pyrithione, copper acetate, copper naphthenate, oxine copper, copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzensulfonate) and copper bis(pentachlorophenolate); dithiocarbamate compounds such as zinc bis(dimethyldithiocarbamate) [ziram], zinc ethylenebis(dithiocarbamate) [zineb], manganese ethylenebis(dithiocarbamate) [maneb] and manganese ethylene bis(dithiocarbamate) complexed with zinc salt [mancozeb].
• organocopper compounds such as copper pyrithione, copper acetate, copper naphthenate, oxine copper, copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzensul
• organic antifouling agents include heterocyclic compounds such as 2-(t-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1 ,3,5-triazine [cybutryne], 4,5- dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 1 ,2-benzisothiazolin-3-one, 2- (thiocyanatomethylthio)-1 ,3-benzothiazole [benthiazole] and 2,3,5,6-tetrachloro-4- (methylsulphonyl) pyridine; urea derivatives such as 3-(3,4-dichlorophenyl)-1 ,1 - dimethylurea [diuron]; amides and imides of carboxylic acids, sulphonic acids and sulphenic acids such as N-(dichlorofluoromethylthio)phthalimide, N- dichlorofluoromethylthio-N
• antifouling agents include tetraalkylphosphonium halogenides, guanidine derivatives, imidazole containing compounds such as 4-[1 -(2,3- dimethylphenyl)ethyl]-1 H-imidazole [medetomidine] and derivatives, macrocyclic lactones includes avermectins and derivatives thereof such as ivermectine and spinosyns and derivatives thereof such as spinosad, and enzymes such as oxidase, proteolytically, hemicellulolytically, cellulolytically, lipolytically and amylolytically active enzymes.
• Preferred further antifouling agents are copper(l) oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [zineb], 2-(t- butylamino)-4-(cyclopropylamino)-6-(methylthio)-1 ,3,5-triazine [cybutryne], 4,5-dichloro- 2-n-octyl-4-isothiazolin-3-one [DCOIT], N-dichlorofluoromethylthio-N',N'-dimethyl-N- phenylsulfamide [dichlofluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-N-p- tolylsulfamide [tolylfluanid] and 4-[1 -(2,3-dimethylphenyl)ethyl]-1 H-imidazole [medetomidine].
• Especially preferred further antifouling agents are copper(l) oxide, copper(l) thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [zineb], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT] and 4-[1 -(2,3- dimethylphenyl)ethyl]-1 H-imidazole [medetomidine].
• the antifouling agents may be used alone or in mixtures as different antifouling agents operate against different marine fouling organisms. Mixtures of antifouling agents are generally preferred.
• One preferred mixture of antifouling agents is active against marine invertebrates, such as barnacles, tubeworms, bryozoans and hydroids; and plants, such as algae (seaweed and diatoms); and bacteria
• compositions of the present invention are free of an inorganic copper antifouling agent.
• Such compositions preferably comprise a combination of tralopyril and one or more agents selected from zinc pyrithione, zineb and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.
• compositions comprise tralopyril, copper(l) oxide and/or copper(l) thiocyanate and one or more agents selected from copper pyrithione, zineb and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.
• the combined amount of antifouling agents present in the antifouling composition may form up to 60 wt% of the coating composition, such as 0.1 to 50 wt%, e.g. 0.2 to 45 wt%, based on the total weight of the composition.
• a suitable amount of antifouling agent might be 5 to 60 wt% in the coating composition.
• lower amounts might be used such as 0.1 to 25 wt%, e.g. 0.2 to 20 wt%. It will be appreciated that the amount of antifouling agent will vary depending on the end use and the antifouling agent used.
• antifouling agents are known in antifouling coatings and their use would be familiar to the skilled man.
• the antifouling agent may be encapsulated or adsorbed on an inert carrier or bonded to other materials for controlled release. These percentages refer to the amount of active antifouling agent present and not therefore to any carrier used.
• Preferred antifouling coating compositions of the invention comprise:
• Binder components wherein wt% is based on the total weight of the composition.
• an additional binder may optionally be used to adjust the properties of the antifouling coating composition.
• binders that can be used include:
• (meth)acrylic polymers and copolymers in particular acrylate binders, such as poly(n-butyl acrylate), poly(n-butyl acrylate-co-isobutyl vinyl ether) and others as described in WO03/070832 and EP2128208;
• acrylate binders such as poly(n-butyl acrylate), poly(n-butyl acrylate-co-isobutyl vinyl ether) and others as described in WO03/070832 and EP2128208;
• hydrophilic copolymers for example (meth)acrylate copolymers as described in GB2152947 and poly(N-vinyl pyrrolidone) copolymers and other copolymers as described in EP0526441 ;
• vinyl ether polymers and copolymers such as poly(methyl vinyl ether), poly(ethyl vinyl ether), poly(isobutyl vinyl ether), polyvinyl chloride-co-isobutyl vinyl ether);
• aliphatic polyesters such as poly(lactic acid), poly(glycolic acid), poly(2- hydroxybutyric acid), poly(3-hydroxybutyric acid), poly(4-hydroxyvaleric acid), polycaprolactone and aliphatic polyester copolymer containing two or more of the units selected from the above mentioned units;
• hydrocarbon resin e.g. as described in WO201 1/092143, such as hydrocarbon resin formed only from the polymerisation of at least one monomer selected from a C5 aliphatic monomer, a C9 aromatic monomer, an indene coumarone monomer, or a terpene or mixtures thereof.
• Especially suitable additional binders are (meth)acrylic polymers and copolymers. Extenders and pigments
• extender is used herein to encompass extenders as well as fillers. These compounds increase the bulk of the composition.
• extenders and fillers are minerals such as dolomite, plastorite, calcite, quartz, barite, magnesite, aragonite, silica, wollastonite, talc, chlorite, mica, kaolin and feldspar; synthetic inorganic compounds such as zinc phosphates, calcium carbonate, magnesium carbonate, barium sulphate, calcium silicate and silica; polymeric and inorganic microspheres such as uncoated or coated hollow and solid glass beads, uncoated or coated hollow and solid ceramic beads, hollow, porous and compact beads of polymeric materials such as poly(methyl methacrylate), poly(methyl methacrylate-co- ethylene glycol dimethacrylate), poly(styrene-co-ethylene glycol dimethacrylate), poly(styrene-co-divinylbenzene), polystyrene and polyvinyl
• the pigments may be inorganic pigments, organic pigments or a mixture thereof.
• Inorganic pigments are preferred.
• examples of inorganic pigments include titanium dioxide, iron oxides and zinc oxide.
• Examples of organic pigments are naphthol red, phthalocyanine compounds, azo pigments and carbon black.
• the total amount of extender, filler and/or pigment present in the compositions of the invention is 0-70 wt%, more preferably 1 -60 wt% and still more preferably 2-50 wt%, based on the total weight of the composition.
• the extender and pigment content will vary depending on the other components present and the end use of the coating composition.
• the antifouling coating composition of the present invention optionally comprises a dehydrating agent, also referred to as water scavenger or drying agent.
• a dehydrating agent also referred to as water scavenger or drying agent.
• the dehydrating agent is a compound which removes water from the composition in which it is present.
• Dehydrating agents improve the storage stability of the antifouling coating composition by removing moisture introduced from raw materials, such as pigments and solvents, or water formed by reaction between carboxylic acid compounds and bivalent and trivalent metal compounds in the antifouling coating composition.
• the dehydrating agents and desiccants that may be used in the antifouling coating compositions include organic and inorganic compounds.
• the dehydrating agents can be hygroscopic materials that absorbs water or binds water as crystal water, often referred to as desiccants.
• desiccants include calcium sulphate hemihydrate, anhydrous calcium sulphate, anhydrous magnesium sulphate, anhydrous sodium sulphate, anhydrous zinc sulphate, molecular sieves and zeolites.
• the dehydrating agent can be a compound that chemically reacts with water.
• dehydrating agents that reacts with water include orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate and triethyl orthopropionate; ketals; acetals; enolethers; orthoborates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate and tri-t-butyl borate; organosilanes such as trimethoxymethyl silane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane and ethyl polysilicate.
• Preferred dehydrating agents are those that chemically react with water.
• Particularly preferred dehydrating agents are organosilanes.
• Organosilanes are particularly preferred in antifouling coating compositions comprising inorganic copper antifouling agent.
• the dehydrating agent is present in the compositions of the invention in an amount of 0-5 wt%, more preferably 0.5-2.5 wt% and still more preferably 1 .0-2.0 wt%, based on the total weight of the composition.
• the antifouling coating compositions of the present invention do not comprise a carbodiimide compound.
• the antifouling coating composition of the present invention preferably comprises one or more other components.
• other components that can be added to the antifouling coating composition are reinforcing agents, thixotropic agents, thickening agents, anti-settling agents, dispersing agents, wetting agents and plasticizers.
• Fibres include natural and synthetic inorganic fibres such as silicon-containing fibres, carbon fibres, oxide fibres, carbide fibres, nitride fibres, sulphide fibres, phosphate fibres, mineral fibres; metallic fibres; natural and synthetic organic fibres such as cellulose fibres, rubber fibres, acrylic fibres, polyamide fibres, polyimide fibres, polyester fibres, polyhydrazide fibres, polyvinylchloride fibres, polyethylene fibres and others as described in WO 00/77102.
• the fibres have an average length of 25 to 2,000 ⁇ and an average thickness of 1 to 50 ⁇ with a ratio between the average length and the average thickness of at least 5.
• reinforcing agents are present in the compositions of the invention in an amount of 0-20 wt%, more preferably 0.5-15 wt% and still more preferably 1 -10 wt%, based on the total weight of the composition.
• thixotropic agents examples include silicas such as fumed silicas, organo-modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidised polyethylene waxes, hydrogenated castor oil wax, ethyl cellulose, aluminium stearates and mixtures thereof.
• thixotropic agents, thickening agents and anti-settling agents are each present in the composition of the invention in an amount of 0-10 wt%, more preferably 0.5-6 wt% and still more preferably 1.0-3.0 wt%, based on the total weight of the composition.
• plasticizers are chlorinated paraffins, phthalates, phosphate esters, sulphonamides, adipates and epoxidised vegetable oils.
• plasticizers are present in the compostions of the invention in an amount of 0-20 wt%, more preferably 1 -15 wt% and still more preferably 1 -10 wt%, based on the total weight of the composition.
• the antifouling coating composition of the present invention preferably comprises a solvent.
• the solvent is preferably volatile.
• the solvent is organic. That said the components of the antifouling coating composition can alternatively be dispersed in an organic non-solvent for the film-forming components (i.e. the polymers) in the coating composition or in an aqueous dispersion. Suitable solvents for use in the compositions of the invention are commercially available.
• suitable organic solvents and thinners are aromatic hydrocarbons such as xylene, toluene, mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone; esters such as butyl acetate, t-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran; alcohols such as n-butanol, isobutanol, benzyl alcohol; ether alcohols such as butoxyethanol, 1 -methoxy-2-propanol; aliphatic hydrocarbons
• the amount of solvent present in the antifouling coating compositions of the present invention is preferably as low as possible as this minimizes the VOC content.
• solvent is present in the compositions of the invention in an amount of 0-35 wt%, more preferably 1 -30 wt% and still more preferably 2-28 wt% based on the total weight of the composition.
• solvent content will vary depending on the other components present.
• the present invention also relates to a method of preparing the composition as hereinbefore described wherein the components present in the composition are mixed.
• trialkylsilyl (meth)acrylate polymer and metal carboxylate and other optional ingredients are dispersed, milled and cooled prior to mixing with tralopyril.
• the tralopyril may optionally be provided in a solvent.
• composition as described herein may be prepared in a suitable concentration for use, e.g. in spray painting.
• the composition is itself a paint.
• the composition may be a concentrate for preparation of paint.
• further solvent is added to the composition described herein to form paint.
• Preferred solvents are as hereinbefore described in relation to the composition.
• the antifouling coating composition or paint is preferably filled into a container.
• suitable containers include cans, drums and tanks.
• the antifouling coating composition is preferably supplied as a one-pack.
• the composition is preferably supplied in a ready-mixed or ready to use form.
• the one-pack product may be thinned with solvents prior to application.
• the antifouling coating composition and paint of the invention preferably has a solids content of 40-80 vol%, more preferably 45-70 vol% and still more preferably 50-
• the antifouling coating composition and paint of the invention has a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, still more preferably 100-900 cP and still more preferably 150-800 cP.
• viscosity is measured using a Cone and Plate viscometer (ISO 2884-1 :1999) as described in the examples.
• the antifouling coating composition and paint of the invention has a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, still more preferably 100-900 cP and still more preferably 150-800 cP after storage for 1 week at 52°C according to ASTM D1849-95(2014).
• the antifouling coating composition and paint of the invention has a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, still more preferably 100-900 cP and still more preferably 150-800 cP after storage for 2 weeks at 52°C according to ASTM D1849-95(2014).
• the antifouling coating composition and paint of the invention has a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, still more preferably 100-900 cP and still more preferably 150- 800 cP after storage for 4 weeks at 52°C according to ASTM D1849-95(2014).
• the antifouling coating composition of the invention does not form a gel during storage for 4 weeks at 52°C according to ASTM D1849-95(2014).
• viscosity is measured using a Cone and Plate viscometer (ISO 2884-1 :1999) as described in the examples.
• the antifouling coating composition and paint of the invention has a content of volatile organic compounds (VOC) of 50 to 500 g/L, preferably 50 to 420 g/L, e.g. 50 to 390 g/L.
• VOC content can be calculated (ASTM D5201 -01 ) or measured (EPA, method 24).
• the antifouling coating composition and paint of the invention has a viscosity of 50-1000 cP and a content of VOCs of 50 to 500 g/L, more preferably a viscosity of 100-900 cP and a content of VOCs of 50 to 420 g/L and more preferably a viscosity of 150-800 cP and a content of VOCs of 50 to 390 g/L.
• the antifouling coating composition and paint of the invention can be applied to a whole or part of any article surface which is subject to fouling.
• the surface may be permanently or intermittently underwater (e.g. through tide movement, different cargo loading or swell).
• the article surface will typically be the hull of a vessel or surface of a fixed marine object such as an oil platform or buoy.
• Application of the coating composition and paint can be accomplished by any convenient means, e.g. via painting (e.g. with brush or roller) or more preferably spraying the coating onto the article.
• the surface will need to be separated from the seawater to allow coating.
• the application of the coating can be achieved as conventionally known in the art. After the coating is applied, it is preferably dried.
• the viscosity of the polymer solutions was determined in accordance with ASTM D2196-15 Test method A using a Brookfield DV-I viscometer with LV-2 or LV-4 spindle at 12 rpm. The polymers were tempered to 23.0°C ⁇ 0.5°C before the measurements.
• the solids content of the polymer solutions was determined in accordance with ISO 3251 :2008. A test sample of 0.4 g ⁇ 0.1 g was taken out and dried in a ventilated oven. Trialkylsilyl (meth)acrylate copolymers and other acrylic copolymers are dried at 150°C for 30 minutes. Metal carboxylates are dried at 105 °C for 3 hours. The weight of the residual material is considered to be the non-volatile matter (NVM). The nonvolatile matter content is expressed in weight percent. The result given is the average of three parallels.
• the polymers were characterised by Gel Permeation Chromatography (GPC) measurement.
• GPC Gel Permeation Chromatography
• MWD molecular weight distribution
• the analysis conditions were as set out in the table below.
• the glass transition temperature (Tg) was obtained by Differential Scanning Calorimetry (DSC) measurements.
• DSC Differential Scanning Calorimetry
• the DSC measurements were performed on a TA Instrument DSC Q200. Dry polymer samples were prepared by making drawdown on a glass panel using a film applicator with 100 ⁇ gap size. The glass panels were dried at room temperature for at least 24 hour with subsequent drying at 50 °C for 24 hours. Approximately 10 mg dry polymer material was collected from the glass panels and transferred to an aluminium pan. The measurements were done in open aluminium pans with an empty pan as reference. Scans were recorded at a heating rate of 10 °C/min and cooling rate of 10 °C/min in a temperature range from -50 °C to 120 °C. The data were processed using Universal Analysis software from TA Instruments. The inflection point of the glass transition range, as defined in ASTM E1356-08, of the second heating is reported as the Tg of the polymers.
• a quantity of solvent was charged to a temperature-controlled reaction vessel equipped with a stirrer, a condenser, a nitrogen inlet and a feed inlet.
• the reaction vessel was heated and maintained at the reaction temperature of 85 C.
• a pre-mix of monomers, initiator and solvent was prepared. The pre-mix was charged to the reaction vessel at a constant rate over 2 hours under a nitrogen atmosphere. After a further 1 hour, post-addition of a boost initiator solution was added.
• the reaction vessel was maintained at the reaction temperature of 85 C for a further 2 hours. The temperature was then increased to 1 10°C and maintained for a further 30 minutes.
• the copolymer solution was then cooled to room temperature.
• the zinc rosinate solution had a non-volatile matter of 60.8 wt%.
• the zinc rosinate solution had a non-volatile matter of 60.4 wt%.
• the zinc rosinate solution had a non-volatile matter of 66.1 wt%.
• Table 1 The zinc rosinate solution had a non-volatile matter of 66.1 wt%.
• the viscosity of the antifouling coating compositions were determined according to ISO 2884-1 :1999 using a Cone and Plate viscometer set at a temperature of 23 °C, working at a shear rate of 10000 s "1 and providing viscosity measurement in the range of 0-10 P. The result is given as the average of three measurements.
• the consistency of the antifouling coating compositions was determined according to ASTM D562-10(2014) Method B using a digital Stormer-type viscometer. The measurement was done on samples in 500 ml container at 23 °C.
• VOC (g/L) of the antifouling coating compositions was calculated according to ASTM D5201 -01 .
• the storage stability of the antifouling paint compositions were determined according to the conditions described in ASTM D1849-95(2014). The samples were stored in 250 ml containers at 52°C. After storage, the samples were cooled to room temperature before the containers were opened. The consistency of the paints was evaluated. Liquid samples were stirred to homogenous quality and the viscosities were recorded using Cone and Plate viscometer. Storage for 1 month at 52°C simulates some of the effects of storage for 6 months to 1 year at 23°C.
• Silyl copolymer S-1 24.5 24.5 24.5 24.5 24.5
• Antifouling coating compositions P1 -P28 all comprise a trialkylsilyl (meth)acrylate, tralopyril, a metal carboxylate and optionally a carboxylic acid, wherein the weight ratio of carboxylic acid to metal carboxylate is 0:100 to 45:55.
• Table 2 show the stability of antifouling coating compositions comprising zinc salts of various rosin types and comprising various trialkylsilyl (meth)acrylate copolymers.
• Table 3 show the stability of antifouling coating compositions comprising different solvents and comprising different levels of tralopyril and zinc salt of rosin.
• Table 4 show the stability of antifouling coating compositions comprising different levels of carboxylic acid in combination with different levels of tralopyril.
• Table 5 show the stability of different types of antifouling coating compositions with different biocides. All of these coatings are stable to storage. Thus even after storage for 4 weeks in accelerated storage conditions, the compositions have not formed a gel which indicates that they are still applicable to a surface by spraying.
• Comparative example CP-1 which comprises trialkylsilyl (meth)acrylate, but lacks tralopyril and metal carboxylate, is stable during storage. This shows that it is the combination of tralopyril and trialkylsilyl (meth)acrylate which causes instability in antifouling compositions during storage.
• Comparative examples CP-2 to CP-4 which comprise trialkylsilyl (meth)acrylate and tralopyril, but lack metal carboxylate and instead comprise different types of rosin all lack stability and form a gel after 1 week of storage. This demonstrates that it is the addition of the metal carboxylate to the coating composition which provides the storage stability.
• Comparative example CP-5 which comprises trialkylsilyl (meth)acrylate, tralopyril, metal carboxylate and carboxylic acid, wherein the weight ratio of carboxylic acid to metal carboxylate is 47:53, lacks stability and forms a gel after 1 week of storage. This demonstrates that ratio of carboxylic acid to metal carboxylate is crucial in determining the long term stability of the coating composition Preparation of antifouling coating composition
• An antifouling coating composition was prepared using a dissolver. 120 g copper pyrithione, 500 g silyl (meth)acrylate polymer solution S-1 , 300 g zinc rosinate solution Z-1 (60% in xylene) and 130 g xylene were mixed in a 3 L paint container. 1400 g copper(l) oxide, 240 g talc, 240 g zinc oxide, 80 g iron oxide red, 40 g titanium dioxide, 20 g oxidized polyether wax (25% in xylene), 20 g tetraethoxysilane and 30 g Solvesso 100 were added.
• the mixture was dispersed at high speed until the mill base had a fineness of grind of 40 ⁇ and a temperature of 55°C.
• 480 g silyl (meth)acrylate polymer solution S-1 , 40 g polyamide wax (20% in xylene) and 120 g xylene were added under stirring.
• the mixture was cooled and a pre-mix of 120 g tralopyril and 120 g xylene was added.
• the paint was cooled to room temperature and transferred to smaller containers for viscosity measurements and storage stability testing. The viscosity was measured the next day.
• the paint composition had a calculated VOC of 402 g/L and a measured Stormer viscosity of 92 KU, a Cone and Plate viscosity of 442 cP and a fineness of grind of 40 ⁇ .
• the paint composition After 4 weeks of storage at 35°C the paint composition had a Stormer viscosity of 92 KU, a Cone and Plate viscosity of 476 cP and a fineness of grind of 50-60 ⁇ .

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