EP4126335A1 - Composition de revêtement antisalissure - Google Patents

Composition de revêtement antisalissure

Info

Publication number
EP4126335A1
EP4126335A1 EP21713698.5A EP21713698A EP4126335A1 EP 4126335 A1 EP4126335 A1 EP 4126335A1 EP 21713698 A EP21713698 A EP 21713698A EP 4126335 A1 EP4126335 A1 EP 4126335A1
Authority
EP
European Patent Office
Prior art keywords
meth
polymer
acrylate
ethylenically unsaturated
core
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21713698.5A
Other languages
German (de)
English (en)
Inventor
Marit Dahling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jotun AS
Original Assignee
Jotun AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jotun AS filed Critical Jotun AS
Publication of EP4126335A1 publication Critical patent/EP4126335A1/fr
Pending legal-status Critical Current

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    • 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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C09D5/165—Macromolecular compounds containing hydrolysable groups
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • C08F2/08—Organic solvent with the aid of dispersing agents for the polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • 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
    • C09D5/1687—Use of special additives
    • 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
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/015—Biocides
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the invention relates to an antifouling coating composition
  • an antifouling coating composition comprising a polymeric binder component comprising a plurality of ester functional groups and an organic marine biocide in the core of a core-shell polymer particle.
  • the invention also relates to a method of preparing such an antifouling coating composition, and to a marine structure coated with such an antifouling coating composition.
  • the invention also relates to the core-shell polymer particles per se.
  • antifouling paints are used. These paints generally comprise a film-forming binder, together with different components such as pigments, fillers, additives and solvents together with biologically active substances (biocides).
  • Many antifouling coating compositions are based on a polymeric binder which contains a plurality of ester groups.
  • the ester-based polymers can either having esters as pendant groups on the polymer chains such as acrylic and methacrylic polymers (e.g. as described in GB2558739, GB2559454,
  • WO2015/114091 and WO2015/114092 and poly(siloxane-co-ester) (e.g. as described in WO2017/009297).
  • Polymers that have ester groups as part of the polymer structure can degrade in the presence of organic biocides, such as medetomidine, tralopyril and similar compounds. Degradation of the polymeric binder in the antifouling coating formulation will negatively affect the storage stability, the mechanical properties, the polishing properties and the antifouling performance of the coatings.
  • Organic biocides may also react with reactive groups in the polymer intended for curing or initiate the curing reaction in the can during storage.
  • the organic biocides can be supplied as a separate component (and added prior to application) or the biocide can be encapsulated.
  • the first solution is not desirable as it increases complexity during product application, and it requires handling of a concentrated biocide component by the operators in dock.
  • the later solution can be complex and costly as many techniques for encapsulation require several process steps or are performed in water. Water is undesirable in solvent borne antifouling coating formulations with hydrolysable ester containing binders, so the water has to be removed from the encapsulated biocide particles. The presence of even small amounts of water is undesirable as it may cause degradation of the binder.
  • the present inventors sought a solution to the problem of ester degradation by organic biocides.
  • WO2010/133548 describes microparticles prepared by forming an aqueous emulsion with an organic phase comprising a polymer for forming microparticle walls.
  • the microparticles comprise a polymeric shell with oil core.
  • W02018/055102 describes covalent immobilization of biocides within a core-shell structure.
  • the biocide is immobilized in the core of a microparticle in which a polymer, such as a polyurethane/polyurea polymer, forms the shell.
  • WO201 1/151025 describes microparticles with a core-shell structure.
  • An active agent is present in the core along in an aqueous or a non-aqueous dispersion medium with encapsulating polymer shell.
  • the invention offers improved storage stability (i.e. in-can), and maintained or increased biocide performance.
  • Core-shell polymeric particles containing the biocide can be obtained using non-aqueous dispersion polymerization reactions. Encapsulation of medetomidine, tralopyril and similar organic biocide compounds by non-aqueous dispersion polymerization is an easy, inexpensive, industrial applicable process that can be done in large scale. Non-aqueous dispersion polymerization following the protocols described herein produces polymeric particles having a “core-shell” structure as further defined herein. The biocide will in this process be a part of the core material and will be protected or stabilized by a polymeric shell polymer.
  • the core-shell polymer particles of the invention can be regarded as a colloid.
  • the colloid will separate the active compound from the binder phase in the antifouling coating formulation.
  • an antifouling coating composition comprising:
  • a plurality of core-shell polymer particles wherein the core comprises an organic biocide and a polymer of one or more ethylenically unsaturated monomers wherein at least one of said ethylenically unsaturated monomers comprises a polar group selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido and wherein said polymer comprises more than 30 % by weight of monomer residues comprising polar groups; and a shell polymeric dispersant comprising a polymer of one or more ethylenically unsaturated monomers wherein said polymer comprises less than 20 % by weight of ethylenically unsaturated monomer residues comprising polar groups selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido; and
  • an antifouling coating composition comprising:
  • a plurality of core-shell polymer particles wherein the core comprises an organic biocide and a polymer of one or more ethylenically unsaturated monomers wherein at least one of said ethylenically unsaturated monomers comprises a polar group selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido and wherein said polymer comprises more than 30 % by weight of monomer residues comprising polar groups; and a shell polymeric dispersant comprising a polymer, such as a macromonomer, of one or more ethylenically unsaturated monomers wherein said polymer comprises less than 20 % by weight of ethylenically unsaturated monomer residues comprising polar groups selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido; and
  • the invention provides an antifouling coating composition
  • an antifouling coating composition comprising: (i) a polymeric binder component comprising a plurality of ester functional groups;
  • a plurality of core-shell polymer particles wherein the core comprises an organic biocide and a polymer consisting of one or more ethylenically unsaturated monomers wherein said ethylenically unsaturated monomers comprises a polar group selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido; and a shell polymeric dispersant consisting of a polymer of one or more ethylenically unsaturated monomers wherein said ethylenically unsaturated monomers are free of polar groups selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido; and a non-aqueous solvent; and
  • the invention provides a process for the manufacture of the antifouling coating composition as herein before defined comprising blending:
  • the invention provides a process for protecting an object from fouling, comprising coating at least a part of said object which is subject to fouling with an antifouling coating composition as hereinbefore defined.
  • the invention provides an object coated with the antifouling coating composition as hereinbefore defined.
  • the object is preferably a marine object such as the hull of a ship or other substrate exposed repeatedly to sea water.
  • the invention provides the use of an antifouling coating composition as hereinbefore defined to prevent fouling of a marine surface.
  • the core-shell particles themselves form a still yet further aspect of the invention.
  • the invention provides core-shell particles comprising
  • a core comprising an organic biocide and a polymer of one or more ethylenically unsaturated monomers wherein at least one of said ethylenically unsaturated monomers comprises a polar group selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido and wherein said polymer comprises more than 30 % by weight of monomer residues comprising polar groups; and
  • a shell polymeric dispersant comprising a polymer of one or more ethylenically unsaturated monomers wherein said polymer comprises less than 20 % by weight of ethylenically unsaturated monomer residues comprising polar groups selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido.
  • the core-shell polymer particles comprise
  • a core comprising an organic biocide and a polymer consisting of one or more ethylenically unsaturated monomers wherein said ethylenically unsaturated monomers comprises a polar group selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido;
  • a shell polymeric dispersant consisting of a polymer of one or more ethylenically unsaturated monomers wherein said ethylenically unsaturated monomers are free of polar groups selected from hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido; and a non-aqueous solvent.
  • marine antifouling coating composition As used herein the terms “marine antifouling coating composition”, “antifouling coating composition” or simply “coating composition” refer to a composition that, when applied to a surface, prevents or minimises growth of marine organisms on the surface.
  • the coating composition may be a self-polishing coating or a fouling release coating.
  • solid organic biocide refers to a biocide having melting point above 23°C at ambient pressure (1 atm).
  • shell refers to a polymeric dispersant that surrounds the core particles.
  • the core particles can be considered dispersed within the polymeric dispersant.
  • the polymeric dispersant can be physically absorbed or chemically anchored to the core particles.
  • the polymeric dispersant typically contains a polymer and a non-aqueous solvent.
  • the non-aqueous dispersion polymerization process used to form the “core shell” particles of the invention gives rise to a shell in the form of a polymeric dispersant.
  • the polymeric dispersant can be a polymer soluble in the disperse medium (solvent), but also macromonomers or other suitable dispersants soluble in the solvent phase.
  • a non-aqueous dispersion process can be used to form the polymer particles of the core.
  • the core comprises a polymer and biocide.
  • the polymeric dispersant such as a macromonomer, may be anchored to the “core” surface, while other polymeric dispersants are held on the core surface due to thermodynamics.
  • core-shell particle refers to a core polymer particle stabilised with a polymeric dispersant “shell”.
  • the core-shell particles may be colloidal. There is not necessarily a defined boundary between the core particle and the polymeric dispersant shell.
  • Macromonomer refers to a polymer or oligomer molecule which on average has between one and two ethylenically unsaturated end- groups that can react as a monomer molecule.
  • binder refers to the film forming components of the composition.
  • 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 coating composition may be a concentrate to which solvent is added to produce a paint.
  • polysiloxane refers to a polymer comprising siloxane, i.e. -Si-O- repeat units.
  • alkyl refers to saturated, straight chained, branched or cyclic groups. Alkyl groups may be substituted or unsubstituted.
  • cycloalkyl refers to a cyclic alkyl group.
  • alkylene refers to a bivalent alkyl group.
  • alkenyl refers to unsaturated, straight chained, branched or cyclic groups. Alkenyl groups may be substituted or unsubstituted.
  • aryl refers to a group comprising at least one aromatic ring.
  • Aryl groups may be substituted or unsubstituted.
  • An example of an aryl group is phenyl, i.e. C6H5. Phenyl groups may be substituted or unsubstituted.
  • polyether refers to a compound comprising two or more -O- linkages interrupted by alkylene units.
  • (meth)acrylate encompasses both methacrylate and acrylate.
  • wt% is based on the dry weight of the coating composition, unless otherwise specified
  • volatile organic compound refers to a compound having a boiling point of 250 °C or less at standard atmospheric pressure of 1 atm.
  • anti-antifouling agent or “biocide” refers to a biologically active compound or mixture of biologically active 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.
  • non-polar monomer implies the absence of a functional group that is chemically polar such as hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido.
  • non-polar monomers will contain carbon and hydrogen atoms only but may contain the group R-COO-R group present in a (meth)acrylate.
  • R- COO-R is not regarded as polar herein.
  • polar monomer implies the presence of a polar functional group in the monomer such as hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido.
  • ester implies the presence of the group R1-C0-0-R2 where R2 is not H. Polyoxalates are regarded as a type of ester herein.
  • This invention relates to antifouling coating compositions comprising core shell polymer particles prepared by non-aqueous dispersion polymerization.
  • Non- aqueous dispersion polymerization for encapsulation of organic biocides such as medetomidine, tralopyril and similar compounds is an easy, inexpensive, industrial applicable process that can be carried out in large scale.
  • the method preferably forms colloidal particles with the organic biocide and provides improved stabilization of the coating formulation and/or improved and prolonged release of the biocide during the lifetime of the coating.
  • the core-shell polymer particles of the invention may also be employed in fouling release coatings.
  • fouling release coatings may be based on a polysiloxane binder as described further below. Encapsulation of organic biocides such as medetomidine, tralopyril and similar compounds by non-aqueous dispersions will therefore increase the possible areas of use for these biocides.
  • the core-shell particles comprise:
  • a polar core component comprising an organic biocide and a polymer comprising one or more ethylenically unsaturated monomers wherein at least one of said monomers comprises a polar group selected from a hydroxyl, carboxylic acid, ether, sulfonic acid, amino, or amido group and wherein more than 30 % by weight, such as more than 50 wt%, of monomer residues present in the polymer comprise polar groups;
  • a polymeric dispersant shell component comprising a polymer of one or more ethylenically unsaturated monomers wherein less than 20 % by weight of monomer residues in the polymer comprise polar groups selected from a hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido groups; and a non-aqueous solvent.
  • Core-shell polymer particles according to the invention may be colloidal.
  • the core-shell particles may have a shape and volume that is stable.
  • the core-shell particles are preferably non-crystalline and comprise one substance (the core) dispersed through a second substance (the polymeric dispersant).
  • the shell polymeric dispersant can be physically absorbed or chemically anchored to the core particles. We can imagine that the biocide and core polymer are immobilised within the shell polymeric dispersant.
  • the polymer particles may have a diameter of 10 nm to 100 pm, more preferred 100 nm to 10 pm. More preferably particles have a diameter of 150 to 2000 nm.
  • the diameter refers to the Z-average diameter and is measured e.g. with a Malvern Zetasizer as described in the experimental section.
  • the diameter refers to the D50 diameter and is measured e.g. with a Malvern Mastersizer.
  • the particles are preferably non-aqueous. By non-aqueous is meant that no water is used to prepare the polymer particles and hence the final polymer particles contain no water.
  • the polymer particles are preferably prepared in a two-step process described herein.
  • a shell polymeric dispersant can be prepared as described below or, alternatively, a pre-prepared commercial polymer can be used in the shell polymeric dispersant, e.g. a macromonomer can be used as the shell polymeric dispersant.
  • the core of the polymer particle is then prepared in the presence of the shell polymeric dispersant by combining the organic biocide and the monomer(s) required to make the core polymer and subjecting the mixture to a polymerization reaction.
  • the shell polymeric dispersant is typically used in an amount sufficient to sterically stabilize the core particles.
  • the weight ratio between the shell polymeric dispersant /core components can e.g. be 20/80, preferably 30/70 to 80/20, preferably 70/30, such as 50/50.
  • the weight ratio between the shell polymeric dispersant /core components can e.g. be 25/70 to 45/55, or 30/70 to 45/55.
  • the invention provides a process for the preparation of a plurality of core-shell polymer particles comprising:
  • the shell polymeric dispersant is preferably prepared as a dispersant solution of the polymer in a non-aqueous solvent such as a hydrocarbon solvent, e.g. white spirit.
  • a non-aqueous solvent such as a hydrocarbon solvent, e.g. white spirit.
  • the polymer forming the outer stabilizing layer or polymeric dispersant shell of the polymer particles of the invention is prepared from the polymerization of one or more ethylenically unsaturated non-polar monomers or may be a commercial polymer or macromonomer.
  • non-polar means herein that there are no hydroxyl, carboxylic acid, ether, sulfonic acid, amino, or amido functional groups present on the monomers.
  • the shell polymer comprises 100 wt% of non-polar monomers, i.e. there are no polar monomers present at all.
  • non-polar ethylenically unsaturated monomers include unsubstituted and substituted aliphatic (meth)acrylates or polydimethoxysilane (meth)acrylates.
  • the monomer for use in the preparation of the shell polymer is most preferably an aliphatic (meth)acrylate. It is preferred if the shell polymer consists of the residues of one or more aliphatic (meth)acrylates only.
  • Suitable monomers for the shell dispersant include aliphatic (meth)acrylates monomers such as methyl methacrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2- propylheptyl (meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, stearyl (meth)acrylate and cyclohexyl (meth)acrylate; substituted aliphatic (meth)acrylates monomers such as 2,2,2- trifluoroethyl (meth)acrylate and lH,lH,
  • the polymer should preferably contain less than 10 wt% of residues from an ethylenically unsaturated polar monomer as defined herein.
  • the shell polymer is one based on the polymerization of non-polar alkyl (meth)acrylate monomers only such as Ci-20 alkyl(meth)acrylate monomers, preferably Ci-12 alkyl(meth)acrylate monomers.
  • Preferred monomers include methyl methacrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate and dodecyl (meth)acrylate.
  • the shell polymer may have an Mw of 5,000 to 150,000, preferably 25,000 to 130,000, especially 50,000 to 120,000 (measured as described in the experimental section).
  • the shell polymer may have a Tg (measured as described in the experimental section) of -50 to 60 °C, preferably -45 to 25 °C, especially -40 to 0 °C.
  • the solvent used for the preparation of the polymeric dispersant may be a non-aqueous solvent, preferably a major amount of non-polar solvent such as a non polar organic solvent, e.g. aliphatic hydrocarbon, alicyclic hydrocarbons, aromatic hydrocarbon, or silicone oil or modified silicone oil or mixture thereof.
  • a non polar organic solvent e.g. aliphatic hydrocarbon, alicyclic hydrocarbons, aromatic hydrocarbon, or silicone oil or modified silicone oil or mixture thereof.
  • Preferred solvents are hydrocarbon solvents such as mixtures of normal-, iso- and cyclo- paraffins in the Ce to Cio range, mineral spirits, white spirit, xylene, and toluene.
  • Examples of commercial products include, VM&P Naphtha, Shellsol D38, Shellsol D40, SPB 140/165, Shellsol D60, Shellsol A100 and Shellsol A150 by Shell Chemicals; Exxsol Heptane, Exxsol D30, Exxsol D40, Exxsol D60, Exxsol DSP 145/160, Exxsol D180/200, Isopar E, Isopar G, Varsol 30, Varsol 40, Varsol 60, Solvesso 100 and Solvesso 150 by ExxonMobil Chemicals; Spirdane D30, Spirdane D40 and Spirdane D60 by Total Special Fluids.
  • the polymeric dispersant is ideally provided with a Brookfield viscosity of 50 to 5000 cP.
  • the solids content of the polymeric dispersant is ideally 30 to 100 wt%, such as 40 to 60 wt%.
  • the shell polymer monomer is a C4-10 alkyl(meth)acrylate monomer, such as n-butyl(meth)acrylate, 2- ethylhexyl(meth)acrylate or 2-propylheptyl (meth)acrylate.
  • the core of the polymer particle contains an organic biocide, preferably a solid organic biocide.
  • organic biocides include N-[(4-hydroxy-3- methoxyphenyl)methyl]-8-methyl-6-nonenamide [Capsaicin], N-[(4-hydroxy-3- methoxyphenyl)methyl]-7-phenyl-6-heptynamide [Phenylcapsaicin, aXiphen-bio®], 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-l,3,5-triazine [Cybutryne], 2-(thiocyanatomethylthio)-l,3-benzothiazole [TCMTB], 2, 3,5,6- tetrachloro-4-(m ethyl sulfonyl) pyridine, 3-(3,4-dichlorophenyl)-l, 1-dimethylurea [Diuron], N-(2,4,6-trichlorophenyl)maleimide, pyridine triphenylborane [
  • the biocide is preferably soluble in a polar medium formed by the monomer mixture.
  • the biocide is medetomidine or tralopyril.
  • the core polymer component is formed by polymerising an ethylenically unsaturated polar monomer or a mixture of ethylenically unsaturated polar monomers in the presence of the dispersant shell polymer solution and in the presence of the organic biocide.
  • Ethylenically unsaturated polar monomers are monomers comprising at least one hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido functionality.
  • Ethylenically unsaturated polar monomers are preferably monomers comprising at least one hydroxyl, carboxylic acid, ether, amino or amido functionality.
  • Ethylenically unsaturated polar monomers are most preferably monomers comprising at least one hydroxyl, carboxylic acid or amido functionality.
  • ethylenically unsaturated polar monomers are polar
  • Suitable monomers for the core polymer are hydroxy functional monomers, especially hydroxyl functional (meth)acrylate monomers.
  • hydroxyl functional alkyl (meth)acrylate monomers such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2- hydroxy-l-methylethyl acrylate, 4-hydroxybutyl acrylate, hydroxyisobutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, hydroxyisobutyl methacrylate and 2,3-dihydroxypropyl methacrylate.
  • Other monomers include hydroxyethyl caprolactone (meth)acrylate, oligo(ethylene glycol) (meth)acrylate, polyethylene glycol) (meth)acrylate and hydroxybutyl vinyl ether.
  • Suitable ether based monomers include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2- methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, oligo(ethylene glycol) methyl ether acrylate poly(ethylene glycol) methyl ester acrylate, 2- methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, oligo(ethylene glycol) methyl ether methacrylate and polyethylene glycol) methyl ester methacrylate.
  • carboxylic acid functional monomers such as carboxy functional (meth)acrylic monomers.
  • Suitable monomers include acrylic acid, 2- carboxyethyl acrylate, methacrylic acid, carboxymethyl methacrylate, mono-2- (methacryloyloxy)ethyl succinate.
  • Preferred amido monomers are vinyl lactam based monomers, such as 1- vinyl-2-pyrrolidone, 1-vinylcaprolactam, l-(2-acryloyloxyethyl)-2-pyrrolidone, 1- (2-methacryloyloxyethyl)-2-pyrrolidone.
  • Other preferred monomers are 5-methyl-3- vinyl-2-oxazolidinone and 4-acryloylmorpholine.
  • Suitable sulfonic acid monomers include sulfonic acid (meth)acrylic monomers, such as 2-acrylamido-2-methyl-l-propanesulfonic acid and 2-sulfoethyl (meth)acrylate; sulfonic acid vinyl monomers, such as vinyl sulfonic acid and 4-styrenesulfonic acid.
  • ethylenically unsaturated non-polar monomers include methyl (meth)acrylate, ethyl (meth)acrylate and propyl (meth)acrylate.
  • Any monomer mixture should comprise at least 30 wt%, preferably at least 50 wt%, especially at least 80 wt% of the polar monomer(s). That means of course that the final polymer should comprise at least 30 wt% of the polar monomer residues and so on.
  • all monomers that are employed in the manufacture of the core polymer are ethylenically unsaturated polar monomers as herein defined. Ideally, one ethylenically unsaturated polar monomer is used to make the core polymer.
  • the monomer or monomer mixture for the core polymer is a good solvent for the biocide.
  • the amount of biocide in the polymer particle is determined by the solubility of the biocide in the monomer mixture.
  • the solubility of the biocide in core monomer or monomer mixture should be 100 mg/g or more, such as 250 mg/g or more.
  • the core component may optionally be cross-linked.
  • Cross-linking can be achieved by using multifunctional ethylenically unsaturated monomers, preferably di- or trifunctional ethylenically unsaturated monomers in the polymerization process.
  • the use of crosslinking is not preferred and ideally, there is no crosslinking.
  • Polymerization reactions to prepare either core or shell polymeric dispersants can be effected under conventional conditions using conventional initiation. Polymerization is typically effected under elevated temperature of 50 to 150 °C, such as 100 °C. The use of a thermal free-radical initiator, such as an azo or peroxide initiator, is preferred.
  • the shell polymeric dispersant When preparing the core polymer, it is generally preferred if there is as little of the shell polymeric dispersant as possible to ensure the formation of the core-shell structure.
  • the theoretical part of core polymer is the sum by weight of all core polymer monomers and biocide present.
  • the final core-shell polymer particle preferably comprises 1.0 to 45 wt% of the organic biocide, such as 5.0 to 40 wt%, especially 10 to 38 wt%.
  • the final core-shell polymer particle preferably comprises 1.0 to 30 wt% of the organic biocide, such as 5.0 to 28 wt%, especially 10 to 25 wt%.
  • the core polymer monomer is a hydroxyl functional (meth)acrylate monomer, carboxy functional (meth)acrylic monomer, sulfonic acid monomer or vinyl lactam based monomer, such as l-vinyl-2- pyrrolidone.
  • core-shell polymer particles form a still yet further aspect of the invention.
  • the invention provides core-shell particles comprising:
  • a polar core component comprising an organic biocide and a polymer of one or more vinyl lactams or ethylenically unsaturated (meth)acrylate monomers wherein said ethylenically unsaturated (meth)acrylate monomers comprises a polar group selected from a hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido group and wherein more than 30 % by weight of said polymer comprises the residues of said vinyl lactam or ethylenically unsaturated (meth)acrylate monomers;
  • a shell polymeric dispersant comprising a polymer of one or more ethylenically unsaturated (meth)acrylate monomers wherein less than 20 % by weight of said polymeric dispersant comprises the residue of vinyl lactams or ethylenically unsaturated (meth)acrylate monomers comprising a group selected from a hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido groups.
  • core-shell particles comprise:
  • a polar core component comprising an organic biocide and a polymer which consists of one or more ethylenically unsaturated (meth)acrylate monomers wherein said monomers comprises a polar group selected from a hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido group;
  • a shell polymeric dispersant consisting of a polymer of one or more aliphatic ethylenically unsaturated (meth)acrylate monomers wherein said aliphatic ethylenically unsaturated (meth)acrylate monomers are free of hydroxyl, carboxylic acid, ether, sulfonic acid, amino or amido groups; and a non-aqueous solvent.
  • the core-shell polymer particles can be used in a coating composition using any conventional binder.
  • the core-shell polymer particles are preferably provided in the form of a solution for such an application.
  • the solids content of the solution is ideally 30 to 70 wt%, such as 40 to 60 wt%. It may have a Brookfield viscosity of 50 to 1500 cP.
  • the binder in the antifouling paint formulation is one that comprises a polymeric binder component comprising a plurality of ester groups.
  • the binder may therefore comprise a plurality of ester groups in the backbone, side chain or as pendant group of the binder molecule.
  • Preferred paint formulations comprise a binder component such as silyl ester copolymers, polyesters, polyoxalates, hemiacetal ester copolymers and other polymeric material having ester groups.
  • the coating composition of the invention comprises a polymeric binder component comprising a plurality of ester functional groups.
  • the polymeric binder component comprising a plurality of ester functional groups is one that degrades in sea water, i.e. it hydrolyses under the action of sea water.
  • the binder can comprise a single component (i.e. the polymeric binder alone) or comprise multiple components (e.g. the combination of the polymeric binder and a monocarboxylic acid type compound).
  • the binder should comprise at least one polymeric binder compound that comprises a plurality of ester functional groups.
  • the polymeric binder may be one based on a (meth)acrylic polymer having esters in pendant groups or in side chains of the polymer (e.g. as described in GB2558739, GB2559454, WO2019/096926, WO2016/167360 and W02018/086670).
  • the ester functional groups may be present in the backbone of the polymer such as polyesters (e.g. as described in EP1072625 and WO2014/010702) and polyoxalates (e.g. as described in W02009/100908, WO2015/114091 and WO2015/114092).
  • a preferred polymeric binder comprising a plurality of ester groups is a silyl ester copolymer, polyoxalate, polyester, (meth)acrylic hemiacetal ester copolymer, poly(ester-siloxane) or poly(ester-ether-siloxane). More preferably the polymeric binder comprising a plurality of ester groups is a silyl ester copolymer, polyoxalate, (meth)acrylic hemiacetal ester copolymer, poly(ester-siloxane) or poly(ester-ether-siloxane).
  • the polymeric binder comprising a plurality of ester groups is a silyl ester copolymer.
  • silyl ester copolymers in antifouling coating compositions is well known and, in its broadest embodiment, the invention covers any of these well- known hydrolysable binders.
  • Such silyl ester copolymers are well known commercial products.
  • the silyl ester copolymer comprises the residue of at least one monomer (A) of formula (II) wherein
  • R 1 and R 2 are each independently selected from linear or branched Ci- 4 alkyl groups
  • R 3 , R 4 and R 5 are each independently selected from the group consisting of linear or branched Ci-20 alkyl groups, C3-12 cycloalkyl groups, optionally substituted C6-2o aryl groups and -OSi(R 6 ) 3 groups; each R 6 is independently a linear or branched C1-4 alkyl groups, n is an integer from 0 to 5;
  • X is an ethylenically unsaturated group, such as acryloyloxy group, methacryloyloxy group, (methacryloyloxy)alkylcarboxy group, (acryloyloxy)alkylcarboxy group, maleinoyloxy group, fumaroyloxy group, itaconoyloxy group and citraconoyloxy group.
  • the silyl ester copolymer comprises one or more monomers (A) having silyl ester functionality as defined by the general formula (II) in the amount of 1-99 % by weight of the total mixture of monomers, more preferably 15-70 % by weight, most preferably 30-60% by weight.
  • preferred silyl ester monomers are based on compounds of formula (II) in which n is 0, i.e. those of formula X-SiR 3 R 4 R 5 .
  • silyl ester monomers are of formula (III) wherein
  • R 7 is H or CI3 ⁇ 4
  • R 3 , R 4 and R 5 are each independently selected from the group consisting of linear or branched Ci-20 alkyl groups, Ce-20 aryl groups and -OSi(R 6 )3 groups; each R 6 is independently a linear or branched C1-4 alkyl groups.
  • Monomers containing silyl ester functionality are well known.
  • Monomers as defined by the general formula (II) include: silyl ester monomers of acrylic acid and methacrylic acid, such as triisopropylsilyl (meth)acrylate, tri-n-butyl silyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri(2-ethylhexyl)silyl (meth)acrylate, tert-butyldimethylsilyl (meth)acrylate, thexyldimethylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, triisopropylsiloxycarbonylmethyl (meth)acrylate, nonamethyltetrasiloxy (meth)acrylate, bis(trimethylsiloxy)methylsilyl (meth)acrylate, tris(trimethylsiloxy)silyl (meth)acrylate.
  • the silyl ester copolymer preferably comprises 1 to 3 different monomers of formula (II) and more preferably 1 or 2 different monomers of formula (III).
  • the silyl ester copolymer comprises one or more polymerizable monomers other than monomers A.
  • monomers copolymerizable with monomers A include (meth)acrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isopropylideneglycerol (meth)acrylate, glycerolformal (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, hydroxyethyl (meth)acryl
  • the silyl ester copolymer comprises one or more monomers containing two or more polymerizable ethylenically unsaturated bonds, preferably in the combination with one or more chain transfer agents.
  • monomers containing two or more polymerizable ethylenically unsaturated bonds include monomers such as 1,2-ethanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,3-glycerol di(meth)acrylate, methacrylic anhydride, zinc di(meth)acrylate, divinyl benzene, 1,4-butanediol divinyl ether and trimethylolpropane tri(meth)acrylate.
  • Suitable chain transfer agents include thiol compounds such as 1-octanethiol, 1- dodecanethiol, tert-dodecanethiol, 2-ethylhexyl mercaptoacetate, isooctyl mercaptoacetate, butyl 3-mercaptopropionate and isooctyl 3-mercaptopropionate.
  • the proportion of at least one of monomers A represented by formula (II) or (III) to at least one polymerizable monomer other than monomers A can be suitably determined according to the use of the coating composition.
  • the proportion of at least one of monomers A is preferably from 1 to 99% by weight and that of at least one other monomer is preferably from 95 to 1% by weight, preferably 15-70 % by weight, more preferably 30-60 % by weight of the total mixture of monomers.
  • the copolymer containing organosilyl ester groups desirably has a weight- average molecular weight of from 1,000 to 100,000, preferably 5,000 to 70,000, more preferred from 10,000 to 50,000.
  • Preferred silyl ester copolymers have a glass transition temperature (Tg), preferably as measured as described in the experimental section, of 10 °C to 70 °C, more preferably 15 °C to 60 °C and still more preferably 20 °C to 50 °C.
  • Tg glass transition temperature
  • the solution of the polymer desirably has a viscosity of 50 P or lower, preferably 20 P or lower at 23 °C (measured as described in the experimental section).
  • the polymer solution is desirably regulated so as to have a solid content of from 5 to 90% by weight, preferably from 35 to 85% by weight, more preferably from 40 to 75% by weight.
  • the copolymer containing organosilyl ester groups can be linear or branched.
  • a particularly suitable and preferred silyl ester copolymer is triisopropylsilyl (meth)acrylate copolymer.
  • the silyl ester copolymer is a binder component in a physically drying coating, optionally the silyl ester copolymer is a binder component in a curable coating.
  • the silyl ester copolymer is cured using suitable curing agents.
  • curable silyl ester copolymers are silyl ester copolymer having one or more epoxy-functional groups curable in the presence of curing agent e.g. those selected from amines, amine epoxy adducts and polymercaptans, e.g.
  • silyl ester copolymer having one or more hydroxy- functional groups curable in the presence of an isocyanate curing agent which preferably comprises one or more polyisocyanates, e.g. as described in WO2012/048712.
  • Silyl ester copolymers and their use as binders in antifouling coating compositions are further described e.g. in GB2558739, GB2559454, W02009/007276, W02005/005516, EP2781567, WO2019/096926, DE102018128728 and GB2576431.
  • silyl ester copolymers are copolymers of silyl ester monomers and siloxane monomer.
  • the copolymers comprises the residue of silyl ester monomers of the formula (III) above and other polymerizable monomers as described for silyl ester copolymers above and one or more siloxane monomers such as a- (meth)acryloyloxypropyl-co-butyl poly dimethyl siloxane, a- (meth)acryloyloxypropyl-co-trimethyl silyl polydimethylsiloxane, a- (meth)acryloyloxyethyl-co-tri methyl silyl polydimethylsiloxane, a- vinyl-co-butyl polydimethylsiloxane, a-vinyl-co-trimethylsilyl poly dimethyl siloxane, a, a’ -(methyl methacryloyloxypropyl)-bis(co-butyl) polydimethylsiloxanes, 3- tris(trimethylsiloxy)silylpropyl methacryl
  • binders are further described e.g. in WO2011/046087.
  • silyl ester copolymers are copolymers of silyl ester monomers and metal monomer.
  • the copolymers comprises the residue of silyl ester monomers of the formula (III) above and other polymerizable monomers as described for silyl ester copolymers and one or more metal monomers such as zinc (meth)acrylate, zinc acetate (meth)acrylate, zinc octanoate (meth)acrylate, zinc neodecanoate (meth)acrylate, zinc laurate (meth)acrylate, zinc stearate (meth)acrylate, zinc naphthenate (meth)acrylate, copper (meth)acrylate, copper acetate (meth)acrylate, copper octanoate (meth)acrylate, copper neodecanoate (meth)acrylate, copper laurate (meth)acrylate, copper stearate (meth)acrylate, and copper naphthenate (meth)acrylate.
  • metal monomers such as zinc (meth)acrylate, zinc acetate (meth)acrylate, zinc o
  • silyl ester copolymers are copolymers of silyl ester monomers and zwitterionic monomer.
  • the copolymer comprises silyl ester groups and quaternary ammonium groups and/or quaternary phosphonium groups, where the said quaternary ammonium groups and/or quaternary phosphonium groups are neutralised by counter-ions and wherein the counter-ions consist of the conjugate base of an acid having aliphatic, aromatic or alkaryl hydrocarbyl group.
  • the copolymer is obtained by polymerizing monomers comprising silyl ester group(s) and monomers comprising the quaternary ammonium group(s) and/or quaternary phosphonium group(s), where the quaternary ammonium groups and/or quaternary phosphonium groups are being neutralised by counter-ions, wherein the counter-ions consist of the conjugate base of an acid having aliphatic, aromatic or alkaryl hydrocarbyl group , and optionally other monomers.
  • the polymer may be (meth)acrylic polymer.
  • binders are further described e.g. in WO2016/066567.
  • Another preferred group of binders comprising a plurality of ester groups are (meth)acrylic hemiacetal ester copolymer.
  • the (meth)acrylic hemiacetal ester copolymer comprises a residue of at least one monomer of formula (IV): wherein
  • R 1 is H or methyl;
  • R 2 is H or Ci- 4 alkyl;
  • R 3 is Ci - 4 alkyl
  • R 4 is optionally substituted, linear or branched, Ci- 20 alkyl, C 5-10 cycloalkyl or C 6-10 aryl; or
  • R 3 and R 4 together with the O atom to which they are attached, form an optionally substituted C4-8 membered ring.
  • R 2 is H and R 3 is methyl or ethyl, especially methyl.
  • R 4 is optionally substituted, linear or branched, C4-18 alkyl or C5-10 cycloalkyl. Still more preferably R 4 is unsubstituted C4-18 alkyl or unsubstituted C5-10 cycloalkyl.
  • R 4 is selected from butyl, pentyl, hexyl, heptyl, octyl, dodecyl, octadecyl and cyclohexyl and particularly preferably from butyl, octyl, dodecyl, octadecyl and cyclohexyl.
  • R 4 is butyl, it is preferably n-butyl or isobutyl.
  • R 4 is octyl, it is preferably 2-ethylhexyl.
  • R 2 is H
  • R 3 is methyl or ethyl, especially methyl
  • R 4 is selected from butyl, pentyl, hexyl, heptyl, octyl, dodecyl, octadecyl and cyclohexyl.
  • R 4 is butyl, it is preferably n-butyl or isobutyl.
  • R 4 is octyl, it is preferably 2-ethylhexyl.
  • R 3 and R 4 together with the O atom to which they are attached, form an optionally substituted C4-8 membered ring.
  • the ring preferably comprises 4 or 5 carbon atoms, i.e. together with the O atom, a 5 or 6 membered ring is formed.
  • R 3 and R 4 together with the O atom to which they are attached, form an unsubstituted tetrahydrofuranyl or tetrahydropyranyl ring.
  • R 2 is H, and R 3 and R 4 , together with the O atom to which they are attached, form an unsubstituted tetrahydrofuranyl or tetrahydropyranyl ring.
  • Preferred monomers of formula (IV) include 1-w-butoxy ethyl (meth)acrylate, 1-isobutoxyethyl (meth)acrylate, l-(2-ethylhexyloxy)ethyl (meth)acrylate, 1- cyclohexyloxy ethyl (meth)acrylate, 1-dodecyloxy ethyl (meth)acrylate, 1- octadecyloxyethyl (meth)acrylate, 2 -tetrahydrofuranyl (meth)acrylate and 2- tetrahydropyranyl (meth)acrylate.
  • the (meth)acrylic hemiacetal ester copolymer preferably comprises 1 to 3 different monomers of formula (IV) and more preferably 1 or 2 different monomers of formula (IV).
  • the (meth)acrylic hemiacetal ester copolymer comprises one or more polymerizable monomers other than monomers of formula (IV).
  • monomers copolymerizable with monomers of formula (IV) include (meth)acrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(2- ethoxyethoxy)ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isopropylideneglycerol (meth)acrylate, glycerolformal (meth)acrylate, cyclic trimethylolpropane formal (
  • the (meth)acrylic hemiacetal ester copolymer does not comprise repeat units derived from acrylic acid and/or methacrylic acid.
  • the proportion of at least one of monomers of formula (IV) to at least one polymerizable monomer other than monomers of formula (IV) can be suitably determined according to the use of the coating composition.
  • the proportion of at least one of monomers of formula (IV) is preferably from 1 to 99% by weight and that of at least one other monomer is preferably from 95 to 1% by weight, preferably 15-70 % by weight, more preferably 20-50 % by weight, yet more preferably 25-45 wt% monomers of formula (IV), based on the total mixture of comonomers.
  • Suitable (meth)acrylic hemiacetal ester copolymers may be prepared using polymerization reactions known in the art.
  • the (meth)acrylic hemiacetal ester copolymer may be a random copolymer, an alternate copolymer, a gradient copolymer or block copolymer.
  • Preferred (meth)acrylic hemiacetal ester copolymers have a weight average molecular weight of 1,000 to 100,000, preferably 5,000 to 70,000, more preferably 15,000 to 60,000 and still more preferably 20,000 to 50,000, measured as described in the experimental section.
  • Preferred (meth)acrylic hemiacetal ester copolymers have a glass transition temperature (Tg), preferably as measured according to the method set out in the examples, of 10 °C to 70 °C, more preferably 15 °C to 60 °C and still more preferably 20 °C to 50 °C.
  • Tg glass transition temperature
  • the total amount of (meth)acrylic hemiacetal ester copolymer present in the compositions of the invention is 2-60 wt%, more preferably 5-40 wt% and still more preferably 7-30 wt%, based on the total weight of the final composition (i.e. if the composition is supplied as a two-pack, these values refer to the wt% present in the final mixed composition).
  • Hybrid copolymers based (meth)acrylic hemiacetal ester monomers with other monomers, such as silyl ester monomers and polysiloxane monomers, are described e.g. in EP0714957 and WO2017/065172.
  • Another preferred group of binders comprising a plurality of ester groups are acrylic copolymers with polyester segments in the polymer backbone.
  • the copolymers are prepared by polymerizing vinyl monomers, such as silyl ester (meth)acrylates, zinc carboxylate (meth)acrylates, copper carboxylate (meth)acrylate and betaine type of (meth)acrylates, with one or more cyclic monomers, such as lactide, glycolide, caprolactone, 2-methyl-e-caprolactone, butyrolactone, valerolactone, 2-methylene- 1, 3 -dioxepane, ethylene carbonate, propylene carbonate, trimethylene carbonate, 2,2-dimethyl trimethylene carbonate, 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline.
  • vinyl monomers such as silyl ester (meth)acrylates, zinc carboxylate (meth)acrylates, copper carboxylate (meth)acrylate and betaine type of (meth)acrylates
  • cyclic monomers such as lactide, glycolide, caprolactone, 2-methyl-e-caprolactone
  • Such binders are described e.g. in W02015/010390, WO2018/188488, WO20 18/ 196401 and WO2018/196542.
  • silyl ester copolymers prepared by polymerizing silyl ester monomers of the formula (III) and other polymerizable monomers as described for silyl ester copolymers above with one or more cyclic monomers such as lactide, glycolide, caprolactone, 2-methyl-e-caprolactone, butyrolactone, valerolactone, 2- methylene-l,3-dioxepane, ethylene carbonate, propylene carbonate, trimethylene carbonate, 2,2-dimethyl trimethylene carbonate, 2-methyl-2-oxazoline and 2-ethyl- 2-oxazoline.
  • cyclic monomers such as lactide, glycolide, caprolactone, 2-methyl-e-caprolactone, butyrolactone, valerolactone, 2- methylene-l,3-dioxepane, ethylene carbonate, propylene carbonate, trimethylene carbonate, 2,2-dimethyl trimethylene carbonate, 2-methyl-2-oxazoline and
  • polyesters Another preferred binders comprising a plurality of ester groups are polyesters.
  • the term polyester is used herein to define polymers in which the ester groups are present in the backbone of the polymer.
  • the polyester may be obtained by reaction of an acid component with an alcohol component.
  • the acid component for polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid or naphthalenedicarboxylic acid; aliphatic carboxylic acids such as adipic acid, sebacic acid, azelaic acid, succinic acid, or 1,4-cyclohexanedicarboxylic acid; trivalent or greater polybasic acid such as trimellitic acid or pyromellitic acid; or a lower alkyl ester (for example, a Ci - 4 alkyl ester) or acid anhydride of the foregoing.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid or naphthalenedicarboxylic acid
  • aliphatic carboxylic acids such as adipic acid, sebacic acid, azelaic acid, succinic acid, or 1,4-cyclohexanedicarboxylic acid
  • a monocarboxylic acid and a dibasic acid such as an aromatic dicarboxylic acid or saturated aliphatic dicarboxylic acid may each be used alone, or two or more may be used in combination. Trivalent or greater polybasic acids may also be used alone, or in combinations of two or more.
  • the alcohol components for polyester resin include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-l,5-pentanediol, 2-methyl-l, 3- propanediol, 2,2-diethyl- 1 , 3 -propanediol, 2-butyl-2-ethyl- 1 , 3 -propanediol, hydrogenated bisphenol A, ethylene oxide addition products or propylene oxide addition products of bisphenol A and trivalent or greater polyhydric alcohols such as trimethylolethane, trimethylolpropane, glycerine and pent
  • Polyester resins are simply prepared by combining the acid component and alcohol component under esterification or transesterification reaction conditions. Such reactions are trivial and well known.
  • the polyester resin preferably has an acid value of 50 to 250 mg KOH/g, more preferably 100 to 150 mg KOH/g. To obtain an acid value within the preferred range, there may be applied method of introducing a carboxylic acid end groups using dibasic acid, polybasic acid or their anhydrides.
  • the polyester resin preferably has a weight-average molecular weight of 8,000 or less, more preferably 4,000 or less.
  • the acid functional polyester resin may further be reacted with a polyvalent metal compound to form a metal salt crosslinked structure.
  • binders are further described e.g. in W02014/010702 and WO2012/176809.
  • polyester binder are polyoxalates.
  • the polyoxalate may be a linear or branched polymer. It will be appreciated that any polyoxalate comprises at least two oxalate units, preferably at least 5 oxalate units, e.g. at least 8 oxalate units.
  • the polyoxalate will preferably be formed from the polymerization of at least one oxalate monomer and at least one diol monomer, more preferably the polyoxalate will be formed from the polymerization of at least one oxalate monomer, at least one diol monomer, and at least a monomer selected form cyclic dicarboxylic acids and alkyl ester of cyclic dicarboxylic acid.
  • the polyoxalates can be prepared by condensation polymerization using any of various methods known and used in the art.
  • the poly condensation reactions can be carried out as melt or in solution.
  • the polycondensation is carried out in the presence of a catalyst.
  • the starting materials for the preparation of polyoxalates depend on the polymerization process.
  • the polyoxalates are however formed from oxalic acid or a derivative thereof, i.e. an oxalate monomer.
  • derivative thereof is meant a mono or diester thereof, a mono or diacid halide (e.g. chloride) thereof, or salt thereof, e.g. alkali metal salt thereof.
  • the oxalate monomer used in the polymerization reaction may be oxalic acid or an ester of oxalic acid, especially a diester.
  • Esters may be alkyl esters, alkenyl esters or aryl esters.
  • Dialkyl oxalates are preferred. Examples of preferred dialkyl oxalates for the preparation of polyoxalates include dimethyl oxalate and diethyl oxalate.
  • diols for the preparation of polyoxalates include saturated aliphatic and saturated cycloaliphatic diols, unsaturated aliphatic diols or aromatic diols. Linear or branched saturated aliphatic diols and saturated cycloaliphatic diols are preferred.
  • Examples of preferred diols include 1,3-butanediol, 1,4-butanediol, 1,6- hexanediol, 1,9-nonanediol, 2-methyl- 1,3 -propanediol, 2,2-dimethyl-l,3- propanediol, 2,2,4-trimethyl-l,3-pentanediol, 2-ethyl-l,3-hexandiol, 2,4-diethyl- 1,5-pentanediol, 2-butyl-2-ethyl-l, 3 -propanediol, 3 -hydroxy-2, 2-dimethylpropyl 3- hydroxy-2,2-dimethylpropionate, 1 ,4-cyclohexanedimethanol, 4,4'- isopropylidenedicyclohexanol, 2,5-furandimethanol and 4,4'-(propane-2,2- diyl)diphenol.
  • diols 1,6-hexanediol, 2,2-dimethylpropane-l,3-diol, 2-butyl-2-ethyl- 1 ,3 -propanediol, 2,2,4-trimethyl- 1 ,3 -pentanediol, 1 ,4- cyclohexanedimethanol, and 4,4'-isopropylidenedicyclohexanol.
  • diols can be used alone or in combination of two or more diols.
  • a mixture of two or more diols is used to manufacture the polyoxalates.
  • the polyoxalates are prepared from aliphatic or cycloaliphatic diols.
  • at least one diol used to manufacture the polyoxalates is a saturated aliphatic branched diol.
  • at least two saturated branched diols are used or a mixture of a linear or cyclic saturated diol and a saturated branched diol.
  • Aliphatic or cycloaliphatic diols preferably form therefore at least 50 mol%, preferably at least 75 mol%, optionally 100 mol% of the total diols used to form the polyoxalate.
  • Suitable functional compounds can be included as comonomers to adjust the polymer properties of the polyoxalates. Such compounds can be used to adjust parameters such as hydrolysis rate and mechanical properties. These functional compounds preferably possess two reactive functional groups e.g. two ester, acid, amino or hydroxyl groups or mixtures thereof and will be called bifunctional compounds. These compounds can form additional monomers in the polymerization process.
  • bifunctional compounds examples include alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl isophthalate and dimethyl 1,4-cyclohexanedicarboxylate; dicarboxylic acid anhydrides such as phthalic anhydride and tetrahydrophthalic anhydride; and dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid and 1,4- cyclohexanedicarboxylic acid.
  • dicarboxylic acids such as dimethyl terephthalate, dimethyl isophthalate and dimethyl 1,4-cyclohexanedicarboxylate
  • dicarboxylic acid anhydrides such as phthalic anhydride and tetrahydrophthalic anhydride
  • dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,5-furandicarboxylic acid and 1,4- cyclohexanedicarboxylic
  • a particularly preferred combination of use in the manufacture of polyoxalates is that of an oxalate monomer and a bifunctional compound as hereinbefore defined.
  • An especially preferred reactant combination is therefore an oxalate monomer and an alkyl ester of dicarboxylic acid, dicarboxylic acid anhydride or dicarboxylic acid.
  • the polyoxalates preferably have a number average molecular weight (Mn) from 1,000 to 100,000 more preferably 1000 to 40,000, especially 1000 to 10,000.
  • the polyoxalates preferably have a weight average molecular weight (Mw) from 1,000 to 200,000, e.g. from 1,000 to 100,000 more preferably 1,000 to 40,000, especially 1,000 to 25,000. In some embodiments the Mw may be 10,000 to 40,000, e.g. 20,000 to 40,000.
  • Mw weight average molecular weight
  • the polyoxalate binder may be combined with a curing agent in the antifouling coating composition of the invention.
  • Polyoxalates have functional end groups that react with curing agents. Examples of curing agents well known in the art include, for example, monomeric isocyanates, polyisocyanates and isocyanate prepolymers. Polyisocyanates are preferred over monomeric isocyanates. Polyisocyanates can for example be based on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexam ethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) chemistry. Polyisocyanates with different NCO - functionality can be used. The functionality of the curing agent is preferably at least 2, such as an average functionality of 2 to 3.
  • a curing catalyst can be used.
  • catalysts are tin catalysts, e.g. dibutyltin dilaurate.
  • binders comprising a plurality of ester groups are poly(ester-siloxane) and poly(ester-ether-siloxane).
  • the ester groups are present in the backbone of the polymer.
  • the binder comprises a plurality of units of formula (V) or formula (VI): wherein each R 1 is independently an unsubstituted or substituted Ci-20 alkyl, C2-20 alkenyl, C3-20 cycloalkyl, Ce-20 aryl, C7-20 arylalkyl group, or polyoxyalkylene chain, especially methyl; each R is independently Ci- 6 alkyl or H, especially H; m is an integer from 1 to 10, such as 1 to 5, especially 2 to 5, especially 3 to
  • n is an integer from 1-500, more preferably 10-300, especially 15- 100;
  • Q 1 is an aliphatic, cycloalkyl, cycloalkenyl or aromatic group having up to 20 carbon atoms, or a covalent bond;
  • Q 2 is an aliphatic, cycloalkyl, cycloalkenyl, polyoxyalkylene or aromatic group having up to 20 carbon atoms.
  • the binder comprises poly(dimethyl siloxane) segments linked together with ester bonds.
  • the binder comprises polyoxyalkylene segments, such as polyethylene glycol) and polypropylene glycol).
  • the binder can be prepared by polycondensation reaction using any of various methods known in the art.
  • Example of preparation method include transesterification of carbinol terminated polydimethylsiloxane and alkyl ester of dicarboxylic acid monomers, such as diethyl oxalate, diethyl succinate and diethyl adipate.
  • the binder preferably has a number average molecular weight of 2,000 to 100,000 such as 5,000 to 80,000, especially 10,000 to 50,000.
  • the binder polymer may possess a curable end group, such groups include silanol, carbinol, carboxyl, ester, hydride, alkenyl, vinyl ether, allyl ether, alkoxysilane and alkoxy group.
  • the total amount of poly(ester-siloxane) or poly(ester-ether- siloxane) copolymer present in the compositions of the invention is 30-95 wt%, more preferably 40-90 wt% and still more preferably 50-90 wt%, based on the total weight of the final composition (i.e. if the composition is supplied as a two or three- pack, these values refer to the wt% present in the final mixed composition).
  • binder systems such as the silyl ester copolymers and the various hybrids, the (meth)acrylic hemiacetal ester copolymers and the polyester resins, may include one or more further binder components as part of the binder system.
  • polymeric binders such as acrylic resins such as homopolymers and copolymers of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and isobutyl methacrylate, having an acid value of 0 to 40 mg KOH/g; hydrophilic polymers such as (meth)acrylate copolymers containing monomer units of hydroxyalkyl (meth)acrylate, alkoxyalkyl (meth)acrylate or alkylaminoalkyl (meth)acrylates; and homopolymers and copolymers of (meth)acrylamides, homopolymers and copolymers of l-vinyl-2-pyrrolidinone and 1-vinylcaprolactam; polyethylene oxides and polypropylene oxides; vinyl ether homopolymers and copolymers,
  • acrylic resins such as
  • binders include: alkyd resins and modified alkyd resins; esters of gum rosin and hydrogenated gum rosin such as methyl esters of rosin, glycerol esters of rosin and pentaerythritol esters of rosin; hydrocarbon resin, such as hydrocarbon resin formed from the polymerization 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 acrylic resins, esters of gum rosin and polymeric plasticizers.
  • the additional binder is present in an amount of 0-15 wt%, more preferably 0.5-10 wt% and still more preferably 1-7 wt%, based on the total weight of the composition.
  • binder systems such as the silyl ester copolymers and the various hybrids, the (meth)acrylic hemiacetal ester copolymers and the polyester resins, may include one or more monocarboxylic acid or derivative thereof.
  • Monocarboxylic acids and derivatives of monocarboxylic acids have a number of properties that makes them applicable in antifouling coating compositions. They contribute to the controlled release of biocides, adjust the water solubility and mechanical properties of the antifouling coating, and reduce viscosity. They are readily available and many of them originate from renewable, natural resources.
  • the monocarboxylic acid present in the antifouling coating composition of the present invention preferably comprises 5 to 50 carbon atoms, more preferably 10 to 40 carbon atoms and still more preferably 12 to 25 carbon atoms.
  • the monocarboxylic acid present in the antifouling coating composition of the present invention is preferably selected from a resin acid or derivative thereof, e-20 cyclic monocarboxylic acid, C5-24 acyclic aliphatic monocarboxylic acid, C7-20 aromatic monocarboxylic acid, a derivative of any of the monocarboxylic acids, and mixtures thereof.
  • Derivatives of monocarboxylic acid include metal salts of monocarboxylic acid, such as alkali metal carboxylate, alkaline earth metal carboxylate (e.g. calcium carboxylate, magnesium carboxylate) and transition metal carboxylate (e.g. zinc carboxylate, copper carboxylate).
  • the metal carboxylate is a transition metal carboxylate, particularly preferably the metal carboxylate is a zinc carboxylate or copper carboxylate.
  • the metal carboxylate may be added directly to the antifouling coating composition or be generated in situ in the antifouling coating composition.
  • resin acids include abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, communic acid and mercusic acid, secodehydroabietic acid.
  • Resin acids are also referred to as rosin acids.
  • sources of resin acids are gum rosin, wood rosin and tall oil rosin. Gum rosin, also referred to as colophony and colophonium, is particularly preferred.
  • Preferred rosins are those comprising more than 85 % resin acids and still more preferably more than 90 % resin acids.
  • rosin typically have an acid value from 155 to 180 mg KOH/g as specified in ASTM D465 and a softening point (Ring & Ball) of 70 °C to 80 °C as specified in ASTM E28.
  • resin acid derivatives include partly hydrogenated rosin, fully hydrogenated rosin, disproportionated rosin, dihydroabietic acids, dihydropimaric acids and tetrahydroabietic acids.
  • Ce-20 cyclic monocarboxylic acids include naphthenic acid and trimethyl isobutenyl cyclohexene carboxylic acids.
  • C5-24 acyclic aliphatic monocarboxylic 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, 3,5,5-trimethylhexanoic acid, isopalmitic acid, isostearic acid, 16- methylheptadecanoic acid and 12,15-dimethylhexadecanoic acid.
  • VersaticTM acids neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4- di
  • the acyclic aliphatic monocarboxylic acid is preferably selected from liquid, acyclic Cio-24 monocarboxylic acids or liquid, branched Cio-24 monocarboxylic acids. It will be appreciated that many of the acyclic Cio-24 monocarboxylic acids may be derived from natural sources, in which case in isolated form they typically exist as a mixture of acids of differing chain lengths with varying degree of branching.
  • the monocarboxylic acid is gum rosin, derivatives of gum rosin, metal salts of gum rosin and derivatives of gum rosin, acyclic Cio-24 monocarboxylic acids, Cfi-2o cyclic monocarboxylic acids or mixtures thereof.
  • a mixture of acid preferably contains at least one resin acid, gum rosin, derivative of gum rosin or metal salts of gum rosin. Gum rosin and zinc salts of gum rosin is most preferred.
  • the amount of monocarboxylic acid or derivative thereof present in the compositions of the invention is 5 to 40 wt%, preferably 10 to 35 wt%, more preferably 15 to 30 wt%, based on the total weight of the binder system.
  • the final antifouling coating composition of the invention preferably comprises 0.5 to 25 wt% of the monocarboxylic acid or derivative thereof, such as 1 to 20 wt%, in particular 2 to 18 wt% based on the total coating composition.
  • the antifouling coating composition of the present invention may comprise an additional marine biocide (iii).
  • antifouling agent biologically active compounds
  • antifoulant toxicant
  • biocide used in the industry to describe known compounds that act to prevent marine fouling on a surface.
  • the biocide may be inorganic, organometallic or organic, preferably an organometallic or inorganic biocide. Suitable biocides are commercially available.
  • the core-shell particles of the invention wherein the core comprises an organic biocide may be combined with other organic biocides in the antifouling coating composition.
  • inorganic biocides include copper and copper compounds such as copper oxides, e.g. cuprous oxide and cupric oxide, copper thiocyanate and copper sulfide, copper powder and copper flakes.
  • organometallic biocides include zinc pyrithione, copper pyrithione, zinc bis(dimethyldithiocarbamate) [Ziram] and zinc ethylenebis(dithiocarbamate) [Zineb]
  • organic biocides examples include 2-(tert-butylamino)-4- (cyclopropylamino)-6-(methylthio)-l,3,5-triazine [Cybutryne], 2- (thiocy anatomethylthio)- 1 , 3 -benzothiazole [T CMTB ], 2,3,5 , 6-tetrachloro-4- (methylsulfonyl) pyridine, 3-(3,4-dichlorophenyl)-l,l-dimethylurea [Diuron], N- (2,4,6-trichlorophenyl)maleimide, pyridine triphenylborane [PTBP, PK], 3-iodo-2- propynyl N-butylcarbamate [IPBC], 2,4,5,6-tetrachloroisophthalonitrile, dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide [Dichloflu
  • biocides include tetraalkylphosphonium halogenides, guanidine derivatives such as dodecylguanidine monohydrochloride; macrocyclic lactones including avermectins and derivatives thereof such as ivermectine; spinosyns and derivatives such as spinosad; and enzymes such as oxidase, proteolytically, hemicellulolytically, cellulolytically, lipolytically and amylolytically active enzymes.
  • Copper based antifouling coating compositions contain inorganic copper biocides such as metallic copper, cuprous oxide, copper thiocyanate and the like.
  • the cuprous oxide material has a typical particle diameter distribution of 0.1- 70 pm and an average particle size (D50) of 1-25 pm.
  • Examples of commercial available cuprous oxide paint grades include Nordox Cuprous Oxide Red Paint Grade, Nordox XLT from Nordox AS, Cuprous oxide from Furukawa Chemicals Co., Ltd.; Red Copp 97N, Purple Copp, Lolo Tint 97N, Chemet CDC, Chemet LD from American Chemet Corporation; Cuprous Oxide Red from Spiess-Urania; Cuprous oxide Roast, Cuprous oxide Electrolytic from Taixing Smelting Plant Co., Ltd.
  • Preferred biocides are cuprous oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [Zineb], 2-(tert-butylamino)-4- (cyclopropylamino)-6-(methylthio)- 1,3,5 -triazine [Cybutryne] , pyridine triphenylborane [PTBP, PK], dichlorofluoromethylthio-N',N'-dimethyl-N- phenylsulfamide [Dichlofluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-N-p- tolylsulfamide [Tolylfluanid], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT, Sea-Nine TM ], 4-bromo-2-(4-chlorophenyl)-5
  • a mixture of biocides can be used, as is known in the art, as different biocides operate against different marine fouling organisms. Mixtures of biocides are generally preferred.
  • the combined amount of biocides may form up to 60 wt% of the coating composition, such as 0.1 to 50 wt%, e.g. 5 to 45 wt%.
  • a suitable amount of biocide 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 10 wt%. It will be appreciated that the amount of biocide will vary depending on the end use and the biocide used.
  • biocides may be encapsulated (by methods different from the present invention) or adsorbed on an inert carrier or bonded to other materials for controlled release. These percentages refer to the amount of active biocide present and not therefore to any carrier used.
  • the antifouling coating composition of the present invention preferably comprise one or more components selected among pigments, extenders and fillers.
  • the pigments may be inorganic pigments, organic pigments or a mixture thereof.
  • Inorganic pigments are preferred.
  • examples of inorganic pigments include titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, zinc oxide, zinc sulfide, lithopone and graphite.
  • examples of organic pigments include carbon black, phthalocyanine blue, phthalocyanine green, naphthol red and diketopyrrolopyrrole red.
  • the pigments may optionally be surface treated.
  • extenders and fillers are minerals such as dolomite, plastorite, calcite, quartz, baryte, magnesite, aragonite, silica, nepheline syenite, wollastonite, talc, chlorite, mica, kaolin, pyrophyllite, perlite, silica and feldspar; synthetic inorganic compounds such as calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zinc phosphate and silica (colloidal, precipitated, fumed, etc.); polymeric and inorganic microspheres such as uncoated or coated hollow and solid glass beads, uncoated or coated hollow and solid ceramic beads, 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
  • the total amount of extender, fillers and/or pigment present in the compositions of the invention is 2-60 wt%, more preferably 5-50 wt% and still more preferably 7-45 wt%, based on the total weight of the composition.
  • the extender and pigment content will vary depending on the particle size distribution, the particle shape, the surface morphology, the particle surface-resin affinity, the other components present and the end use of the coating composition.
  • the coating composition of the present invention preferably comprises a solvent.
  • This solvent is preferably volatile and is preferably organic. 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; aliphatic and alicyclic hydrocarbons such as mixtures of normal-, iso- and cyclo- paraffins, mineral spirits and white spirit; ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone; esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, propyl propionate, n-butyl propionate, isobutyl isobutyrate; ether esters such as 2-methoxy ethyl acetate, l-methoxy-2-propyl acetate, ethyl
  • the amount of solvent present in the 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% and more preferably 1-30 wt% based on the total weight of the composition.
  • some raw materials comprise solvent and contribute to the total solvent content as specified above and that the solvent type and content will vary depending on the other components present and the end use of the coating composition.
  • the coating composition of the present invention optionally comprises one or more additives.
  • additives that may be present in the coating composition of the invention include rheology modifiers, such as thixotropic agents, thickening agents and anti-settling agents; dehydrating agents and stabilizers; surfactants, such as dispersing agents, wetting agents and defoam ers; plasticizers and reinforcing agents.
  • rheology modifiers include thixotropic agents, thickening agents and anti-settling agents.
  • Representative examples of rheology modifiers are 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.
  • Rheology modifiers that need activation may be added to the coating composition as is and activated during the paint production process or they can be added to the coating composition in a pre-activated form, e.g. solvent paste.
  • rheology modifiers are each present in the composition of the invention in an amount of 0-5 wt%, more preferably 0.2-3.0 wt% and still more preferably 0.5-2.0 wt%, based on the total weight of the coating composition.
  • the dehydrating agent is preferably a compound which removes moisture and water from the coating composition. It is also referred to as water scavenger or drying agent.
  • the dehydrating agents may be hygroscopic materials that absorb water or bind water as crystal water. These are often referred to as desiccants. Examples of desiccants include anhydrous calcium sulphate, calcium sulphate hemihydrate, anhydrous magnesium sulphate, anhydrous sodium sulphate, anhydrous zinc sulphate, molecular sieves and zeolites.
  • the dehydrating agents may also be compounds that chemically react with water.
  • the preferred dehydrating agents will depend on the binder system. Their use would be familiar to the skilled person.
  • Stabilizers are preferably acid scavengers.
  • stabilizers are carbodiimide compounds, such as bis(2,6-diisopropylphenyl)carbodiimide, bis(2- methylphenyl)carbodiimide and 1,3-di-p-tolylcarbodiimide.
  • the dehydrating agents and stabilizers are each 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 coating composition comprises a dehydrating agent and/or a stabiliser, especially a dehydrating agent.
  • plasticizers are polymeric plasticizers, silicone oils, mineral oils, chlorinated paraffins, phthalates, phosphate esters, sulphonamides, adipates, epoxidized vegetable oils and sucrose acetate isobutyrate.
  • plasticizers are present in the compositions of the invention in an amount of 0-20 wt%, more preferably 0.5-10 wt% and still more preferably 1-5 wt%, based on the total weight of the coating composition.
  • Fibres include natural and synthetic inorganic fibres and natural and synthetic organic fibres e.g. as described in WO 00/77102.
  • Representative examples of fibres include mineral glass fibres, wollastonite fibres, montmorillonite fibres, tobermorite fibres, atapulgite fibres, calcined bauxite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, and processed mineral fibres from mineral wool.
  • the fibres have an average length of 25 to 2,000 pm and an average thickness of 1 to 50 pm 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.
  • Coating composition comprising binder, such as poly(ester-siloxane) and poly(ester-ether-siloxane), optionally include one or more additive oils.
  • additive oils include non-reactive polysiloxane oils, such as methylphenyl silicone oil, non-reactive hydrophilic-modified polysiloxane oils, sterols and/or sterol derivatives, such as lanolin and lanolin derivatives, hydrophilic modified sterols and/or sterol derivatives, petroleum oils, polyolefin oils, polyaromatic oils and fluorinated polymers/oligomers.
  • additive oils are present in the coating composition of the present invention in an amount of 0-30 wt% and more preferably 5-20 wt%, based on the solids content of the coating composition.
  • the amount of these additives will depend on the binder technology and will be readily determined by the skilled person.
  • the present invention also relates to a method of preparing the composition as hereinbefore described wherein the components present in the composition are mixed. Any conventional production method may be used. It is preferred that the core-shell particles are added in the let-down phase or as a final addition.
  • 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 and optionally other components are added to the composition described herein to form paint.
  • Preferred solvents are as hereinbefore described in relation to the composition.
  • the coating composition may be supplied as one-pack or as a two-pack or as a three-pack. Curing agent will obviously be kept separate from the curable component until application on a substrate. Whilst the core-shell polymer particles can be kept separate from the binder, it is preferred if these are present together in the supplied formulation.
  • the composition When 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 first container When supplied as a two-pack, the first container preferably comprises a binder, core-shell polymer particles and biocide; and the second container preferably comprises crosslinking agent/curing agent and/or catalyst. Instructions for mixing the contents of the containers may optionally be provided.
  • the amounts of binder, biocide, core-shell particles etc in the coating composition can vary significantly depending on the content of solvent and, more importantly the content of any inorganic biocide. If cuprous oxide is present, it forms a large weight percentage of the coating composition and hence the relative weight percentages of other components is reduced considerably.
  • the coating composition of the invention preferably has a binder content of 10-95 wt%.
  • the coating composition of the invention preferably has a core-shell polymer particles content of 0.25-30 wt%, such as 0.25 to 25 wt%, more preferably 0.5 to 20 wt%, such as 0.5 to 15 wt%.
  • the coating composition of the invention preferably has a biocide content of 1.0-60 wt%.
  • the antifouling coating composition of the invention preferably have solids content above 45 vol%, e.g. above 50 vol%, such as above 52 vol%, preferably above 55 vol%.
  • the viscosity of the coating composition may be in the range of less than 2,000 cP, such as less than 1,000 cP, e.g. less than 800 cP when measured using a Cone and Plate viscometer in accordance with ISO 2884.
  • the antifouling coating composition should have a content of volatile organic compounds (VOC) below 500 g/L, preferably below 420 g/L, more preferably below 400 g/L, e.g. below 380 g/L.
  • VOC content can be calculated as described in e.g. ASTM D5201-05a or measured, e.g. as described in US EPA Method 24 or ISO 11890-2.
  • the coating composition and paint of the invention can be applied to a whole or part of any article surface which is subject to marine 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 and/or cured.
  • the coating composition of the present invention may be applied to any pre treated substrates designed for such coatings.
  • an object e.g. a ship hull
  • the surface of the object is not protected solely by a single coat of antifouling coating composition.
  • the antifouling coating can be applied directly to an existing coating system.
  • Such a coating system may comprise several layers of paint of different generic types (e.g. epoxy, polyester, vinyl or acrylic or mixtures thereof).
  • an uncoated surface e.g. steel, aluminium, plastic, composite, glass fibre or carbon fibre
  • the full coating system will typically comprise one or two layers of an anticorrosive coating (e.g.
  • curable epoxy coating or curable modified epoxy coating one layer of tie-coat (e.g. curable modified epoxy coating or physical drying vinyl coating) and one or two layers of antifouling paint.
  • tie-coat e.g. curable modified epoxy coating or physical drying vinyl coating
  • antifouling paint In exceptional cases further layers of antifouling paint may be applied. If the surface is a clean and intact antifouling coating from a previous application, the new antifouling paint can be applied directly, typically as one or two coats with more in exceptional cases. When two or more coats of antifouling coating composition is applied, the different coats can be antifouling coatings of different compositions. The person skilled in the art will be familiar with these coating layers.
  • the core-shell polymer particles of the invention may also be suitable for use in fouling release coatings.
  • the invention provides a fouling release coating composition
  • a fouling release coating composition comprising: a) a curable polysiloxane based binder comprising at least 50 wt% polysiloxane parts; b) a plurality of core-shell polymer particles as hereinbefore defined.
  • Such a composition preferably additionally comprises a non-reactive polysiloxane.
  • the fouling release coating composition might comprise the non reactive polysiloxane in an amount of 2 to 30 wt% by dry weight, preferably 10- 25 wt% by dry weight, based on the total dry weight of the composition.
  • the non reactive polysiloxane can be non-modified polysiloxane or a hydrophilic modified polysiloxane or mixtures thereof.
  • the fouling release coating composition might be based on a polysiloxane- based binder represented by formula (VII): wherein each R 1 is independently selected from a hydroxyl group, Ci- 6 -alkoxy group, Ci- 6 -epoxy containing group, Ci- 6 amine group or 0-Si(R 5 )3- z (R 6 )z each R 2 is independently selected from Ci-io alkyl, C6-10 aryl, C7-10 alkylaryl or Ci - 6 alkyl substituted by poly(alkylene oxide) and/or a group as described for R 1 ; each R 3 and R 4 is independently selected from Ci-10 alkyl, C6-10 aryl, C7-10 alkylaryl or Ci- 6 alkyl substituted by poly(alkylene oxide); each R 5 is independently a hydrolysable group such as Ci- 6 alkoxy group, an acetoxy group, an enoxy group or ketoxy group; each R 6 is independently selected from an unsubsti
  • Figure 1 shows the panels tested in example 1 and comparative examples 1 and 2.
  • the viscosity of the polymer solutions was determined in accordance with ASTM D2196 Test Method A using a Brookfield DV-I Prime digital viscometer at a rotational speed of 12 rpm and with a LV-2 spindle for solutions with viscosity from 50 to 1000 cP or a LV-4 spindle for solutions with viscosity above 1000 cP.
  • the polymer solutions were tempered to 23.0 °C ⁇ 0.5 °C before the measurements.
  • the non-volatile matter content in the polymer solutions was determined in accordance with ISO 3251.
  • a test sample of 0.5 g ⁇ 0.1 g was taken out and dried in a ventilated oven at 150 °C for 30 minutes for the polymer dispersant solutions and 110 °C in 3 hours for the non-aqueous dispersion and other polymer solutions.
  • the weight of the residual material was considered to be the non-volatile matter (NVM).
  • the non-volatile matter content is expressed in weight percent. The value given is the average of three parallel measurements.
  • 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.
  • Samples were prepared by dissolving an amount of polymer solution corresponding to 25 mg dry polymer in 5 ml THF. The samples were kept for minimum 3 hours at room temperature prior to sampling for the GPC measurements. Before analysis the samples were filtered through 0.45 pm Nylon filters. The weight-average molecular weight (Mw) and the polydispersity index (PDI) are reported.
  • Mw weight-average molecular weight
  • PDI polydispersity index
  • the glass transition temperature (Tg) was obtained by Differential Scanning Calorimetry (DSC) measurements.
  • DSC measurements were performed on a TA Instruments DSC Q200.
  • the measurement was performed by running a heat- cool-heat procedure, within a temperature range from -80 °C to 150 °C, with a heating rate of 10 °C/min and cooling rate of 10 °C/min and using an empty pan as reference.
  • 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.
  • Samples of dispersant resins were prepared by transfer of an amount of polymer solution, corresponding to approx. 10 mg of the dry polymer material, to an aluminium pan and dry the sample over night at 50 °C with subsequent drying for 3 h at 150 °C in ventilated heating cabinets.
  • Samples of other polymer solutions were prepared by drawdown of the polymer solutions on individual glass panels using an applicator with 100 pm gap size.
  • the glass panels were dried over night at room temperature and subsequently 24 hours at 50 °C in a ventilated heating cabinet.
  • the dry polymer material was scraped off the glass panels and approx. 10 mg of the dry polymer material was transferred to an aluminium pan.
  • the pan was sealed with a non-hermetic lid.
  • the average particle size was determined by dynamic light scattering (DLS) using a Malvern Zetasizer Nano S particle size analyser. The instrument was used according to the manufacturer's instructions and with its accompanying software.
  • the samples were prepared by adding 1-2 droplets of the polymer dispersion to approx. 50 mL of white spirit. A sample of the mixed solution was transferred to the cuvette. The measurements were performed at 25 °C. The result is reported as the Z-average particle size. The value given is the average of three consecutive measurements.
  • Disposable PMMA cuvettes were used for the measurements.
  • the refractive index value for the white spirit was 1.438 at 20 °C.
  • Approx. 2 g of the final non-aqueous dispersion was weighed into a vial and added approx. 4 g of white spirit. The accurate weights were recorded using an analytical balance. The mixture was centrifuged at 25,000 rpm for 10 minutes or until separation into a clear upper phase (supernatant).
  • the amount of free biocide in the solvent phase as a fraction of the total amount of biocide added in the preparation of the non-aqueous dispersion (NAD) were calculated using the following formula: where w bs is the weight fraction of biocide in the solvent relative to the total biocide added in wt%, w bNAD weight fraction of biocide added to the non-aqueous dispersion in wt%, c bsn is the concentration of biocide in the supernatant in pg / g, m NAD 1S the mass of the non-aqueous dispersion added to the vial in g, m sol is the mass of the solvent added to the vial in g, and
  • NVM NAD is the non-volatile content of the non-aqueous dispersion in wt%.
  • the viscosity of the antifouling paint composition was determined in accordance with ISO 2884-1 :2006 using a digital Cone and Plate viscometer set at a temperature of 23 °C, working at a shear rate of 10 000 s-1 and providing viscosity measurement range of 0-10 P. The result is given as the average of three measurements.
  • PVC panels (20 cm x 30 cm) were used for the test.
  • the panels were coated with a first coat of a commercial primer/tiecoat (Safeguard Plus, manufactured by Chokwang Jotun Ltd., Korea) using airless spray and a second coat of a commercial antifouling paint (SeaQuantum Ultra S, manufactured by Jotun Paints (Europe) Ltd., England).
  • the curing/drying time and film thicknesses of the first coat and the second coat were within the recommended intervals in the technical data sheets for the products.
  • the antifouling coating compositions of the examples were applied directly to the pre-coated PVC panels as a last coat using a film applicator with a 400 pm gap size.
  • the test areas of the applied coating films were approx. 6 cm x 20 cm.
  • the edges of the panels were sealed with a commercial antifouling product.
  • the antifouling coating compositions of the examples were applied within 1 to 5 days after paint preparation.
  • the panels were exposed on rafts in Florida, USA or Singapore where the panels were submerged 0.5 - 1.5 m below the sea surface.
  • the panels were evaluated by visual inspection and rated according to the scale below. Macroalgae, such as seaweed, and animal fouling, such as barnacles, tubeworms, mussels, sponges and hydroids, were rated separately.
  • Microfouling organisms such as biofilm or slime, which can easily be removed by hand, is not included in the rating.
  • Example 1 Preparation of polymeric core-shell particles containing medetomidine
  • Preparation of polymeric dispersant solution - A1 45.0 parts of white spirit 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 100 °C.
  • a post addition of a boost initiator solution of 0.50 parts te/V-butyl peroxy-2-ethylhexanoate and 22.0 parts white spirit was fed to the reaction vessel at a constant rate over 1 hour.
  • the reaction vessel was maintained at the reaction temperature for a further 2 hours. 33.8 parts of white spirit was added to dilute the reaction mixture.
  • the reaction vessel was then cooled to room temperature.
  • the parts given above are all parts by weight.
  • the prepared dispersant solution A1 had the following properties:
  • the reaction vessel was maintained at the reaction temperature for a further 2 hours. 28.3 parts of white spirit was added to dilute the reaction mixture. The reaction vessel was then cooled to room temperature. The parts given above are all parts by weight.
  • the prepared non-aqueous dispersion solution B1 has the following properties: Solution viscosity 210 cP; NVM 50.9 wt%; Z-average particle size 555 nm.
  • the other non-aqueous dispersions were prepared by the same process using the ingredients and amounts as listed in Table 1 A, Table IB and Table 1C. All ingredients are given in parts by weight.
  • the prepared silyl ester copolymer solution had the following properties: Solution viscosity 210 cP; NVM 50.6 wt%; Mw 33 400, PDI 3.48; Tg 40 °C.
  • the prepared silyl ester copolymer solution had the following properties: Solution viscosity 1402 cP; NVM 55.6 wt%; Mw 49 000, PDI 2.70; Tg 50 °C.
  • the prepared silyl ester copolymer solution had the following properties: Solution viscosity 1955 cP; NVM 59.9 wt%; Mw 31 100, PDI 3.03; Tg 48 °C.
  • the non-aqueous dispersion resin solutions and the comparative biocide solution were added to the base paint and mixed.
  • the amounts in parts by weight are given in Table 3A, Table 3B, Table 3C, Table 4A and Table 4B.
  • Example Ml of the invention show good storage stability and antifouling performance.
  • the comparative example CM1 shows poor storage stability, while the comparative example CM2 without added medetomidine shows poor fouling resistance against barnacles. Panels tested are shown in figure 1.
  • Example M2 of the invention show good storage stability and antifouling performance.
  • the comparative example CM3 shows poor storage stability, while the comparative example CM4 without added medetomidine shows poor fouling resistance against barnacles.
  • Examples Tl, T2 and T3 of the invention show good storage stability and antifouling performance.
  • the comparative example CT1 shows poor fouling resistance against animal fouling.
  • the comparative examples CT1 and CT2 show significant change in the paint consistency at the initial viscosity measurement indicating a reaction between tralopyril and the other paint ingredients. No viscosity measurements were made.

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Abstract

L'invention concerne une composition de revêtement antisalissure comprenant : (I) un composant liant polymère comprenant une pluralité de groupes fonctionnels ester ; (ii) une pluralité de particules de polymère à noyau et enveloppe, le noyau comprenant un biocide organique et un polymère d'un ou de plusieurs monomères éthyléniquement insaturés, au moins l'un desdits monomères éthyléniquement insaturés comprenant un groupe polaire choisi parmi hydroxyle, acide carboxylique, éther, acide sulfonique, amino ou amido et ledit polymère comprenant plus de 30 % en poids de résidus monomères comprenant des groupes polaires ; et un dispersant polymère à enveloppe comprenant un polymère d'un ou plusieurs monomères à insaturation éthylénique, ledit dispersant polymère comprenant moins de 20 % en poids de résidus de monomères à insaturation éthylénique comprenant des groupes polaires choisis parmi hydroxyle, acide carboxylique, éther, acide sulfonique, amino ou amido ; et (iii) éventuellement, un biocide supplémentaire.
EP21713698.5A 2020-03-27 2021-03-25 Composition de revêtement antisalissure Pending EP4126335A1 (fr)

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Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5767171A (en) 1994-11-21 1998-06-16 Nof Corporation Coating composition
JPH10168350A (ja) 1996-12-10 1998-06-23 Mitsubishi Rayon Co Ltd 防汚性塗料組成物
AU5061800A (en) 1999-06-11 2001-01-02 J.C. Hempel's Skibsfarve-Fabrik A/S Self-polishing marine antifouling paint composition comprising silicon-containing co-polymers and fibres
NO327258B1 (no) 1999-07-27 2009-05-25 Ishikawajima Harima Heavy Ind Polyesterharpiks for anvendelse i en grohemmende maling samt grohemmende maling omfattende polyesterharpiksen
WO2003027194A2 (fr) * 2001-12-20 2003-04-03 Hempel A/S Dispersion non aqueuse reposant sur une composition de peinture antisalissure
WO2005005516A1 (fr) 2003-07-07 2005-01-20 Akzo Nobel Coatings International B.V. Compositions de copolymere d'ester de silyle
WO2009007276A1 (fr) 2007-07-06 2009-01-15 Jotun A/S Polymère ramifié et composition de revêtement anti-salissures comprenant le polymère
PL2247642T3 (pl) 2008-02-13 2014-01-31 Jotun As Kompozycja przeciwporostowa
US20110274763A1 (en) 2009-05-19 2011-11-10 Nyden Bo Magnus Slow releasing microcapsules and microspheres containing an active substance
CN102686683B (zh) 2009-10-13 2014-12-31 日本油漆船舶涂料公司 防污涂料组合物以及防污涂膜、复合涂膜和水中结构物
EP2392543A1 (fr) 2010-06-02 2011-12-07 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Revêtements actifs à rétroaction avec conteneurs sensibles basés sur des nano, micro, mini et macro-émulsions de type direct ou inversé
EP2627721B1 (fr) 2010-10-14 2017-04-05 Hempel A/S Composition de peinture antisalissure à haute teneur en matières solides
WO2012176809A1 (fr) 2011-06-23 2012-12-27 中国塗料株式会社 Composition de peinture anti-salissures de type à hydrolyse à deux composants, film de revêtement anti-salissures et procédé de fabrication d'un substrat anti-salissures
WO2013000476A1 (fr) 2011-06-30 2013-01-03 Hempel A/S Composition de peinture antisalissures à teneur élevée en matières solides
KR101647903B1 (ko) 2011-11-14 2016-08-11 주고꾸 도료 가부시키가이샤 방오도료 조성물, 방오도막, 방오기재 및 방오기재의 제조방법
JP5989774B2 (ja) 2012-07-12 2016-09-07 中国塗料株式会社 防汚塗料用ポリエステル樹脂、その製造方法、防汚塗料組成物、防汚塗膜、防汚基材
KR102042240B1 (ko) 2013-03-27 2019-11-08 주식회사 케이씨씨 가수분해성 금속함유 공중합체 바인더, 그 제조방법 및 이를 이용한 방오도료 조성물
CN103396513B (zh) 2013-07-24 2016-03-02 华南理工大学 一种主链断裂型聚丙烯酸类硅烷酯树脂的制备方法及应用
WO2015082397A1 (fr) 2013-12-05 2015-06-11 Ppg Coatings Europe B.V. Composition de revêtement
EP2902452A1 (fr) 2014-01-31 2015-08-05 Jotun A/S Composition antisalissure
EP2902453A1 (fr) 2014-01-31 2015-08-05 Jotun A/S Composition antisalissure
JP6595494B2 (ja) 2014-10-22 2019-10-23 日東化成株式会社 防汚塗料組成物用共重合体、防汚塗料組成物、防汚塗膜
EP3212680B1 (fr) 2014-10-28 2018-09-05 Akzo Nobel Coatings International B.V. Compositions de peintures antisalissures comprenant un polymère contenant un ester de silyl et un groupe ammonium ou phosphonium quaternaire
SG11201707659QA (en) 2015-04-16 2017-10-30 Mitsubishi Chem Corp Antifouling coating composition
KR20180030999A (ko) 2015-07-13 2018-03-27 에보니크 데구사 게엠베하 가수분해가능한 결합제
JPWO2017065172A1 (ja) 2015-10-13 2018-07-26 三菱ケミカル株式会社 （メタ）アクリル系共重合体、樹脂組成物、防汚塗料組成物及び（メタ）アクリル系共重合体の製造方法
EP3298895A1 (fr) 2016-09-22 2018-03-28 Greenseal Research Ltd Microcapsules biocides pour la lutte contre l'encrassement biologique
JP7178167B2 (ja) 2016-11-11 2022-11-25 ヨトゥン アーエス 防汚組成物
CN108070055B (zh) 2016-11-11 2022-10-04 佐敦公司 防污组合物
KR20190082884A (ko) 2016-11-11 2019-07-10 헴펠 에이/에스 신규 가수분해성 탄소계 폴리머를 포함하는 방오용 코팅 조성물
GB2573944B (en) 2017-01-19 2022-11-09 Jotun As Antifouling composition
GB201703455D0 (en) * 2017-03-03 2017-04-19 Jotun As Composition
CN107033278B (zh) 2017-04-14 2019-05-14 华南理工大学 一种具有主链降解性的自抛光两性离子防污树脂及其制备与应用
CN106986969B (zh) 2017-04-28 2022-02-11 华南理工大学 一种主链降解型聚丙烯酸铜树脂及其制备方法与应用
CN107056990A (zh) 2017-04-28 2017-08-18 华南理工大学 一种单体法制备的主链降解型聚丙烯酸锌树脂及其方法与应用
WO2019081495A1 (fr) * 2017-10-23 2019-05-02 Hempel A/S Composition de revêtement antisalissure autopolissante comprenant un alcoxysilane
GB201718899D0 (en) 2017-11-15 2017-12-27 Jotun As Antifouling coating composition
US10225643B1 (en) 2017-12-15 2019-03-05 Intel Corporation Secure audio acquisition system with limited frequency range for privacy
GB201804434D0 (en) 2018-03-20 2018-05-02 Jotun As Composition
GB201813454D0 (en) 2018-08-17 2018-10-03 Jotun As Antifouling composition

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