WO2024115765A1 - Processus - Google Patents

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Publication number
WO2024115765A1
WO2024115765A1 PCT/EP2023/083990 EP2023083990W WO2024115765A1 WO 2024115765 A1 WO2024115765 A1 WO 2024115765A1 EP 2023083990 W EP2023083990 W EP 2023083990W WO 2024115765 A1 WO2024115765 A1 WO 2024115765A1
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WO
WIPO (PCT)
Prior art keywords
polysiloxane
coating
group
layer
coating layer
Prior art date
Application number
PCT/EP2023/083990
Other languages
English (en)
Inventor
Marit Seim
Henrik Holthe KRINGHAUG
Anita BØRVE
Original Assignee
Jotun A/S
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Publication date
Application filed by Jotun A/S filed Critical Jotun A/S
Publication of WO2024115765A1 publication Critical patent/WO2024115765A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/542—No clear coat specified the two layers being cured or baked together
    • 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
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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
    • C09D7/65—Additives macromolecular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2420/00—Indexing scheme corresponding to the position of each layer within a multilayer coating relative to the substrate
    • B05D2420/01—Indexing scheme corresponding to the position of each layer within a multilayer coating relative to the substrate first layer from the substrate side
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2425/00—Indexing scheme corresponding to the position of each layer within a multilayer coating relative to the surface
    • B05D2425/01—Indexing scheme corresponding to the position of each layer within a multilayer coating relative to the surface top layer/ last layer, i.e. first layer from the top surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2425/00—Indexing scheme corresponding to the position of each layer within a multilayer coating relative to the surface
    • B05D2425/02—Indexing scheme corresponding to the position of each layer within a multilayer coating relative to the surface second layer from the top surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • B05D7/587—No clear coat specified some layers being coated "wet-on-wet", the others not

Definitions

  • This invention relates to a process for preparing a multilayer coating system.
  • the invention provides a process in which at least two coating layers comprising a polysiloxane-based coating composition are applied and wherein the second coating layer is applied a specific time interval after the first coating layer.
  • Fouling release coatings are used on marine vessels to prevent fouling by marine organisms. These work on the principle that the fouling release surface has a very low coefficient of friction and hence it is challenging for marine organisms to cling to the surface, especially when a vessel is underway and hence the action of the sea can wash marine organisms from the hull.
  • Fouling release coatings are therefore characterized by low surface tension and low modulus of elasticity so that biofouling does not stick to the surface or the biofouling is easily washed off by the friction of the water against the surface.
  • Such coatings often comprise polysiloxane-based binders having reactive (curable) groups such as hydroxyl or silyl units.
  • a polysiloxane-based binder can be hydrolysed and condensed in the presence of moisture and catalysts.
  • a fouling release coating system is applied as a system with two coats of primer, one coat of tie coat and one coat of top coat.
  • the paint is spray applied with a small overlapping pattern (typically 10 - 15 cm).
  • US6048580 describes application of a tie coat and a top coat to a substrate.
  • EP3974482 describes a fouling release coating based on a combination of polysiloxane binders with biocide and catalyst to encourage curing. The coating is applied in one layer.
  • the overcoating window for polysiloxane-based fouling release coatings is narrow, and atmospheric conditions may interrupt application of the coatings, causing the second coat to be applied outside the overcoating window with the result of poor adhesion, or even leading to failure to apply the second coat. It also takes a longer time to apply and cure two coats versus one coat with same total thickness.
  • topcoat coatings which are designed to be applied as two coats specify at least 8 hours between the application of the two layers.
  • the challenge with polysiloxane- based coatings is that if the first layer has fully dried/cured, the next layer will have poor adhesion even if the next layer is also a polysiloxane-based coating.
  • the polysiloxane topcoat is designed to prevent objects (e.g. marine organisms) sticking to the surface. Once cured, it possesses a surface which will deter the adhesion of other materials.
  • the inventors have found that it is possible to apply a second coating layer shortly after the first coating layer has been applied. This method will save time in dock and reduce the risk of weather complications and poor adhesion.
  • the invention is to apply two coats of topcoat in one go, without waiting for the coating to cure before applying a second coat.
  • the application of the second coat can start 5 minutes after the first coat has been applied, allowing some solvents to evaporate and the curing to start. It will thus be understood that, in the processes of the invention, the first coating layer does not fully cure before the second coating layer is applied.
  • the process of the invention also offers the potential advantages of more uniform film thickness and reduced risk of sagging in overlap areas where the film thickness is higher than specified. Furthermore, it allows for the achievement of higher film thickness with a lower sag resistance paint.
  • the invention provides a process for preparing a multilayer coating system comprising at least two coating layers wherein i) a first coating layer is applied by spray application to a wet film thickness of 50-300 pm; and ii) a second coating layer is applied by spray application to a wet film thickness of 50-300 pm; wherein the second coating layer is applied directly on top of the first coating layer 5 min - 6 hours after the first coating layer is applied; and wherein the first and the second coating layers independently comprise a polysiloxane-based coating composition comprising a) a polysiloxane-based binder system b) a curing agent or crosslinking agent.
  • fouling release composition or “fouling release coating composition” refers to a composition which, when applied to a surface, provides a fouling release surface to which it is difficult for sea organisms to permanently stick.
  • fouling release coating system will be understood to refer to a coating system with an analogous definition.
  • top-coat refers to the polysiloxane-based coating composition.
  • the polysiloxane-based coating composition is a fouling release coating composition.
  • binder system refers to the film forming components of the composition.
  • the polysiloxane-based binder(s) of the composition is the main binder in the binder system, i.e. it forms at least 50 wt% of the binder system, such as at least 75 wt%.
  • binder system does not encompass additive oils. Additive oils are not considered herein to be film-forming components.
  • the binder system consists of polysiloxane-based binder(s).
  • the term “paint” refers to a composition comprising the coating composition as herein described and optionally solvent which is ready for use, e.g. for spraying.
  • the 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.
  • polysiloxane-based binder refers to a binder that comprises at least 50 wt%, preferably at least 60 wt% and more preferably at least 70 wt% repeat units comprising the motif -Si-O-, based on the total weight of the polymer.
  • Polysiloxane-based binders may comprise up to 99.99 wt% repeat units comprising the motif -Si-O-, based on the total weight of the polymer.
  • the repeat units, -Si-O- may be connected in a single sequence or alternatively may be interrupted by non-siloxane parts, e.g. organic-based parts.
  • non-degradable polysiloxane-based binder refers to a polysiloxane-based binder which does not undergo hydrolytic degradation or erosion in sea water.
  • alkyl refers to saturated, straight chained, branched or cyclic groups.
  • cycloalkyl refers to a cyclic alkyl group.
  • alkylene refers to a bivalent alkyl group.
  • alkenyl refers to unsaturated, straight chained, branched or cyclic groups.
  • aryl refers to a group comprising at least one aromatic ring.
  • aryl encompasses fused ring systems wherein one or more aromatic ring is fused to a cycloalkyl ring.
  • An example of an aryl group is phenyl, i.e. CeHs.
  • substituted refers to a group wherein one or more, for example up to 6, more particularly 1 , 2, 3, 4, 5 or 6, of the hydrogen atoms in the group are replaced independently of each other by the corresponding number of the described substituents.
  • arylalkyl group refers to groups wherein the bond to the Si is via the alkyl portion.
  • polyether refers to a compound comprising two or more -O- linkages interrupted by alkylene units.
  • poly(alkylene oxide) refers to a compound comprising -alkylene-O- repeat units.
  • alkylene is ethylene or propylene.
  • wt.% is based on the dry weight of the coating composition, unless otherwise specified
  • PDI polydispersity index
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • volatile organic compound refers to a compound having a boiling point of 250 °C or less.
  • anti-antifouling agent 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.
  • This invention relates to a process for preparing a coating system comprising at least two coating layers wherein a second coating layer is applied directly on top of a first coating layer 5 min - 6 hours after the first coating layer is applied and wherein the first and the second coating layers independently comprise a polysiloxane-based coating composition comprising a) a polysiloxane-based binder system b) a curing agent or crosslinking agent.
  • the binder system in the coating composition comprises at least one curable polysiloxane-based binder .
  • Any polysiloxane-based binder is preferably a non-degradable curable polysiloxane-based binder.
  • Any polysiloxane-based binder present in the coating compositions of the present invention comprises at least 50 wt% polysiloxane parts, preferably more than 60 wt% polysiloxane parts and still more preferably more than 70 wt% polysiloxane parts such as 99.99 wt% polysiloxane parts or more, relative to the total weight of the binder.
  • Typical ranges include 50-100 wt% polysiloxane parts, 60-99.999 wt% polysiloxane parts, or 70-99.99 wt% polysiloxane parts in the polysiloxane-based binder.
  • the polysiloxane parts are defined as repeat units comprising the motif -Si-O- based on the total weight of the polysiloxane-based binder.
  • the wt% of polysiloxane parts can be determined based on the stoichiometric wt ratio of starting materials in the polysiloxane synthesis.
  • the polysiloxane content can be determined using analytical techniques such as IR or NMR.
  • the wt.% of polysiloxane parts is calculated based on the molar ratio of reactive starting materials in the polysiloxane synthesis. If a molar excess of a monomer is present in the reaction mixture then such a molar excess is not counted. Only those monomers that can react based on the stoichiometry of the reaction are counted.
  • the polysiloxane-based binder can consist of a single repeating sequence of siloxane units or be interrupted by non-siloxane parts, e.g. organic parts. It is preferred if the polysiloxane-based binder contains only Si- O repeating units.
  • the organic parts may comprise, for example, alkylene, arylene, poly(alkylene oxide), amide, thioether or combinations thereof, preferably the organic parts may comprise, for example, alkylene, arylene, poly(alkylene oxide), amide, or combinations thereof.
  • the polysiloxane-based binder comprises functional groups that enable a crosslinking reaction to take place either between polysiloxane-based binder molecules or via a crosslinking agent.
  • Any polysiloxane-based binder is preferably an organopolysiloxane with terminal and/or pendant curing-reactive functional groups.
  • a minimum of two curing-reactive functional groups per molecule is preferred.
  • Examples of curing- reactive functional groups are silanol, alkoxy, acetoxy, enoxy, ketoxime, amineoxy, amine, epoxy, vinyl and/or isocyanate.
  • a preferred polysiloxane-based binder contains curing-reactive functional groups selected from silanol, alkoxy or acetoxy groups.
  • the curing reaction is typically a condensation cure reaction.
  • the polysiloxane-based binder optionally comprises more than one type of curing- reactive group and may be cured, for example, via both condensation cure and amine/epoxy curing.
  • the polysiloxane-based binder may consist of only one type of polysiloxane or be a mixture of different polysiloxanes as long as the requirements of the invention are fulfilled.
  • the polysiloxane-based binder may be a linear or branched polysiloxane- based binder.
  • branched is meant that the polysiloxane chain is branched.
  • the branched polysiloxane-based binder may also comprise cage-like polysiloxane structures also known as polysiloxane resins.
  • polysiloxane-based binder is linear.
  • a preferred polysiloxane-based binder, present in the fouling release coating compositions of the present invention is represented by formula (D1) below: wherein each R 1 is independently selected from a hydroxyl group, Ci-6-alkoxy group, O- Si(R 5 )3-z (R 6 )z, Ci-6-hydroxyl group, Ci-6-epoxy containing group, C1-6 amine group, C1-10 alkyl group, Ce-w aryl or C?-w alkaryl.
  • each R 1 is independently selected from hydroxyl group, Ci-6-alkoxy group, O-Si(R 5 )3-z (R 6 ) z .
  • each R 2 is independently selected from C1-10 alkyl, Ce- aryl, C?-w alkylaryl or C1-6 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- alkyl, Ce- aryl, C?-w alkylaryl or C1-6 alkyl substituted by poly(alkylene oxide); each R 5 is independently a hydrolysable group such as C1-6 alkoxy group, an acetoxy group, an enoxy group or ketoxy group; each R 6 is independently selected from a C1-6 alkyl group; z is 0 or an integer from 1-2; x is an integer of at least 2; y is an integer of at least 2.
  • R 1 is selected from a hydroxyl group and O-Si(R 5 )3-z(R 6 )z, wherein R 5 is a Ci-Ce alkoxy group, R 6 is C1-6 alkyl and z is 0 or an integer from 1-2. More preferably R 1 is selected from a hydroxyl group and O-Si(R 5 )3-z(R 6 )z, wherein R 5 is a C1-C3 alkoxy group, R 6 is C1-3 alkyl and z is 0 or an integer from 1-2. Still more preferably R 1 is a hydroxyl group.
  • R 2 is a C1-10 alkyl group. More preferably R 2 is a C1-4 alkyl group, still more preferably a C1-2 alkyl group, and yet more preferably a methyl group. Preferably each R 2 is the same.
  • R 3 is a C1-10 alkyl group. More preferably R 3 is a C1-4 alkyl group, still more preferably a C1-2 alkyl group, and yet more preferably a methyl group. Preferably each R 3 is the same.
  • R 4 is a C1-10 alkyl group. More preferably R 4 is a C1-4 alkyl group, still more preferably a C1-2 alkyl group, and yet more preferably a methyl group. Preferably each R 4 is the same.
  • R 1 is a hydroxyl group and R 2 , R 3 and R 4 are each methyl groups.
  • each R 1 is independently selected from a hydroxyl group, Ci-6-alkoxy group or O- Si(R 5 ) 3 -z (R 6 ) z each R 2 to R 4 are methyl; each R 5 is independently a hydrolysable group such as C1-6 alkoxy group, an acetoxy group, an enoxy group or ketoxy group; each R 6 is independently selected from a C1-6 alkyl group; z is 0 or an integer from 1-2; x is an integer of at least 2; y is an integer of at least 2.
  • Another preferred polysiloxane-based binder, present in the fouling release coating compositions of the present invention is represented by formula (D3) below:
  • R 1 , R 2 , R 3 , R 4 and x and y are as defined for (D1), R x is C2-3 alkyl, each L1 is 0 to 50, each L2 is 0 to 50 with the proviso that L1+L2 is 2 to 50, preferably 4 to 40, more preferably 4 - 20, most preferably 4-10 and L3 is 1-200, preferably 2-100, most preferably 5-50.
  • the polysiloxane parts must form a minimum of 50 wt% of the molecule.
  • polysiloxane-based binder of the present invention is represented by formula (D1).
  • any polysiloxane-based binder of the present invention is a polydimethylsiloxane.
  • the polysiloxane-based binder may contain low amounts of impurities, such as cyclic siloxanes, such as D4, D5 and D6 cyclosiloxanes, that are residues from polysiloxane synthesis, where the name (D4, D5, or D6) refers to the number of repeating Si-0 units in the cyclic polysiloxane (i.e. 4, 5 or 6 repeating Si-0 units in the cyclic polysiloxane respectively). From a health, safety, and environmental aspect, it is preferred to limit the amount of cyclic polysiloxanes present in the coating.
  • impurities such as cyclic siloxanes, such as D4, D5 and D6 cyclosiloxanes, that are residues from polysiloxane synthesis, where the name (D4, D5, or D6) refers to the number of repeating Si-0 units in the cyclic polysiloxane (i.e. 4, 5 or 6 repeating Si-0 units in
  • the polysiloxane-based binder contains less than 5% of cyclic polysiloxanes, preferable less than 2%, more preferably less than 1%. In one particularly preferred embodiment, the polysiloxane-based binder is free of cyclic polysiloxanes.
  • the weight average molecular weight of the polysiloxane-based binder or any combination of polysiloxane-based binders present in the fouling release coating compositions of the present invention is preferably 400-150,000 g/mol, more preferably 1000-120,000 g/mol, and still more preferably 5000-110,000 g/mol.
  • the polysiloxane-based binder or combination of polysiloxane-based binders typically forms at least 35 wt% of the polysiloxane-based coating composition (dry weight), such as at least 40 wt%, especially at least 45 wt%, e.g. 35 to 75 wt% of the fouling release coating composition (dry weight).
  • the required polysiloxane-based binder system comprises two separate polysiloxane polymers A and B with differing molecular weights or viscosities, wherein each of the polysiloxane polymers A and B may be as defined herein and as described in WO2022069482 A1 and WO2022069487 A1. In one embodiment the required polysiloxane-based binder system comprises three separate polysiloxane polymers A, B and C as described in WO2022069487 A1.
  • a combination of a polysiloxane-based binder A and a polysiloxane-based binder B is present the preferred molecular weight and viscosities are as outlined below.
  • the weight average molecular weight (Mw) of the polysiloxane-based binder A is preferably 50,000 g/mol or less, such as 3,500 to 50,000, preferably 8,000 to 50,000 g/mol. In a more preferred embodiment, the weight average molecular weight of the polysiloxane-based binder A is 10,000 to 48,000, more preferably 15,000 to 45,000, especially 20,000 to 40,000 g/mol.
  • the number average molecular weight (Mn) of the polysiloxane-based binder A is less than 25,000 g/mol, such as 1,000 to 24,000 g/mol, preferably 2,000 to 24,000 g/mol. In a more preferred embodiment, the number average molecular weight of the polysiloxane-based binder A is 3,000 to 19,500 g/mol, more preferably 4,000 to 19,500 g/mol, especially 5,000 to 19,500 g/mol.
  • the molecular weight (Mn and Mw) values referred to herein correspond to the experimentally obtained values, e.g. by GPC measured relative to a polystyrene standard. The method is given in the experimental section below.
  • the weight average Mw of polysiloxane-based binder B is preferably 55,000 or more, such as 60,000 to 120,000 g/mol, still more preferably 65,000-110,000 g/mol.
  • the viscosity of the polysiloxane-based binder A is preferably 2,800 mPas or less, such as 400 to 2,800, more preferably 400 to 2,000, especially 500 to 1500 mPas.
  • the viscosity of polysiloxane-based binder B is preferably 3,500 mPas or more, such as 4,000 to 30,000 mPas, still more preferably 5,000-25,000 mPas.
  • each binder forms at least 27 wt% of the binder system, preferably each forms at least 40 wt% of the binder system. It is preferred that the ratio of binder A to binder B is in the range of 30:70 to 70:30, preferably 40:60 to 60:40, more preferably 45:55 to 55:45.
  • each binder forms at least 20 wt% of the coating composition.
  • the PDI of the binder mixture is at least 2.5, such as 2.5 to 10, especially 3.0 to 8.0.
  • the viscosity of the binder system is 400 to 30,000 mPas, more preferably 1000 to 25,000 mPas, even more preferred 2000 to 15,000 mPas, such as 2500 to 11 ,000 mPas.
  • the coating compositions of the invention may comprise additive oils. These additive oils do not comprise any curing reactive groups, hence the additive oils are intended to be non-reactive in the curing reaction. Depending on the curing mechanism for the binder system the functional groups on the additive oils should be chosen so that they do not react in the curing reaction of the polysiloxane-based binder.
  • the additive oils are intended to be free in the coating film so that they can migrate to the surface of the coating film and improve the antifouling properties of the coating film.
  • suitable additive oils are hydrophilic modified polysiloxane oils and hydrophobic modified polysiloxane oils.
  • Other additive oils may also be used such as petroleum oils, polyolefin oils, polyaromatic oils, fluoro resins such as polytetra- fluoroethylene or fluid fluorinated alkyl- or alkoxy-containing polymers, or lanolin and lanolin derivatives and other sterol(s) and/or sterol derivative(s) as disclosed in WO2013024106A1 , or poly(oxyalkylene) modified alcohols such as poly(oxy alkylene) modified sterols as disclosed in W02016004961 A1 or combinations thereof.
  • a further additive oil optionally present in the coating compositions of the invention is fluorinated amphiphilic polymers/oligomers as described in WO2014131695.
  • a suitable additive oil may also be based on (meth)acrylate co-polymers having polysiloxane side chains and polyether or nitrogen containing hydrophilic groups such as described in W02019101912 A1 and W02019101920 A1.
  • the additive oil is a hydrophilic modified polysiloxane oil and/or a hydrophobic modified polysiloxane oil.
  • the hydrophilic modified polysiloxane oils and the hydrophobic modified polysiloxane oil may be used in combination. Suitable hydrophilic modified polysiloxane oils and hydrophobic modified polysiloxane oils are described in more detail below.
  • the coating composition of the invention may additionally comprise a hydrophilic modified polysiloxane. It will be appreciated that this component is different from the polysiloxane-based binder discussed above.
  • hydrophilic modified polysiloxane does not contain silicone reactive groups such as Si-OH groups, Si-OR (alkoxy) groups etc. that can react with the binder or the cross-linker (if present) at relevant curing temperatures (0 - 40 °C), hence the hydrophilic-modified polysiloxane is intended to be non-reactive in the curing reaction, in particular with respect to the binder components. This component is not regarded as part of the binder system.
  • the functional groups on the hydrophilic modified polysiloxane should be chosen so that, depending on the curing mechanism, they do not react in the curing reaction.
  • Hydrophilic-modified polysiloxanes are widely used as surfactants and emulsifiers due to the content of both hydrophilic and lipophilic groups in the same molecule.
  • a hydrophilic modified polysiloxane according to the present invention is a polysiloxane that is modified with hydrophilic groups to make it more hydrophilic compared to the corresponding unsubstituted polysiloxane having the same number of polysiloxane units.
  • the hydrophilicity can be obtained by modification with hydrophilic groups such as ethers (e.g. polyoxyalkylene groups such as polyethylene glycol and polypropylene glycol), alcohols (e.g. poly(glycerol), amides (e.g.
  • the hydrophilic-modified polysiloxane is an oil.
  • hydrophilic groups are non-ionic.
  • Non-ionic herein means that the hydrophilic-modified polysiloxane does not contain any salt moieties; in particular, it typically does not contain any metal cations.
  • the hydrophilicity of non-ionic hydrophilic modified polysiloxanes can be determined in accordance with the HLB (hydrophilic-lipophilic balance) parameter. If the hydrophilic modified polysiloxane of the present invention is non-ionic, the HLB (hydrophilic-lipophilic balance) is in the range 0.5-12, preferably 0.5-10, more preferably 0.5-8.0, most preferably 0.5-7.0. In a particular embodiment, the non- ionic hydrophilic modified polysiloxane has an HLB in the range 3.0-6.0.
  • the HLB is herein typically determined according to Griffin’s model using the equation “wt% hydrophilic groups”/5 (Reference: Griffin, W. C. Calculation of HLB values of non-ionic surfactants, J. Soc. Cosmet. Chem. 1954, 5, 249 - 256).
  • the HLB parameter is a well-established parameter for non-ionic surfactants and is readily available from the suppliers of commercially available hydrophilic modified polysiloxanes. The higher surfactant HLB value, the more hydrophilic it is.
  • wt% hydrophilic groups means the wt% of hydrophilic groups in the hydrophilic modified polysiloxane.
  • hydrophilic modified polysiloxane One function of the hydrophilic modified polysiloxane is to facilitate the dissolution and transport of any biocide to the surface of the coating film. In addition, it is also well known that formation of a hydrated layer at the coating-water interphase is important for the fouling protection performance.
  • hydrophilicity of the hydrophilic modified polysiloxane is too high, for example due to a high amount of hydrophilic groups in the molecule, this could lead to an early depletion of the biocide(s) and the hydrophilic modified polysiloxane due to a too high leaching rate.
  • a high hydrophilicity will also give poor compatibility with the polysiloxane based binder matrix, especially if high oil amounts (more than 10 wt.%) are used, giving poor film homogeneity and poor adhesion.
  • the ways to control the leach rate of the biocide and the hydrophilic modified polysiloxane include the molecular weight of the hydrophilic modified polysiloxane, the hydrophilicity and the miscibility with the binder.
  • a very low molecular weight hydrophilic modified polysiloxane tends to allow a high leach rate, while too high molecular weight may not allow the leaching of the biocide and the hydrophilic modified polysiloxane to be of the desired rate.
  • the hydrophilic modified polysiloxane has a number average molecular weight (Mn) in the range of 500-18,000 g/mol, such as in the range of 1000-16,000 g/mol, particularly in the ranges 2000-15,050 g/mol or 4000-15,050 g/mol.
  • Mn ranges for the hydrophilic modified polysiloxane include 500-15,000 g/mol, 1,000-13,000 g/mol or 3,000-10,000 g/mol.
  • Number average molecular weight (Mn) values referred to herein correspond to the experimentally obtained values, e.g. by GPC measured relative to a polystyrene standard. The method is given in the experimental section below.
  • the hydrophilic modified polysiloxane has a weight average molecular weight (Mw) of 1,000-50,000 g/mol, preferably in the ranges of 2,000-45,000 g/mol, 3,000-42,000 g/mol, 4,000-40,000 g/mol, or 5,000- 40,000 g/mol. Further suitable ranges include 5,000-30,000 g/mol, e.g. 5, DOO- 25, 000 g/mol or 10,000-20,000 g/mol. Weight average molecular weight (Mw) values referred to herein correspond to the experimentally obtained values, e.g. by GPC measured relative to a polystyrene standard. The method is given in the experimental section below.
  • hydrophilic modified polysiloxane has a viscosity in the range of 20-4,000 mPa-s, such as in the range of 30-3,000 mPa-s, in particular in the range of 50-2,500 mPa-s
  • the hydrophilic modified polysiloxane may be included in the coating composition in an amount of 1.0 to 30 wt% by dry weight, preferably 2.0 to 20 wt% by dry weight, further preferred 4 to 15 wt% by dry weight. Where there are two or more different types of hydrophilic modified polysiloxanes, these amounts refer to the total sum of hydrophilic modified polysiloxane components.
  • hydrophilic-modified polysiloxanes in which the relative weight of the hydrophilic moieties is 5% or more of the total weight (e.g. 5-60%), such as 6% or more (e.g. 6-50%), in particular 10% or more (e.g. 10-40%) of the total weight of the hydrophilic-modified polysiloxane.
  • the wt.% of the hydrophilic moieties can be calculated based on the stoichiometric ratio of starting materials in the hydrophilic modified polysiloxane synthesis, or it can be determined using analytical techniques such as IR or NMR. If there is a molar excess of a reactant then such a molar excess is not counted when determining the wt.% of hydrophilic moieties. Only those monomers that can react based on the stoichiometry of the reaction are counted.
  • the hydrophilic modified polysiloxane may contain low amounts of impurities, such as cyclic siloxanes, such as D4, D5 and D6 cyclosiloxanes, that are residues from polysiloxane synthesis, where the name (D4, D5 and D6) refers to the number of repeating Si-0 units in the cyclic polysiloxane (i.e. 4, 5 or 6 repeating Si-0 units in the cyclic polysiloxane respectively). From a health, safety, and environmental aspect it is preferred to limit the amount of cyclic polysiloxanes present in the coating composition.
  • impurities such as cyclic siloxanes, such as D4, D5 and D6 cyclosiloxanes, that are residues from polysiloxane synthesis, where the name (D4, D5 and D6) refers to the number of repeating Si-0 units in the cyclic polysiloxane (i.e. 4, 5 or 6 repeating Si-0 units in
  • the hydrophilic modified polysiloxane contains less than 5% of cyclic polysiloxanes, preferable less than 2%, more preferably less than 1%. In one particularly preferred embodiment, the hydrophilic modified polysiloxane is free of cyclic polysiloxanes.
  • hydrophilic modified polysiloxane is a polyether modified polysiloxane.
  • the polyether groups include at least 3 repeating units, such as at least 5 repeating units.
  • the oligomers or polymers include 5-100 repeating units, such as 5-50, or 8-50, or 8-20 repeating units.
  • the polyether groups (I.e. oligomeric or polymeric groups) have a number average molecular weight (n) in the range of 100- 2500 g/mol, such as in the range of 200-2000 g/mol, in particular in the range of 300-2000 g/mol, or in the range of 400-1000 g/mol.
  • polyether-modified polysiloxanes in which the relative weight of the polyether moieties is 5% or more of the total weight (e.g. 5- 60%), such as 6% or more (e.g. 6-50%), in particular 10% or more (e.g. 10-40%) of the total weight of the polyether-modified polysiloxane.
  • the polyether-modified polysiloxane is a polysiloxane having grafted thereto poly(oxyalkylene) chains.
  • An illustrative example of the structure of such polyether-modified polysiloxane is formula (A): wherein each R 7 is independently selected from Ci-s-alkyl (including linear or branched hydrocarbon groups) and aryl (e.g. phenyl (-CeHs)), in particular methyl; each R 8 is independently selected from -H, Ci-4-alkyl (e.g.
  • each R 9 is independently selected from C2-s-alkylene (e.g.
  • arylene e.g. 1 ,4-phenylene
  • C2-s-alkylene substituted with aryl e.g. 1-phenyl ethylene
  • k is 0-240
  • I is 1-60 and k+l is 1-240
  • n is 0-50, m is 0-50 and m+n is 1-50.
  • R 7 groups are the same.
  • examples of commercially available polyether-modified polysiloxanes of this type are KF352A, KF353, KF945, KF6012, KF6017 from ShinEtsu.
  • the polyether-modified polysiloxane is a polysiloxane having incorporated in the backbone thereof poly(oxyalkylene) chains.
  • An illustrative example of the structure of such hydrophilic-modified polysiloxanes is formula (B): wherein each R 7 is independently selected from Ci-s-alkyl (including linear or branched hydrocarbon groups) and aryl (e.g. phenyl (-CeHs)), in particular methyl; each R 8 is independently selected from -H, Ci-4-alkyl (e.g.
  • each R 9 is independently selected from C2-5-alkylene (e.g.
  • arylene e.g. 1 ,4-phenylene
  • C2-5-alkylene substituted with aryl e.g. 1-phenyl ethylene
  • k is 0-240
  • n is 0-50
  • m is 0-50
  • m+n is 1-50.
  • hydrophilic-modified polysiloxanes of this type are DOWSIL 2-8692 and XIAMETER OFX-3667 from DOW.
  • the polyether-modified polysiloxane is a polysiloxane having incorporated in the backbone thereof polyoxyalkylene chains and having grafted thereto polyoxyalkylene chains.
  • An illustrative example of the structure of such hydrophilic- modified polysiloxanes is formula (C): wherein each R 7 is independently selected from Ci-s-alkyl (including linear or branched hydrocarbon groups) and aryl (e.g. phenyl (-CeHs)), In particular methyl; each R 8 is independently selected from -H, Ci-4-alkyl (e.g.
  • each R 9 is independently selected from C2-s-alkylene (e.g.
  • arylene e.g. 1 ,4-phenylene
  • C2-s-alkylene substituted with aryl e.g. 1-phenyl ethylene
  • k is 0-240, I is 1-60 and k+l is 1-240;
  • n is 0-50, m is 0-50 and m + n is 1-50.
  • the groups -CH2CH(CH3)-, - CH2CH(CH2CH3)-, etc. may be present in any of the two possible orientations.
  • the segments present k and I times typically are randomly distributed in the polysiloxane structure.
  • the polyether or poly(oxyalkylene) is preferably selected from polyoxyethylene, polyoxypropylene and poly(oxyethylene- co-oxypropylene), which sometimes are referred to as polyethylene glycol, polypropylene glycol and poly(ethylene glycol-co-propylene glycol).
  • each R 9 linking two oxygen atoms is preferably selected from -CH2CH2- and -CH2CH(CH3)-, whereas each R 9 linking a silicon atom and an oxygen atom preferably is selected from C2-s-alkyl.
  • R 8 is preferably not hydrogen.
  • the one or more polyether modified polysiloxanes may be of different types, e.g. two or more of the types described above.
  • hydrophilic modified polysiloxane comprises polyglycerol groups or pyrrolidone groups.
  • the coating composition of the present invention optionally further comprises a hydrophobic modified polysiloxane oil.
  • the hydrophobic modified polysiloxane does not contain curing reactive groups such as Si-OH groups, Si-OR (alkoxy) groups etc. that can react with the binder at relevant curing temperatures (0 - 40 °C), hence the hydrophobic modified polysiloxane is intended to be non-reactive in the curing reaction, in particular with respect to the binder components. Generally, this component is not regarded as part of the binder system.
  • the functional groups on the hydrophobic modified polysiloxane should be chosen so that, depending on the curing mechanism, they do not react in the curing reaction.
  • a hydrophobic modified polysiloxane according to the present invention is a polysiloxane that is modified with hydrophobic groups to make it more hydrophobic compared to the corresponding unsubstituted polysiloxane having the same number of polysiloxane units.
  • the hydrophobicity can be obtained by modification with hydrophobic groups such as alkyl, cycloalkyl and aryl groups.
  • the hydrophobic-modified polysiloxane is an oil.
  • Preferred hydrophobic modified polysiloxanes are methylphenyl functional polysiloxanes and methyl aryl functional polysiloxanes. If present, the hydrophobic modified polysiloxane is preferably present in an amount of 2.5 to 30 wt%, more preferably 5 to 25 wt%, relative to the total dry weight of the composition.
  • the hydrophobic modified polysiloxane is preferably present in an amount of 1.0 - 30 wt.%, more preferably 4 - 20 wt.% relative to the total weight of the composition as a whole.
  • the coating composition comprises a mixture of a hydrophilic modified polysiloxane and a hydrophobic modified polysiloxane.
  • each of the hydrophilic modified polysiloxane and hydrophobic modified polysiloxane may individually be present in an amount of 2.5 to 20 wt%, such as 5 to 15 wt%, relative to the total dry weight of the composition.
  • the polysiloxane-based binder of the present invention is curable and contains curing-reactive functional groups such as silanol, alkoxysilane, ketoxime, carbinol, amine, epoxy and/or alkoxy groups.
  • the polysiloxane-based binder contains at least two curing- reactive functional groups.
  • the polysiloxane-based binder comprises more than one type of curing-reactive functional group.
  • the polysiloxane- based binder comprises a single type of curing-reactive functional group.
  • the curing-reactive functional groups are silanol and/or alkoxysilane. In still further preferred polysiloxane-based binders the curing-reactive functional groups are silanol.
  • crosslinking agent is an organosilicon compound represented by the general formula (I) shown below, a partial hydrolysis-condensation product thereof, or a mixture of the two:
  • each R is independently selected from a monovalent hydrocarbon group of 1 to 6 carbon atoms, C1-6 alkyl substituted by poly(alkylene oxide) or a polysiloxane of the structure (O-(CR D 2)r)rr - (O-(CR D 2)s)si -(Si (R pp )2-O) t -Si(R pp )3; wherein r’, rT, s’ and sT is an integer from 0-10, each R D is independently selected from H or Ci- 4 alkyl, each R pp is independently selected from C1-10 alkyl, Ce- aryl, C7-10 alkylaryl and t’ is an integer from 1 to 50.; each K is independently selected from a hydrolysable group such as an alkoxy group; and d is 0, 1 or 2, more preferably 0 or 1.
  • Preferred crosslinkers of this type include tetraethoxysilane, vinyltris(methylethyloximo)silane, methyltris(methylethyloximo)silane, vinyltrimethoxysilane, methyltrimethoxysilane and vinyltriisopropenoxysilane as well as hydrolysis-condensation products thereof.
  • the curing-reactive functional groups are di or tri-alkoxy, a separate crosslinking agent is generally not required.
  • the crosslinking agent is preferably present in amount of up to 10 wt% of the total dry weight of the coating composition, preferably 2.0 to 8.0 wt%.
  • Suitable crosslinking agents are commercially available, such as Silicate TES-40 WN from Wacker and Dynasylan A from Evonik.
  • preferred crosslinking agents are monomeric isocyanates, polymeric isocyanates and isocyanate prepolymers.
  • Polyisocyanates are preferred over monomeric isocyanates because of lower toxicity.
  • Polyisocyanates can for example be based on diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (I PDI) chemistry. These are, for example, supplied under the tradename Desmodur by Covestro and Tolonate by Vencorex.
  • polyisocyanates examples include Desmodur N3300, Desmodur 3390 BA/SN, Desmodur N3400, Desmodur N3600 Desmodur N75, Desmodur XP2580, Desmodur Z4470, Desmodur XP2565 and Desmodur VL, supplied by Covestro.
  • Polyisocyanates can be made with different NCO-functionality.
  • the NCO- functionality is the amount of NCO-groups per polyisocyanate molecule or isocyanate prepolymer molecule.
  • Polyisocyanates curing agents with different NCO-functionality can be used.
  • the crosslinking agent is preferably present in an amount of 0.8-2.5 equivalents (equiv) NCO groups relative the amount of hydroxyl groups, preferably 0.9-2.0 equiv, more preferably 0.95-1.7 equiv, even more preferably 1-1.5 equiv.
  • the crosslinking agents are preferably amine, sulfur or epoxy functional.
  • crosslinking agents/curing agents can also be dual crosslinking agents/curing agents containing, for example, both amine/sulphur/epoxy/isocyanate and an alkoxysilane.
  • Preferred dual curing agents are represented by the general formula (II) below: wherein
  • LL is independently selected from an unsubstituted or substituted monovalent hydrocarbon group of 1 to 6 carbon atoms; each M is independently selected from a hydrolysable group such as an alkoxy group; a is 0, 1 or 2, preferably 0 or 1 ; b an integer from 1 to 6; and
  • Fn is an amine, epoxy, glycidyl ether, isocyanate or sulphur group.
  • Preferred examples of such dual curing agents include 3- isocyanatopropyltrimethoxysilane, 3- isocyanatopropyltriethoxysilane, 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (3- glycidoxypropyl)trimethoxysilane, 3-mercaptopropyltrimethoxysilane.
  • One particularly preferred curing agent is 3-aminopropyltriethyoxysilane such as Dynasylan AMEO from Evonik.
  • This type of dual-curing agents can be used as a separate curing agent or be used to end-cap the polysiloxane-based binder so that the end-groups of the polysiloxane-based binder are modified prior to the curing reaction.
  • compositions comprises a crosslinker of formula I or a dual crosslinker of formula II or a mixture thereof.
  • the binder is not one component room temperature vulcanising (RTV-1) or self-curing binder.
  • the crosslinking/curing agent in the present application is not water.
  • the coating composition of the invention may comprise a catalyst component.
  • the catalyst can be organic or inorganic or an organometallic catalyst.
  • the coating composition of the invention comprises a metal catalyst.
  • catalysts that can be used include Sn, Zn, Li, K, Bi, Fe, Ce or Zr containing catalysts, e.g. salts and organometallic complexes thereof.
  • the salts preferably are salts of long-chain carboxylic acids and/or chelates or organometal salts.
  • the metal catalysts are preferably tin (IV), bismuth(lll), iron(ll), iron(lll), zinc(ll), zirconium(IV), cerium (III), potassium or lithium compounds. Tin (IV), bismuth (III), zinc (II) and cerium (III) being particularly preferred.
  • anionic organic radicals include methoxide, ethoxide, n- propoxide, isopropoxide, n-butoxide, isobutoxide, sec-butoxide, tert-butoxide, triethanolaminate, and 2-ethylhexyloxide radicals; carboxylate radicals such as the acetate, formate, n-octoate, 2-ethylhexanoate, 2,4,4-trimethylpentanoate, 2,2,4- trimethylpentanoate, 6-methylheptanoate, oleate, ricinoleate, palmitate, hexoate, hexadecanate, 2-ethylhexanoate, benzoate, 1,4-dibenzoate, stearate, acrylate, laurate, methacrylate, 2-carboxyethylacrylate, oxalate, 10-undecylenate, dodecanoate, citrate, 3-oxopen
  • metal salt compounds are dibutyltin diacetate, dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin oxide, bismuth(lll) 2-ethylhexanoate, bismuth(lll) neodecanoate, bismuth(lll) acetate, bismuth (III) octanoate, iron(ll) acetate, iron(lll) tert-butoxide, iron(lll) citrate, iron(ll) lactate, iron(ll) oxalate, iron(lll) oxalate, iron(lll) 2-ethylhexanoate, cerium (III) neodecanoate, zinc(ll) acetate, zinc(ll) formate, zinc(ll) benzoate, zinc(ll) 2-ethylhexanoate, zinc(ll) n-octoate, zinc(ll) stearate,
  • metal chelate compounds bismuth(lll) 2,2,6,6-tetramethyl-3,5- heptanedionate, bismuth(lll) acetylacetonate, iron(ll) acetylacetonate, iron(lll) acetylacetonate, iron(lll) 2,2,6,6-tetramethyl-3,5-heptanedionate, iron(ll) 2, 2,6,6- tetramethyl-3,5-heptanedionate, zinc(ll) hexafl uoroacetylacetonate, zinc(ll) 1,3- diphenyl-1 ,3-propanedionate, zinc(ll) 1-phenyl-5-methyl-1,3-hexanedionate, zinc(ll) 1 ,3-cyclohexanedionate, zinc(ll) 2-acetylcyclohexanonate, zinc(ll) 2-acetyl-1,3- cyclohexane
  • tin catalysts examples include dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dioctyltin dilaurate.
  • suitable tin catalysts include BNT-CAT 400 and BNT-CAT 500 from BNT Chemicals, FASCAT 4202 from PMC Organometallix and Metatin Katalysator 702 from DOW.
  • lithium catalysts examples include lithium 2-ethylhexanoate and lithium neodecanoate.
  • Example of commercially available lithium catalyst includes Borchers Deca Lithium 2 manufactured by Borchers.
  • potassium catalysts examples include potassium 2-ethylhexanoate and potassium neodecanoate.
  • Examples of commercially available potassium catalysts include 15% Potassium Hex-Cem® Ell manufactured by Borchers and TIB KAT K30 from TIB Chemicals.
  • Suitable zinc catalysts are zinc 2-ethylhexanoate, zinc naphthenate and zinc stearate.
  • Examples of commercially available zinc catalysts include K-KAT XK-672 and K-KAT670 from King Industries and Borchi Kat 22 from Borchers.
  • suitable bismuth catalysts are organobismuth compounds such as bismuth 2-ethylhexanoate, bismuth octanoate and bismuth neodecanoate.
  • organobismuth catalysts are Borchi Kat 24 and Borchi Kat 315 from Borchers. K-KAT XK-651 from King Industries, Reaxis C739E50 from Reaxis and TIB KAT 716 from TIB Chemicals.
  • cerium catalysts examples include Cerium (III) neodecanoate.
  • Suitable catalysts are iron catalysts such as iron stearate and iron 2- ethylhexanoate, and zirconium catalysts such as zirconium naphthenate, tetrabutyl zirconate, tetrakis(2- ethylhexyl) zirconate, triethanolamine zirconate, tetra(isopropenyloxy)-zirconate, zirconium tetrabutanolate, zirconium tetrapropanolate and zirconium tetraisopropanolate.
  • Further suitable catalysts are zirconate esters.
  • the metal additive is a tin, zinc and/or cerium catalyst.
  • the catalyst is tin free.
  • the metal catalyst is present in the coating composition of the invention in an amount of 0.05 to 5.0 wt% based on the total dry weight of the coating composition, more preferably 0.1 to 2.0 wt%.
  • the catalyst may also be organic, such as a low molecular weight amidine or a low molecular weight amine compound such as an aminosilane.
  • the term low molecular weight means that its molecular weight is less than 1000g/mol, such as 50 to 500 g/mol, preferably 100 to 400g/mol.
  • the low molecular weight amidine or low molecular weight amine compound is not guanidine or a guanidine derivative.
  • the coating composition disclosed herein is free from any guanidine-based catalyst.
  • Guanadine derivatives are compounds comprising the motif:
  • Suitable amidines are compounds comprising the motif:
  • amidine is represented by the following general formula: wherein Ri, R2, R4 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups, and combinations thereof;
  • R3 is a monovalent organic group, monovalent heteroorganic groups, and combinations thereof; and/or wherein any two or more of R1, R2, R3, R4 optionally can be bonded together to form a ring structure.
  • R1, R2 and R4 are preferably hydrogen or C1-6 alkyl or phenyl groups.
  • R3 is C1-6 alkyl or phenyl groups. Still more preferably R2+R4 taken together form a ring and/or R1+R3 taken together form a ring. Such rings are preferably aliphatic 5-7 membered rings.
  • DBU 1,8-diazabicyclo-5.4.0-7-undecene
  • the catalyst may also be a low molecular weight organic amine compound, such as triethylamine, a cyclic amine, tetramethylethylenediamine, 1,4- ethylenepiperazine and pentamethyldiethylenetriamine.
  • organic amine compound such as triethylamine, a cyclic amine, tetramethylethylenediamine, 1,4- ethylenepiperazine and pentamethyldiethylenetriamine.
  • Preferred amines are however aminosilanes such as aminoalkyltrialkoxysilane such as 3-aminopropyltriethoxysilane or 3- aminopropyltrimethoxy silane, or bis(alkyltrialkoxysilyl)amine preferably comprises bis(3-propyltrimethoxysilyl)amine or bis(3-propyltriethoxysilyl)amine.
  • aminosilanes such as aminoalkyltrialkoxysilane such as 3-aminopropyltriethoxysilane or 3- aminopropyltrimethoxy silane
  • bis(alkyltrialkoxysilyl)amine preferably comprises bis(3-propyltrimethoxysilyl)amine or bis(3-propyltriethoxysilyl)amine.
  • Another option is N,N-dibutylaminomethyl-triethoxysilane.
  • Suitable aminosilanes are of general formula (I) or (II)
  • each R is a hydrocarbyl group having 1 to 12 C atoms optionally containing an ether or amino linker
  • R 1 is a hydrocarbyl group having 1 to 12 C atoms; each X independently represents an alkoxy group.
  • Y is an amino bound to R.
  • the Y group can bind to any part of the chain R.
  • the amino groups are preferably N-di-C1 -6-alkyl or NH2. It is especially preferred if X is a C1-6 alkoxy group, especially methoxy or ethoxy group. It is also especially preferred if there are two or three alkoxy groups present. Thus, z is ideally 2 or 3, especially 3.
  • Subscript y is preferably 2.
  • R 1 is preferably C1-4 alkyl such as methyl.
  • R is a hydrocarbyl group having up to 12 carbon atoms.
  • hydrocarbyl is meant a group comprising C and H atoms only. It may comprise an alkylene chain or a combination of an alkylene chain and rings such as phenyl or cyclohexyl rings.
  • the term "optionally containing an ether or amino linker" implies that the carbon chain can be interrupted by a -O- or -NH- group in the chain.
  • R is preferably an unsubstituted (other than Y obviously), unbranched alkyl chain having 2 to 8 C atoms.
  • a preferred silane general formula is therefore of structure (III)
  • R' is an unsubstituted, unbranched alkyl chain having 2 to 8 C atoms optionally containing an ether or amino linker
  • Y' is an amino functional group bound to the R' group
  • X' represents an alkoxy group
  • silanes examples are the many representatives of the products manufactured by Degussa in Rheinfelden and marketed under the brand name of Dynasylan(R)D, the Silquest(R) silanes manufactured by Momentive, and the GENOSIL(R) silanes manufactured by Wacker.
  • Preferred aminosilanes include aminopropyltrimethoxysilane (Dynasylan AMMO; Silquest A-l 110), aminopropyltriethoxysilane (Dynasylan AMEO) or N-(2- aminoethyl)-3-aminopropyltrimethoxysilane (Dynasylan DAMO, Silquest A-l 120), N-(2-aminoethyl)-3-aminopropyltriethoxysilane, triamino- functional trimethoxysilane (Silquest A- 1130), bis(gamma- trimethoxysilylpropyl)amine (Silquest A-l 170), N- ethyl-gamma- aminoisobytyltrimethoxy silane (Silquest A-Link 15), N-phenyl- gamma- aminopropyltrimethoxysilane (Silquest Y-9669), 4-amino-3,
  • silanes of interest include 3 -Aminopropyltriethoxysilane, 3 - Aminopropyltrimethoxysilane, N-(Aminoethyl)-aminopropyltrimethoxysilane H2NCH2CH2NHCH2CH2CH 2Si(OCH3)3, 3-aminopropylmethyldiethoxysilane, 3-(2- aminoethylamino)propylmethyldimethoxysilane (H 2 NCH2CH2NHCH2CH2CH2SiCH3(OCH 3 )2).
  • amino silane may both act as a catalyst and a crosslinking agent due to the alkoxy silane groups present.
  • the amount of organic catalyst present in the coating composition may be present in an amount of 0.05 to 5.0 wt%, preferably 0.1 to 4.0 wt.%, such as 0.25 to 4.0 wt.%, more preferred 0.5 to 3.0 wt.% of the coating composition (dry weight).
  • the fouling release coating composition of the present invention may comprise an antifouling agent/biocide.
  • antifouling agent biologically active compounds, antifoulant, biocide, toxicant are used in the industry to describe known compounds that act to prevent marine fouling on a surface. These terms are used interchangeably here.
  • the antifouling agent may be inorganic, organometallic or organic.
  • the antifouling agent is an organometallic antifouling agent. Suitable antifouling agents are commercially available.
  • inorganic antifouling agents include copper and copper compounds such as copper oxides, e.g. cuprous oxide and cupric oxide; copper alloys, e.g. copper-nickel alloys; copper salts, e.g. copper thiocyanate and copper sulphide.
  • copper oxides e.g. cuprous oxide and cupric oxide
  • copper alloys e.g. copper-nickel alloys
  • copper salts e.g. copper thiocyanate and copper sulphide.
  • organometallic antifouling agents include zinc pyrithione; organocopper compounds such as copper pyrithione, copper acetate, copper di(ethyl 4,4,4-trifluoro acetoacetate), copper naphthenate, oxine copper, copper nonylphenolsulfonate, copper bis(ethylenediamine)bis(dodecylbenzensulfonate) and copper bis(pentachlorophenolate); dithiocarbamate compounds such as zinc bis(dimethyldithiocarbamate) [ziram], zinc ethylenebis(dithiocarbamate) [zineb], manganese ethylenebis(dithiocarbamate) [maneb] and manganese ethylene bis(dithiocarbamate) complexed with zinc salt [mancozeb].
  • organocopper compounds such as copper pyrithione, copper acetate, copper di(ethyl 4,4,4-trifluoro acetoacetate), copper nap
  • organic antifouling agents include heterocyclic compounds such as 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5- triazine [cybutryne], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], encapsulated 4,5- dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 1,2-benzisothiazolin-3-one, 2- (thiocyanatomethylthio)-1,3-benzothiazole [benthiazole] and 2,3,5,6-tetrachloro-4- (methylsulphonyl) pyridine; urea derivatives such as 3-(3,4-dichlorophenyl)-1 ,1- dimethylurea [diuron]; amides and imides of carboxylic acids, sulphonic acids and sulphenic acids such
  • antifouling agents include tetraalkylphosphonium halogenides, guanidine derivatives, imidazole containing compounds such as 4-[1- (2,3-dimethylphenyl)ethyl]-1 H-imidazole [medetomidine] and derivatives thereof, macrocyclic lactones including avermectins and derivatives thereof such as ivermectine, spinosyns and derivatives thereof such as spinosad, capsaicins and derivatives thereof such as phenyl capsaicin, and enzymes such as oxidase, proteolytically, hemicellulolytically, cellulolytically, lipolytically and amylolytically active enzymes.
  • imidazole containing compounds such as 4-[1- (2,3-dimethylphenyl)ethyl]-1 H-imidazole [medetomidine] and derivatives thereof
  • macrocyclic lactones including avermectins
  • Preferred antifouling agents are zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [zineb], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT] and encapsulated 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], Particularly preferred antifouling agents are zinc pyrithione and copper pyrithione, particularly copper pyrithione.
  • the biocide may form 1-20 % by dry weight of the total coating composition, preferably 1-15 %, 2-15 % or 3-12 % by dry weight of the total coating composition.
  • This component is not regarded as part of the binder system.
  • the coating composition of the invention preferably comprises one or more pigments.
  • the pigments may be inorganic pigments, organic pigments or a mixture thereof. Inorganic pigments are preferred.
  • the pigments may be surface treated.
  • pigments include black iron oxide, red iron oxide, yellow iron oxide, titanium dioxide, zinc oxide, carbon black, graphite, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminium sulfosilicates, quinacridones, phthalocyanine blue, phthalocyanine green, indanthrone blue, cobalt aluminium oxide, carbazoledioxazine, isoindoline orange, bis-acetoaceto-tolidiole, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone, and quinophthalone yellow, metallic flake materials (e.g. aluminium flakes).
  • metallic flake materials e.g. aluminium flakes.
  • Preferred pigments are black iron oxide, red iron oxide, yellow iron oxide, phthalocyanine blue and titanium dioxide.
  • the titanium dioxide is surface treaded with a silicone compound, a zirconium compound, an aluminum compound and/or a zinc compound.
  • the amount of pigment present in the coating composition of the present invention is preferably 0 to 25 wt% and more preferably 0.5 to 15 wt% based on the total dry weight of the coating composition.
  • This component is not regarded as part of the binder system.
  • the coating composition of the present invention preferably comprises a solvent.
  • Suitable solvents for use in the compositions of the invention are commercially available.
  • suitable organic solvents and thinners are aromatic hydrocarbons such as xylene, toluene, mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone; esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran; alcohols such as n-butanol, isobutanol, benzyl alcohol; ether alcohols such as butoxyethanol, 1-methoxy-2-propanol; aliphatic hydrocarbons such as
  • the amount of solvent present in the fouling release 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. The skilled man will appreciate that the solvent content will vary depending on the other components present.
  • This component is not regarded as part of the binder system.
  • the coating composition of the present invention optionally comprises fillers.
  • fillers that can be used in the coating composition according to the present invention are zinc oxide, barium sulphate, calcium sulphate, calcium carbonate, silicas or silicates (such as talc, feldspar, china clay and nepheline syenite) including fumed silica, bentonite and other clays, and solid silicone resins, which are generally condensed branched polysiloxanes.
  • Some fillers such as fumed silica may have a thickening effect on the coating composition.
  • Preferred fillers are fumed silica fillers.
  • the fumed silica fillers may have an untreated surface or a hydrophobically modified surface.
  • Preferably the fumed silica filler has a hydrophobically modified surface.
  • Examples of commercially available fumed silica fillers are TS-610, TS-530, EH-5, H-5, and M-5 from Cabot and Aerosil® R972, Aerosil® R974, Aerosil® R976, Aerosil® R104, Aerosil® R202, Aerosil® R208, Aerosil® R805, Aerosil® R812, Aerosil® 816, Aerosil® R7200, Aerosil® R8200, Aerosil® R9200, Aerosil® R711 from Evonik.
  • the amount of fillers present in the coating composition of the present invention is preferably 0 to 25 wt%, more preferably 0.1 to 10 wt% and still more preferably 0.15 to 5.0 wt%, based on the total dry weight of the coating composition.
  • This component is not regarded as part of the binder system.
  • 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 reinforcing agents, thixotropic agents, thickening agents, anti-settling agents, dehydrating agents, dispersing agents, wetting agents, surfactants, binders, plasticizers, and dyes.
  • thixotropic agents examples include silicas such as fumed silicas, organo-modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil wax and mixtures thereof.
  • thixotropic agents, thickening agents and anti-settling agents are each present in the composition of the invention in an amount of 0-10 wt%, more preferably 0.1-6 wt% and still more preferably 0.1 -2.0 wt%, based on the total dry weight of the composition.
  • the dehydrating agents and desiccants that may be used in the coating compositions include organic and inorganic compounds.
  • the dehydrating agents can be hygroscopic materials that absorb water or binds water as crystal water, often referred to as desiccants.
  • desiccants include calcium sulphate hemihydrate, anhydrous calcium sulphate, anhydrous magnesium sulphate, anhydrous sodium sulphate, anhydrous zinc sulphate, molecular sieves and zeolites.
  • the dehydrating agent can be a compound that chemically reacts with water.
  • orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropy
  • the dehydrating agent is present in the compositions of the invention in an amount of 0-5 wt%, more preferably 0.5-2.5 wt% and still more preferably 1.0-2.0 wt%, based on the total dry weight of the composition.
  • the coating 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 fouling release coating composition or paint is preferably filled into a container.
  • suitable containers include cans, drums and tanks.
  • the coating composition may be supplied as one-pack, as a two- pack or as a three-pack.
  • the composition is supplied as a two-pack or as a three- pack.
  • the first container When supplied as a two pack, the first container preferably comprises a polysiloxane-based binder(s) and the second container preferably comprises any curing agent and the catalyst. Instructions for mixing the contents of the containers may optionally be provided. Any hydrophilic-modified polysiloxane is preferably part of the first container. Any catalyst is preferably part of the second container.
  • the coating composition and paint of the invention preferably has a solids content of 50-99 wt%, more preferably 60-99 wt% and still more preferably 65-99 wt%.
  • the coating composition and paint of the invention has a content of volatile organic compounds (VOC) of 0 to 400 g/L, preferably 0 to 350 g/L, e.g. 0 to 300 g/L.
  • VOC content can be calculated (ASTM D5201-05A) or measured (US EPA method 24 or ISO 11890-1).
  • the coating composition of the present invention may be applied to any pretreated coating layers designed for polysiloxane based fouling release coatings.
  • coating layers are epoxy anticorrosive primer layers and silicone containing tie-layers designed to ensure adhesion between the substrate and the final polysiloxane based coating composition layers.
  • tielayer is described in WO2013/107827.
  • the tie-layer may contain an antifouling agent.
  • epoxy primers and tie coats are well known in the art and can be purchased commercially.
  • the process of the invention comprises applying at least two coats of a polysiloxane based coating composition as hereinbefore defined.
  • the process is characterised by the following: i) a first coating layer is applied by spray application to a wet film thickness of 50-300 pm; and ii) a second coating layer is applied by spray application to a wet film thickness of 50-300 pm; wherein the second coating layer is applied directly on top of the first coating layer 5 min - 6 hours after the first coating layer is applied.
  • the polysiloxane based coating composition of the first coating layer may be the same or different to the polysiloxane based coating composition of the second coating layer.
  • the first coating layer and the second coating layer will be identical. In the case where the first coating layer and the second coating layer are not identical, it is preferred if they are substantially the same. “Substantially the same” as used herein refers to coating layers differing only in the type and amount of pigmentation and/or additives which may be present. If the coating layers are substantial the same, they will have the same type and amount of crosslinker, binder, additive oil and biocide. They may differ however in pigmentation.
  • first and second coating compositions have the same crosslinker, binder, additive oil and biocide (whichever present). These may be present in different amounts in the first and second coating compositions or they may be present in the same amounts in the first and second coating compositions.
  • wet film thickness of 50-300 pm, preferably 100-2750 pm, such as 125-275 pm are applied instead of one thick one (i.e. wet film thickness of more than 250 pm, especially more than 300 pm such as 300 to 600 pm). It is further preferred if the wet film thickness of both coating layers are equal, or within 50 pm of each other.
  • first coating layer and the second coating layer are top coat layers, which are present in addition to any tie layer and/or primer layer which may be present.
  • the coating composition of the present invention will typically be applied (and cured) at a temperature of 5 to 50 °C, preferably 10 to 40 °C, further preferred 10 to 30 °C.
  • the coating composition of the present invention will typically be applied (and cured) at a humidity of 20 - 90 %, preferably 30 - 85 %, more preferred 40 - 85 %.
  • 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.
  • the coating composition and paint can be accomplished by any convenient spray application means.
  • the first and second coating layers may be applied by two separate cherrypickers following each other along the vessel.
  • the application may also be performed by automated processes or paint application robots.
  • 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 system of the invention is ideally a fouling release coating system.
  • the coating system of the invention comprises at least the first coating layer and second coating layer as hereinbefore described.
  • the coating system may comprise further layers, such as at least one tie coat layer and/or at least one epoxy primer layer.
  • the tie coat layer and the epoxy primer layer are typically allowed to cure for at least 24 hours before the application of the subsequent layer.
  • the first and second coating layers form the outermost layers of the coating system. Furthermore, it is preferable if that second coating layer is the outermost layer of the coating system.
  • the coating system of the present invention is typically applied to the surface of a marine substrate, preferably the part of a marine structure which is submerged when in use.
  • Typical marine substrates include vessels (including but not limited to boats, ships, yachts, motorboats, motor launches, ocean liners, tugboats, tankers, container ships and other cargo ships, submarines, and naval vessels of all types), pipes, shore and off-shore machinery, constructions and objects of all types such as piers, pilings, bridge substructures, water-power installations and structures, underwater oil well structures, nets and other aquatic culture installations, and buoys, etc.
  • the surface of the substrate may be the "native" surface (e.g. the steel surface).
  • the viscosity of the binders was determined in accordance with ASTM D2196 Test Method A using a Brookfield DV-I Prime digital viscometer with LV-2 or LV-4 spindle at 12 rpm.
  • the binders were tempered to 23.0 °C ⁇ 0.5 °C before the 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 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 a minimum of 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 number- average molecular weight (Mn), weight-average molecular weight (Mw) and polydispersity index are reported.
  • the coating compositions were prepared by first mixing the components in part (A) shown in Table 1 below using a high-speed dissolver equipped with an impeller disc. First the polysiloxane-based binders, copper pyrithione, hydrophobic silica and red iron oxide was stirred at high speed until a finess of grind of less than 20 pm was reached. Then the remaining components were added while stirring at low speed. The components in part (B) were mixed with the components in part (A) shortly before application of the coating.
  • Fouling Release Coating topcoat (formulation given in Table 1) was applied by airless spray onto standing PVC panels coated with commercial system of 1 x 200 pm epoxy primer (Jotacoat Universal N10 from Jotun) and 1 x 160 pm fouling release coating tiecoat (Safeguard FRC PE from Jotun) according to corresponding product technical datasheets. Both the epoxy primer and the tiecoat was cured for 24 hours before the next layers was applied. The topcoat was cured under various conditions by use of climate chambers controlling temperature and relative humidity. The two layers of topcoat were applied with set time intervals ranging from 5 to 120 minutes. The sag resistance and adhesion were measured for 23 Examples and 2 Comparative examples and are reported in Table 2.
  • the topcoat was applied with airless spray pump using a pressure of 4.5 bar and nozzle size 627 pm. Application was performed on standing panels with 50% overlapping to achieve a uniform film thickness. Immediately after application, the film thickness was measures with a WFT comb. The sag was controlled by making a horizontal line in the paint, using a spatula at the bottom part of the panel. Sag was observed in the line created. Sagging was evaluated and reported for the applied WFT when the coating was fully cured, typically the day after application.
  • Adhesion of the two topcoats was evaluated both on panels immersed in seawater 24 hours after application of the last coat (wet adhesion) and on panels not immersed in seawater after application (dry adhesion).
  • Panels of the coating system were prepared with airless spray according to the overcoating intervals given in the product Technical data sheets and the selected overcoating intervals between the topcoats. Panels were set to cure at the selected curing conditions for 24 hours.
  • the panels were immersed in seawater for 48 hours.
  • the panels were kept at RT/50°C for at least 48 hours.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un processus de préparation d'un système de revêtement multicouche comprenant au moins deux couches de revêtement dans lesquelles : i) une première couche de revêtement est appliquée par application par pulvérisation à une épaisseur de film humide de 50 à 300 pm ; et ii) une seconde couche de revêtement est appliquée par application par pulvérisation à une épaisseur de film humide de 50 à 300 pm ; la seconde couche de revêtement étant appliquée directement sur la première couche de revêtement 5 min à 6 heures après l'application de la première couche de revêtement ; et les première et seconde couches de revêtement comprenant une composition de revêtement à base de polysiloxane comprenant a) un système de liant à base de polysiloxane ; et b) un agent de durcissement ou un agent de réticulation.
PCT/EP2023/083990 2022-12-02 2023-12-01 Processus WO2024115765A1 (fr)

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6048580A (en) 1997-12-03 2000-04-11 Excelda Manufacturing Company Fouling release coating for marine vessels and method of application
WO2011076856A1 (fr) 2009-12-22 2011-06-30 Hempel A/S Nouvelle composition de revêtement anti-encrassement
WO2013024106A1 (fr) 2011-08-18 2013-02-21 Akzo Nobel Coatings International B.V. Composition anti-encrassement comprenant des stérols et/ou des dérivés de ceux-ci
WO2013107827A1 (fr) 2012-01-19 2013-07-25 Jotun A/S Revêtements anti-salissures
WO2014131695A1 (fr) 2013-02-26 2014-09-04 Akzo Nobel Coatings International B.V. Compositions antisalissure avec un polymère ou oligomère contenant un oxyalkylène fluoré
WO2016004961A1 (fr) 2014-07-11 2016-01-14 Hempel A/S Nouveaux revêtements anti-salissures à base de polysiloxane comprenant des alcools modifiés au poly(oxyalkylène)
US20160024314A1 (en) * 2013-03-20 2016-01-28 Hempel A/S Novel polysiloxane-based fouling control coating systems
WO2019101912A1 (fr) 2017-11-24 2019-05-31 Jotun A/S Composition antisalissures
WO2019101920A1 (fr) 2017-11-24 2019-05-31 Jotun A/S Composition antisalissure
US20190382581A1 (en) * 2017-02-06 2019-12-19 Dow Silicones Corporation Emulsion, composition comprising same, film formed therewith, and related methods
EP3974482A1 (fr) 2020-09-29 2022-03-30 Jotun A/S Composition de revêtement anti-salissures
WO2022069482A1 (fr) 2020-09-29 2022-04-07 Jotun A/S Composition de revêtement anti-salissures

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6048580A (en) 1997-12-03 2000-04-11 Excelda Manufacturing Company Fouling release coating for marine vessels and method of application
WO2011076856A1 (fr) 2009-12-22 2011-06-30 Hempel A/S Nouvelle composition de revêtement anti-encrassement
WO2013024106A1 (fr) 2011-08-18 2013-02-21 Akzo Nobel Coatings International B.V. Composition anti-encrassement comprenant des stérols et/ou des dérivés de ceux-ci
WO2013107827A1 (fr) 2012-01-19 2013-07-25 Jotun A/S Revêtements anti-salissures
WO2014131695A1 (fr) 2013-02-26 2014-09-04 Akzo Nobel Coatings International B.V. Compositions antisalissure avec un polymère ou oligomère contenant un oxyalkylène fluoré
US20160024314A1 (en) * 2013-03-20 2016-01-28 Hempel A/S Novel polysiloxane-based fouling control coating systems
WO2016004961A1 (fr) 2014-07-11 2016-01-14 Hempel A/S Nouveaux revêtements anti-salissures à base de polysiloxane comprenant des alcools modifiés au poly(oxyalkylène)
US20170130064A1 (en) * 2014-07-11 2017-05-11 Hempel A/S Novel polysiloxane-based fouling-release coats comprising poly(oxyalkylene)-modified alcohols
US20190382581A1 (en) * 2017-02-06 2019-12-19 Dow Silicones Corporation Emulsion, composition comprising same, film formed therewith, and related methods
WO2019101912A1 (fr) 2017-11-24 2019-05-31 Jotun A/S Composition antisalissures
WO2019101920A1 (fr) 2017-11-24 2019-05-31 Jotun A/S Composition antisalissure
EP3974482A1 (fr) 2020-09-29 2022-03-30 Jotun A/S Composition de revêtement anti-salissures
WO2022069482A1 (fr) 2020-09-29 2022-04-07 Jotun A/S Composition de revêtement anti-salissures
WO2022069487A1 (fr) 2020-09-29 2022-04-07 Jotun A/S Composition de revêtement anti-salissures

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GRIFFIN, W. C.: "Calculation of HLB values of non-ionic surfactants", J. SOC. COSMET. CHEM., vol. 5, 1954, pages 249 - 256, XP000671451

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