WO2017220097A1 - Composition de revêtement anticontamination à libération contrôlée par interaction biocide - Google Patents

Composition de revêtement anticontamination à libération contrôlée par interaction biocide Download PDF

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Publication number
WO2017220097A1
WO2017220097A1 PCT/DK2017/050204 DK2017050204W WO2017220097A1 WO 2017220097 A1 WO2017220097 A1 WO 2017220097A1 DK 2017050204 W DK2017050204 W DK 2017050204W WO 2017220097 A1 WO2017220097 A1 WO 2017220097A1
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WIPO (PCT)
Prior art keywords
coating composition
coat
modified silicone
polyoxyalkylene
metal
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Application number
PCT/DK2017/050204
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English (en)
Inventor
Eduardo Andres Martinez
Markus Hoffmann
Original Assignee
Hempel A/S
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 Hempel A/S filed Critical Hempel A/S
Priority to CN201780045298.XA priority Critical patent/CN109803533A/zh
Priority to KR1020187038024A priority patent/KR20190021273A/ko
Priority to EP17814790.6A priority patent/EP3474668A4/fr
Priority to SG11201811257SA priority patent/SG11201811257SA/en
Publication of WO2017220097A1 publication Critical patent/WO2017220097A1/fr

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    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • C09D5/1618—Non-macromolecular compounds 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
    • 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
    • C09D5/1656—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
    • 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

Definitions

  • the present invention relates to antifouling coating compositions having included therein metal-containing biocides and certain polyoxyalkylene-modified silicone oils, as well as to coating systems comprising a coat having included such metal-containing biocides and silicone oils.
  • Biocides and in particular metal-containing biocides like cuprous oxide and pyrithiones are typically used in erodible antifouling coating compositions, in particular those being based on an erodible non-silicone based binder system.
  • One significant challenge in designing such coating compositions is the fact that erodible antifouling coats build up a leach layer which allows for free diffusion of the biocide. Due to the free diffusion through the leach layer, a significant amount of the biocide may be liberated too fast from the coating, whereby a higher amount of the biocide is needed in order to maintain a sufficient level of antifouling activity over time.
  • JP 2006-052284 discloses the manufacture of an aqueous dispersion of a resin containing a triorganosilyl group.
  • the aqueous dispersion may comprise a silicone oil and optionally a biocide.
  • the silicone oil may among others be a polyether-modified silicone oil. It is understood as a water-borne mini-emulsion polymerisation (as described in the Japanese patent application), namely an approach where polymerisation is carried out inside emulsified oil droplets (50-500 nm) in a water.
  • Such droplets contain the monomers to be polymerised and are stabilised with low HLB oil-in-water surfactants (such as KF-945) that will encapsulate the monomers and stabilise the oil-in-water emulsion.
  • HLB oil-in-water surfactants such as KF-945
  • Such water-borne polymerisation will define the size of the polymer by the size of the encapsulation.
  • the polymer, by the water system in which it is polymerised and formulated will no longer form the homogeneous film which is a characteristic of solvent polymerisation polymers in solvent- borne formulations.
  • water-borne mini-emulsion polymers will be heterogeneously distributed as discrete domains surrounded by the surfactant pronounced of their emulsion polymerisation.
  • WO 2015/150249 Al discloses an erodible antifouling coating composition comprising an erodible binder system, one or more antifouling agents and at least one silicone oil.
  • the applied silicone oils are conventional linear and branched alkyl/aryl polysiloxanes.
  • WO 2011/076856 discloses a fouling control coating composition comprising a polysiloxane- based binder system, one or more hydrophilic-modified polysiloxanes, and one or more biocides. It is disclosed that hydrophilic-modified polysiloxane serves to facilitate the dissolution and transport of biocide to the surface of a coating.
  • KR 2014/0117922 discloses an antifouling paint composition comprising a metal ester binder, a polyether modified silicone oil and fumed silica.
  • the present inventors have now found that by re-designing erodible antifouling coating compositions by including therein polyoxyalkylene-modified silicone oils of the nature specified herein, it is possible to retard the otherwise free diffusion of biocide along the leach layer. This provides a more efficient use of metal-containing biocides leading to improved antifouling performance by using the same level of biocide, and/or reduction of the amount of biocide needed for obtaining the same antifouling performance, as this controlled release will increase bioavailability of biocide against fouling species for a prolonged period of time.
  • the function of the non-reactive polyoxyalkylene-modified silicone oils is to create an interaction with the metal- containing biocide which improves the antifouling performance and/or durability of the antifouling effect.
  • the ways to control the leach rate include the molecule size of the polyoxyalkylene-modified silicone oils, the overall hydrophilicity and the miscibility with the binder. The latter may be expressed by the so-called HLB value (hydrophilic-lipophilic balance). A very small molecule tends to diffuse and leach out of the film without achieving the intended effect, while a too large molecule would modify the film interaction with water and alter the desired leaching of biocides.
  • the present invention relates to a solvent-borne antifouling coating composition, cf. claim 1.
  • a second aspect of the invention relates to an antifouling coat, cf. claim 11.
  • a third aspect of the invention relates to an antifouling coating system, cf. claim 12.
  • a fourth aspect of the invention relates to a marine structure, cf. claim 14.
  • a fifth aspect of the invention relates to the use of the combination of one or more non- reactive polyoxyalkylene-modified silicone oils and one or more metal-containing biocides for improving the antifouling properties of a coating composition comprising an erodible non- silicone based binder system, cf. claim 15. DETAILED DESCRIPTION OF THE INVENTION
  • the solvent-borne antifouling coating composition is the solvent-borne antifouling coating composition
  • the present invention i. a. provides a solvent-borne antifouling coating composition
  • a solvent-borne antifouling coating composition comprising a. an erodible non-silicone based binder system, b. one or more metal-containing biocides, and c. one or more non-reactive polyoxyalkylene-modified silicone oils, wherein the one or more non-reactive polyoxyalkylene-modified silicone oils are present in a total amount of 0.05-10 % by dry weight based on the coating composition.
  • Coating compositions typically consists of a binder phase (which forms the paint film upon drying and thereby corresponds to the continuous phase of the final paint coat) and a pigments phase (corresponding to the discontinuous phase of the final paint coat).
  • a binder phase which forms the paint film upon drying and thereby corresponds to the continuous phase of the final paint coat
  • a pigments phase corresponding to the discontinuous phase of the final paint coat
  • the term "solvent-borne” is understood as coating compositions in which the components of the binder system is dissolved in a non-aqueous solvent, and wherein a coat corresponding to the coating composition is formed upon evaporation of the solvent and, in some instance, further upon curing of the binder components.
  • the solvent-borne coating composition comprises a physically drying binder system which differs from a chemically hardening binder system (see below) in that the binder components (i.e. individual molecules) of the binder system in the dry coat are already present in the same form in the wet coating composition. There is no change in the binder composition or the molecular structure or size of the binder
  • the solvent-borne coating composition comprises a chemically hardening binder system characterised in that the final binder molecules in the dry/cured paint film are not present in the wet film.
  • the relatively smaller binder component molecules e.g. monomer
  • the relatively smaller binder component molecules take part in a chemical reaction to form larger molecules, e.g. by chain extension, and possibly involving crosslinking binder components.
  • non-silicone based binder system is understood in the sense that the binder system of the antifouling coating composition is essentially free of silicone and polysiloxane parts.
  • any organosilicon parts of the coating composition (when disregarding the polyoxyalkylene-modified silicone oil(s) and any ester- linked silyl groups of the binder) preferably constitute less than 5 % by dry weight of the binder system, such as less that 2 % by dry weight, or less than 1 % by dry weight, in particular around 0 % by dry weight.
  • any such organosilicon-containing constituents are not part of the backbone of the binder(s), but may represent groups/chains pendant to the binder component backbone.
  • the binder system The binder systems applicable in the present invention are erodible non-silicone based binder systems.
  • the non-silicone based binder system constitutes 25-80 % by solids volume of the coating composition. In preferred embodiments, the non-silicone based binder system constitutes 20-70 % by solids volume, such as 18-55 % by solids volume of the coating composition.
  • the non-silicone based binder system When expressed by dry weight, typically the non-silicone based binder system constitutes 18-75 % by dry weight of the coating composition. In preferred embodiments, the non- silicone based binder system constitutes 16-60 %, such as 15-40 %, by dry weight of the coating composition.
  • the binder systems described herein are of the erodible type ("self-polishing"). When used herein, the term “erodible” (occasionally referred to as “self-polishing") is intended to mean that the paint coat (i.e. the dried film of the coating composition) should have a polishing rate of at least 1 pm per 10,000 Nautical miles (18,520 km) determined in accordance with the "Polishing rate test" specified in the Examples section. In preferred embodiments, the polishing rate is in the range of 1-50 pm, in particular in the range of 1-30 pm, per 10,000 Nautical miles (18,520 km).
  • the binder phase of the coating composition forms the paint film upon drying and thereby corresponds to the continuous phase of the final (dry) paint coat. It is envisaged that all erodible binder systems conventionally used in "self-polishing" coating compositions may be used as the binder system of the present coating composition. It is also found that with respect to the relative amounts of binder system vs. pigments/fillers/etc. , only minor modifications (optimizations) may be necessary in order to obtain suitable polishing rates with respect to the marine environment to which the paint coat will be exposed.
  • binder systems for marine purposes and yacht purposes, are provided in the following.
  • non-aqueous dispersion binder systems silylated acrylate binder systems, metal acrylate binder system, hybrids of silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, zwitterion binder systems, hybrids of silylated acrylate, zwitterion binder systems, polyester binder system, (natural) rosin, rosin derivatives, disproportionated rosin, partly polymerised rosin, hydrogenated rosin, gum rosin, disproportionated gum rosin, acrylic resins, polyvinyl methyl ether, and vinyl acetate- vinylchloride-ethylene terpolymers.
  • rosin binder systems non-aqueous dispersion binder systems, silylated acrylate binder systems, metal acrylate binder system, hybrids of silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, zwitterion binder systems, hybrids of silylated acrylate, zwitterion binder systems and polyester binder systems, are especially interesting.
  • Particularly preferred binder systems are non-silicone based binder system comprising constituents selected from rosin based binder systems, silyl acrylate binder systems, nonaqueous dispersion based binder systems, and metal-acrylate based binder systems.
  • Non-aaueous dispersion binder system The terms “non-aqueous dispersion resin”, “NAD” and similar expressions are intended to mean a shell-core structure that includes a resin obtained by stably dispersing a high- polarity, high-molecular weight resin particulate component (the “core component”) into a non-aqueous liquid medium in a low-polarity solvent using a high-molecular weight component (the “shell component”).
  • the non-aqueous dispersion resin may be prepared by a method wherein a polymerisable ethylenically unsaturated monomer which is soluble in a hydrocarbon solvent and which is polymerisable to form a polymer (the core component) which is insoluble in the hydrocarbon solvent, is subjected to dispersion polymerisation in accordance with a conventional method in the hydrocarbon solvent in the presence of a shell component (the dispersion stabiliser) made of a polymer which dissolves or swells in the solvent.
  • a shell component the dispersion stabiliser
  • the non-aqueous dispersion-type resin utilised in this invention can be a resin known per se; or it can be produced like the known resins.
  • Such non-aqueous dispersion-type resins and method for their preparation are described in, e.g. , US 3,607,821, US 4, 147,688, US
  • shell components such as an acrylic resin or a vinyl resin may be used.
  • a copolymer of an ethylenically unsaturated monomer having a high polarity is generally applicable.
  • the core component of the non-aqueous dispersion-type resin has free acid groups or silyl ester groups that are convertible into the acid group by hydrolysis in sea water or combinations thereof.
  • 5-75 % by weight, e.g. 5-60 % by weight or 7-50 % by weight, of the monomers of the core polymer should carry free acid groups or silyl ester groups or combinations thereof.
  • silyl ester monomers are silyl esters of acrylic or methacrylic acid.
  • a smaller proportion of the free acid groups or silyl ester groups may also be contained in the shell component.
  • free acid group is intended to cover the acid group in the acid form. It should be understood that such acid groups temporarily may exist on salt form if a suitable counter ion is present in the composition or in the environment. As an illustrative example, it is envisaged that some free acid groups may be present in the sodium salt form if such groups are exposed to salt water.
  • the non-aqueous dispersion-type resin has a resin acid value of usually 15-400 mg KOH/g, preferably 15 to 300 mg KOH/g, such as 18 to 300 mg KOH/g. If the total acid value of the NAD resin is below 15 mg KOH/g, the polishing rate of the paint coat is too low and the antifouling property will often be unsatisfactory. On the other hand, if the total acid value is above 400 mg KOH/g, the polishing rate is too high for that reason a problem of water resistance (durability of the paint coat in seawater) becomes a problem. (When the core component and/or the shell component contain the acid precursor group, the resin acid value is one given after the group is converted into the acid group by hydrolysis).
  • the "resin acid value” here referred to is an amount (mg) of KOH consumed to neutralise 1 g of a resin (solids content), expressing a content of an acid group (in case of the acid precursor group, a content of an acid group formed by hydrolysis) of the resin (solids content). It is advisable that the acid group and/or the acid precursor group is contained in the core component such that the content thereof is, as a resin acid value, at least 80 %, preferably at least 90 %, more preferably at least 95 % of the total resin acid value of the non-aqueous dispersion-type resin. This being said, it is normally preferred that the shell component is hydrophobic.
  • the dry weight ratio of the core component to the shell component in the NAD resin is not especially limited, but is normally in the range of 90/10 to 10/90, preferably 80/20 to 25/75, such as 60/40 to 25/75.
  • Silylated acrylate binder system is not especially limited, but is normally in the range of 90/10 to 10/90, preferably 80/20 to 25/75, such as 60/40 to 25/75.
  • the binder system to be used in the coating composition according to the invention comprises a silylated acrylate co-polymer having at least one side chain bearing at least one terminal group of the general formula (I) :
  • n is an integer of 0, 1, 2, etc.
  • Ri, R 2 , R 3 , R 4 and R 5 are as defined below
  • n is an integer of 0, 1, 2, 3, 4 or more, it is in these cases preferred that n is 0-100, e.g. 0-50, such as 0 or 1 or 2 or 2-15.
  • Ri-R 5 are each groups being the same or different and being selected from Ci- 20 -alkyl (e.g. methyl, ethyl, propyl, butyl, cycloalkyl such as cyclohexyl); optionally substituted aryl (e.g. substituted phenyl and substituted naphthyl). Examples of substituents for aryl are halogen, Ci_ 5 -alkyl, sulphonyl, nitro, or amino.
  • R1-R5 are each selected from Ci_ 8 -alkyl and optionally substituted phenyl. It is generally preferred that each of the alkyl groups has up to about 5 carbon atoms (Ci_ 5 -alkyl). As indicated above, R1-R5 may be the same or different groups.
  • Monomers comprising the terminal groups of the general formula I above may be synthesised as described in EP 0 297 505 Bl.
  • Such monomers may be co-polymerised with a vinyl polymerisable monomer (A) in order to obtain a co-polymer.
  • suitable vinyl polymerisable monomers (A) include methacrylate esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2- ethylhexyl methacrylate, 2-hydroxyethyl methacrylate and methoxy ethyl methacrylate; acrylate esters such as ethyl acrylate, butyl acrylate, 2 ethylhexyl acrylate and 2- hydroxyethyl acrylate; maleic acid esters such as dimethyl maleate and diethyl maleate; fumaric acid esters such as dimethyl fumarate and diethyl fumarate; styrene, vinyltoluene, a- methylstyrene, vinyl chloride, vinyl acetate, butadiene, acrylamide,
  • the amount of vinyl polymerisable monomers is not more than 95 % by weight of the total weight of the resulting co-polymer, preferably not more than 90 % by weight. Accordingly, the amount of monomers comprising the terminal groups of the general formula I above is at least 5 % by weight, in particular at least 10 % by weight.
  • the co-polymers preferably have weight average molecular weights in the range of 1,000- 1,500,000, such as in the range of 5,000- 1,500,000, e.g. in the range of 5,000-1,000,000, in the range of 5,000-500,000, in the range of 5,000-250,000, or in the range of 5,000- 100,000.
  • Examples of monomers having a terminal group of the general formula II (shown above) are acid functional vinyl polymerisable monomers, such as monomers derived from acrylic acid, methacylic acid, maleic acid (preferably in the form of a monoalkyl ester with 1-6 carbon atoms) or fumaric acid (preferably in the form of a monoalkyl ester with 1-6 carbon atoms).
  • acid functional vinyl polymerisable monomers such as monomers derived from acrylic acid, methacylic acid, maleic acid (preferably in the form of a monoalkyl ester with 1-6 carbon atoms) or fumaric acid (preferably in the form of a monoalkyl ester with 1-6 carbon atoms).
  • a suitable triorganosilyl group i.e. the -Si(R 3 )(R 4 )(R 5 ) group
  • suitable methacrylic acid-derived monomers bearing at least one terminal group of the general formula I or II include trimethylsilyl (meth)acrylate, triethyl- silyl(meth)acrylate, tri-n-propylsilyl(meth)acrylate, triisopropylsilyl (meth)acrylate, tri-n- butylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-tert-butylsilyl(meth)acrylate, tri- n-amylsilyl (meth)acrylate, tri-n-hexylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri- n-dodecylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, tri-p-methylphenylsilyl (meth)- acrylate, tribenzylsilyl (
  • suitable maleic acid-derived and fumaric acid-derived monomers bearing at least one terminal group of the general formula I or II include triisopropylsilyl methyl maleate, triisopropylsilyl amyl maleate, tri-n-butylsilyl n-butyl maleate, tert-butyldiphenylsilyl methyl maleate, t-butyldiphenylsilyl n-butyl maleate, triisopropylsilyl methyl fumarate, triisopropylsilyl amyl fumarate, tri-n-butylsilyl n-butyl fumarate, tert-butyldiphenylsilyl methyl fumarate, and tert-butyldiphenylsilyl n-butyl fumarate.
  • the co-polymer to be used in the binder system comprises monomer units with a terminal group of the general formulae I
  • monomers wherein R A and R B are larger groups, such as C ⁇ o-alkyl or aryl, may also be useful for the purposes described herein.
  • monomer B has in its molecule an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group (preferably in the form of a mono-C ⁇ -alky! ester), or a fumaroyloxy group (preferably in the form of a mono-Ci- 6 -alkyl ester) as an unsaturated group (Y) and also alkoxy- or
  • the degree of polymerisation (p) of the polyethylene glycol is from 1 to 25.
  • monomer B which has a (meth)acryloyloxy group in a molecule examples include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, hexoxyethyl (meth)acrylate, methoxydiethylene glycol
  • monomer B which has a maleinoyloxy or fumaroyloxy group in a molecule include methoxyethyl n-butyl maleate, ethoxydiethylene glycol methyl maleate, ethoxytriethylene glycol methyl maleate, propoxydiethylene glycol methyl maleate, butoxyethyl methyl maleate, hexoxyethyl methyl maleate, methoxyethyl n-butyl fumarate, ethoxydiethylene glycol methyl fumarate, ethoxytriethylene glycol methyl fumarate, propoxydiethylene glycol methyl fumarate, butoxyethyl methyl fumarate, and hexoxyethyl methyl fumarate.
  • vinyl monomers may be incorporated in the resulting co-polymer comprising either monomer units having a terminal group of the general formulae I or II (shown above) or in the resulting co-polymer comprising monomer units having a terminal group of the general formulae I or II (shown above) in combination with the second monomer B of the formula III (shown above) .
  • vinyl monomers such as the vinyl polymerisable monomers (A) discussed above.
  • the proportion of the monomer having a terminal group of the general formulae I or II is from 1-95 % by weight, that of monomer B is from 1-95 % by weight, and that of other monomer(s) co-polymerisable therewith is from 0-95 % by weight on the basis of the total weight of the monomers.
  • the molecular weight of the resulting co-polymer thus obtained is desirably in the range of 1,000- 150,000, such as in the range of 3,000- 100,000, e.g. in the range of 5,000- 100,000 in terms of weight-average molecular weight.
  • the binder system to be used in the coating composition according to the invention comprises a co-polymer having monomer units with a terminal group of the general formulae I or II (as discussed above) in combination with a second monomer C of the general formula IV:
  • methacryloyloxy group a maleinoyloxy group (preferably in the form of a mono-C ⁇ -alky! ester), or a fumaroyloxy group (preferably in the form of a mono-Ci- 6 -alkyl ester) as an unsaturated group (Y) and also a hemi-acetal group.
  • Monomer C can be prepared by an ordinary addition reaction of a carboxy group-containing vinyl monomer selected from acrylic acid, methacrylic acid, maleic acid (or monoester thereof), and fumaric acid (or monoester thereof), with an alkyl vinyl ether (e.g. ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and 2-ethylhexyl vinyl ether), or a cycloalkyl vinyl ether (e.g. cyclohexyl vinyl ether).
  • a carboxy group-containing vinyl monomer selected from acrylic acid, methacrylic acid, maleic acid (or monoester thereof), and fumaric acid (or monoester thereof)
  • an alkyl vinyl ether e.g. ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and 2-ethylhexyl vinyl ether
  • vinyl monomers may be incorporated in the resulting co-polymer comprising monomer units having a terminal group of the general formulae I or II (shown above) in combination with the second monomer C of the formula IV (shown above).
  • vinyl monomers such as the vinyl polymerisable monomers (A) discussed above.
  • the proportion of the monomer having a terminal group of the general formulae I or II is from 1-95 % by weight (preferably from 1-80 % by weight), that of monomer C is from 1-95 % by weight (preferably from 1-80 % by weight), and that of other monomer(s) co-polymerisable therewith is up to 98 % by weight on the basis of the total weight of the monomers.
  • the molecular weight of the co-polymer is desirably in the range of 1,000- 150,000, preferably in the range of 3,000-100,000, such as in the range of 5,000-100,000 in terms of weight-average molecular weight.
  • R 4 is a monovalent organic residue, or L is -OH or combinations thereof;
  • R 3 is hydrogen or a hydrocarbon group having from 1 to 10 carbon atoms.
  • monomers having a terminal group of the general formulae V are acid-functional vinyl polymerisable monomers, such as methacrylic acid, acrylic acid, p- styrene sulfonic acid, 2-methyl-2-acrylamide propane sulfonic acid, methacryl acid phosphoxy propyl, methacryl 3-chloro-2-acid phosphoxy propyl, methacryl acid phosphoxy ethyl, itaconic acid, maleic acid, maleic anhydride, monoalkyl itaconate (e.g.
  • methyl, ethyl, butyl, 2-ethyl hexyl monalkyi maleate (e.g. methyl, ethyl, butyl, 2-ethyl hexyl; half-ester of acid anhydride with hydroxyl containing polymerisable unsaturated monomer (e.g. half-ester of succinic anhydride, maleic anhydride or phthalic anhydride with 2-hydroxy ethyl methacrylate.
  • the above-mentioned monomers may be co-polymerised (in order to obtain the co-polymer with one or more vinyl polymerisable monomers.
  • vinyl polymerisable monomers examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethyl hexyl acrylate, 2-ethyl hexyl methacrylate, methoxy ethyl methacrylate, styrene, vinyl toluene, vinyl pyridine, vinyl pyrolidone, vinyl acetate, acrylonitrile, methacrylonitrile, dimethyl itaconate, dibutyl itaconate, di-2-ethyl hexyl itaconate, dimethyl maleate, di (2-ethyl hexyl) maleate, ethylene, propylene and vinyl chloride.
  • each individual ligand is preferably selected from the group consisting of
  • R 4 is a monovalent organic residue.
  • R 4 is selected from the group consisting of
  • R 5 is hydrogen or a hydrocarbon group having from 1 to 20 carbon atoms
  • R 6 and R 7 each independently represents a hydrocarbon group having from 1 to 12 carbon atoms
  • R 8 is a hydrocarbon group having from 1 to 4 carbon atoms
  • R 9 is cyclic hydrocarbon group having from 5 to 20 carbon atoms, such as abietic acid, pallustric acid, neoabietic acid, levopimaric acid, dehydroabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid and A8,9-isopimaric acid.
  • o— c e.g. aliphatic acids, such as levulinic acid; alicyclic acids, such as naphthenic acid, chaulmoogric acid, hydnocarpusic acid, neo abietic acid, levo pimaric acid, palustric acid, 2- methyl-bicyclo-2,2,l-heptane-2-carboxylic acid; aromatic carboxylic acids such as salicylic acid, cresotic acid, a-naphthoic acid, ⁇ -naphthoic acid, p-oxy benzoic acid; halogen containing aliphatic acids, such as monochloro acetic acid, monofluoro acetic acid; halogen containing aromatic acids, such as 2,4,5-trichloro phenoxy acetic acid, 2,4- dichloro phenoxy acetic acid, 3,5-dichloro benzoic acid; nitrogen-containing organic acids, such as quinoline carboxylic acid, nitro benzo
  • s— c e.g. dimethyl dithiocarbamate and other dithiocarbamates.
  • sulphur containing aromatic compounds such as l-naphthol-4- sulphonic acid, p-phenyl benzene sulphonic acid, ⁇ -naphthalene sulphonic acid and quinoline sulphonic acid.
  • any metal having a valency of 2 or more may be used.
  • suitable metals include Ca, Mg, Zn, Cu, Ba, Te, Pb, Fe, Co, Ni, Bi, Si, Ti, Mn, Al and Sn.
  • Preferred examples are Co, Ni, Cu, Zn, Mn, and Te, in particular Cu and Zn.
  • the metal When synthesising the metal-containing co-polymer, the metal may be employed in the form of its oxide, hydroxide or chloride.
  • the co-polymer to be used in the binder system in the coating composition according to the invention may be prepared as described in e.g. EP 0 471 204 Bl, EP 0 342 276 Bl or EP 0 204 456 Bl.
  • Monomers comprising the terminal groups of the general formula V above may be co-polymerised (in order to obtain the co-polymer) with other polymerisable unsaturated monomers, any customarily used ethylenically unsatured monomer may be used.
  • Examples of such monomers are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethyl hexyl acrylate, 2- ethyl hexyl methacrylate, methoxy ethyl methacrylate, styrene, vinyl toluene, vinyl pyridine, vinyl pyrolidone, vinyl acetate, acrylonitrile, methacrylo nitrile, dimethyl itaconate, dibutyl itaconate, di-2-ethyl hexyl itaconate, dimethyl maleate, di (2-ethyl hexyl) maleate, ethylene, propylene and vinyl chloride.
  • co-monomers are acrylic or methacrylic esters wherein the alcohol residue includes a bulky hydrocarbon radical or a soft segment, for example a branched alkyl ester having 4 or more carbon atoms or a cycloalkyl ester having 6 or more atoms, a polyalkylene glycol monoacrylate or monomethacrylate optionally having a terminal alkyl ether group or an adduct of 2-hydroxyethyl acrylate or methacrylate with caprolactone, e.g. as described in EP 0 779 304 Al.
  • a bulky hydrocarbon radical or a soft segment for example a branched alkyl ester having 4 or more carbon atoms or a cycloalkyl ester having 6 or more atoms
  • a polyalkylene glycol monoacrylate or monomethacrylate optionally having a terminal alkyl ether group or an adduct of 2-hydroxyethyl acrylate or methacrylate with caprolactone
  • hydroxy-containing monomers such as 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl acrylate, 2-hydroxy propyl methacrylate may also be used.
  • the weight average molecular weight of the metal-containing co-polymer is generally in the range of from 1,000 to 150,000, such as in the range of from 3,000 to 100,000, preferably in the range of from 5,000 to 60,000.
  • the coating composition further comprises an amount of an organic ligand at least equal to the ligand-to-metal co-ordination ratio of 1 : 1, said organic ligand being selected from the group consisting of aromatic nitro compounds, nitriles, urea compounds, alcohols, phenols, aldehydes, ketones, carboxylic acids and organic sulphur compounds, whereby the co-polymer defined above forms a polymer complex with the organic ligand in situ.
  • Examples of monobasic organic acids usable for forming the hybrid salt include
  • monocarboxylic acids such as acetic, propionic, butyric, lauric, stearic, linolic, oleic, naphthenic, chloroacetic fluoroacetic, abietic, phenoxyacetic, valeric, dichlorophenoxyacetic, benzoic or napthoic acid; and monosulphonic acids such as benzenesulphonic acid, p- toluenesulphonic acid, dodecylbenzenesulphonic acid, naphthalenesulphonic or p- phenylbenzenesulforic acid.
  • a preferred method for producing the polymeric hybrid salt has been disclosed in Japanese Patent Kokai No. 16809/1989.
  • An interesting further example of an interesting binder is that being based on silyl acrylate monomers (as those described further above) as well as metal acrylate monomers (as those described further above).
  • Such binders will have backbone fragments of the following general formula :
  • a further example of an interesting binder is that based on polyoxalates, e.g. as disclosed in WO 2015/114091.
  • Zwitterionic binders and hybrids with silyl acrylates A still further example of an interesting binder is that based on polymer binders having zwitterion monomers possibly combined with silyl acrylate monomers, e.g. as disclosed in WO 2004/018533 and WO 2016/066567.
  • Polyester binders An even further example of an interesting binder is that based on polyesters, e.g. as disclosed in WO 2014/010702.
  • a further interesting binder system may be than based on rosin and/or rosin derivatives, possibly in combination with any of the before-mentioned binder systems.
  • constituents of such a rosin-based binder system are rosin, rosin derivatives such as metal salts of rosin i.e. resinates.
  • rosin is intended to refer to gum rosin; wood rosin of grades B, C, D, E, F, FF, G, H, I, J, K, L, M, N, W-G, W-W (as defined by the ASTM 0509 standard); virgin rosin; hard rosin; yellow dip rosin; NF wood rosin; tall oil rosin; or colophony or colophonium.
  • rosin and “resinate” and the like are also intended to include suitable types of modified rosin, in particular oligomerisation; hydrogenation;
  • group of further binder components may include polymeric flexibilisers such as those generally and specifically defined in WO 97/44401 that is hereby incorporated by reference.
  • the rosin-based binder system When expressed by dry weight, typically the rosin-based binder system constitutes 5-30 % by dry weight of the coating composition. In preferred embodiments, the non-silicone based binder system constitutes 8-25 %, such as 10-25 %, by dry weight of the coating composition. In most practical embodiments, the rosin based binder system constitutes 10-50 % by solids volume of the coating composition. In preferred embodiments, the non-silicone based binder system constitutes 12-45 % by solids volume, such as 15-40 % by solids volume of the coating composition. Further binder components The above-mentioned binder systems (e.g.,
  • the non-aqueous dispersion binder system, the silylated acrylate binder system and the various hybrids may have included therein - as a part of the binder system - one or more further binder components.
  • the binder components mentioned below may alone also constitute the binder system, cf. the general presentation of the binder system.
  • oils such as linseed oil and derivatives thereof, castor oil and derivatives thereof, soy bean oil and derivatives thereof; and other polymeric binder components such as saturated polyester resins; polyvinylacetate, polyvinylbutyrate, polyvinylchloride- acetate, copolymers of vinyl acetate and vinyl isobutyl ether; vinylchloride; copolymers of vinyl chloride and vinyl isobutyl ether; alkyd resins or modified alkyd resins; hydrocarbon resins such as petroleum fraction condensates;
  • chlorinated polyolefines such as chlorinated rubber, chlorinated polyethylene, chlorinated polypropylene; styrene copolymers such as styrene/butadiene copolymers,
  • styrene/methacrylate and styrene/acrylate copolymers acrylic resins such as homopolymers and copolymers of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and isobutyl methacrylate; hydroxy-acrylate copolymers; polyamide resins such as polyamide based on dimerised fatty acids, such as dimerised tall oil fatty acids; cyclised rubbers; epoxy esters; epoxy urethanes; polyurethanes; epoxy polymers; hydroxy-polyether resins; polyamine resins; etc., as well as copolymers thereof.
  • Such further binder components typically constitutes 0-25 %, such as 5-20 %, by wet weight.
  • Another prominent constituent of the coating compositions of the present invention is the one or more metal-containing biocides.
  • biocide is intended to mean an active substance intended to destroy, deter, render harmless, prevent the action of, or otherwise exert a controlling effect on any harmful organism by chemical or biological means.
  • metal-containing biocides are those selected from metal-containing organic biocides like metallo-dithiocarbamates (such as bis(dimethyldithiocarbamato)zinc, zinc-ethylenebis(dithiocarbamate) (Zineb), ethylene-bis(dithiocarbamato)manganese, dimethyl dithiocarbamate zinc, and complexes between these); bis(l-hydroxy-2(lH)- pyridinethionato-0,S)-copper (copper pyrithione); copper acrylate; bis(l-hydroxy-2(lH)- pyridinethionato-0,S)-zinc (zinc pyrithione); phenyl(bispyridyl)-bismuth dichloride; and
  • the metal-containing biocide is typically included in an amount of 3-65 %, such as 5-60 %, e.g. 10-60 %, or 15-60 %, or 15-40 %, or 20-60 %, by dry weight of the coating composition. Expressed as solids volume, the amount of the metal-containing biocide is typically 3-45 %, such as 5-40 %, e.g. 7-38 %, or 10-35 %, or 15-35 %, by solids volume of the coating composition.
  • the metal-containing biocide includes metal- containing inorganic biocide(s), in particular cuprous oxide.
  • the biocide in particular cuprous oxide
  • the biocide is typically included in an amount of 3-65 %, such as 5-60 %, e.g. 10-60 %, or 15-60 %, or 15-40 %, or 20-60 %, by dry weight of the coating
  • the amount of the inorganic metal-containing biocide is typically 3-45 %, such as 5-40 %, e.g. 7-38 %, or 10- 35 %, or 15-35 %, by solids volume of the coating composition.
  • the metal-containing biocide only includes metal-containing organic biocides.
  • the metal-containing organic biocide(s) is/are typically included in a total amount of 0.25-30 %, such as 0.5-25 %, e.g. 0.75-20 %, or 1-15 %, or even 2-12 %, by dry weight of the coating composition.
  • the amount of the metal-containing organic biocide is typically 0.5-15 %, such as 1-12 %, e.g. 2-10 %, or 4-9 %, by solids volume of the coating composition.
  • the metal-containing biocide is copper pyrithione and/or zinc pyrithione.
  • copper pyrithione and zinc pyrithione is typically included in a total amount of 0.25-30 %, such as 0.5-25 %, e.g. 0.75-20 %, or 1- 15%, or even 2-12 %, by dry weight of the coating composition.
  • the total amount of copper pyrithione and zinc pyrithione is typically 0.5-15 %, such as 1-12 %, e.g. 2-10 %, or 4-9 %, by solids volume of the coating composition.
  • the weight ratio between cuprous oxide and the combined amount of copper pyrithione and/or zinc pyrithione is preferably in the range of 100: 1 to 1 : 2, such as 50: 1 to 1 : 1.5, or 30: 1 to 1 : 1, e.g. 25: 1 to 1 : 1, or 20: 1 to 2: 1.
  • the solids volume ratio between cuprous oxide and the combined amount of copper pyrithione and/or zinc pyrithione is preferably in the range of 30: 1 to 1 : 3, such as 25: 1 to 1 : 2, or 20: 1 to 1 : 1.5, e.g. 15: 1 to 1 : 1.4, or 10: 1 to 1 : 1.2.
  • the metal-containing biocide is zinc- ethylenebis(dithiocarbamate) (Zineb).
  • zinc-ethylenebis(dithiocarbamate) (Zineb) is typically included in an amount of 1-30 %, such as 2-20 %, e.g. 3-15 %, or 4- 10%, or even 5-15 %, by dry weight of the coating composition.
  • the total amount of zinc-ethylenebis(dithiocarbamate) (Zineb) is typically 1-30 %, such as 2- 20 %, e.g. 3-15 %, or 4- 10 %, or 5-15 %, by solids volume of the coating composition.
  • the combined amount of biocides is typically an amount of 3-65 %, such as 5-60 %, e.g. 10-60 %, or 15-60 %, or even 20-60 %, by dry weight of the coating composition.
  • the amount of the cuprous oxide in combination with one or more other metal-containing biocides is typically 3- 45 %, such as 5-40 %, e.g. 7-38 %, or 10-35 %, or 15-35 %, by solids volume of the coating composition.
  • the metal-containing biocide may be combined with one or more non-metal biocides like heterocyclic nitrogen compounds such as 3a,4,7,7a-tetrahydro-2- ((trichloromethyl)-thio)-lH-isoindole-l,3(2H)-dione, pyridine-triphenylborane, l-(2,4,6- trichlorophenyl)-lH-pyrrole-2,5-dione, 2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine, 2- methylthio-4-tert-butylamino-6-cyclopropylamine-s-triazin, and quinoline derivatives;
  • heterocyclic nitrogen compounds such as 3a,4,7,7a-tetrahydro-2- ((trichloromethyl)-thio)-lH-isoindole-l,3(2H)-dione, pyridine-tripheny
  • heterocyclic sulfur compounds such as 2-(4-thiazolyl)benzimidazole, 4,5-dichloro-2-n-octyl- 4-isothiazolin-3-one, 4,5-dichloro-2-octyl-3(2H)-isothiazoline (Sea-Nine ® -211N), 1,2-benz- isothiazolin-3-one, 2-(thiocyanatomethylthio)-benzothiazole, (7?S 4-[l-(2,3- dimethylphenyl)ethyl]-3H-imidazole (Medetomidine, Selektope ® ), and 4-Brom-2-(4- chlorphenyl)-5-(trifluormethyl)-lH-pyrrol-3-carbonitril (Tralopyril, Econea ® ); urea derivatives such as N-( l,3-bis(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl)-
  • phenylcarbamate and N,N-didecyl-N-methyl-poly(oxyethyl)ammonium propionate amines such as dehydroabiethylamines and cocodimethylamine; substituted methane such as di(2- hydroxy-ethoxy) methane, 5,5'-dichloro-2,2'-dihydroxydiphenylmethane, and methylene- bisthiocyanate; substituted benzene such as 2,4,5,6-tetrachloro-l,3-benzenedicarbonitrile, l,l-dichloro-N-((dimethylamino)-sulfonyl)-l-fluoro-N-phenylmethanesulfenamide, and 1- ((diiodomethyl)sulfonyl)-4-methyl-benzene; tetraalkyl phosphonium halogenides such as tri- n-butyltetradecyl
  • Non-reactive polyoxyalkylene-modified silicone oils are non-reactive polyoxyalkylene-modified silicone oils.
  • a prominent constituent of the coating compositions of the present invention is the one or more non-reactive polyoxyalkylene-modified silicone oils.
  • polyoxyalkylene-modified silicone oil is intended to mean a non-reactive silicone oil.
  • Polyoxyalkylene-modified silicone oils are widely used as surfactants and emulsifiers due to the content of both hydrophilic and lipophilic groups in the same molecule. The hydrophilicity is obtained by modification with polyoxyalkylene groups.
  • the polyoxyalkylene-modified silicone oils are non-reactive, i.e. the oils are selected so that they do not contain groups that can react with the binder or any individual binder components.
  • the polyoxyalkylene-modified silicone oils are intended to be non- reactive in particular with respect to the binder components such that the polyoxyalkylene- modified silicone oils do not become covalently linked to the binder, but instead are freely embedded into the binder film in which such silicone oils in principles may migrate more or less freely.
  • the polyoxyalkylene-modified silicone oils are devoid of any reactive groups towards the binder components in accordance with the illustrative description of example of silicone oil (A), (B) and (C) further below. It is accepted that the silicone oils may carry "functional" groups, e.g. C-OH groups, as long as they do not in any significant way form any chemical reaction with the surrounding air or with any binder components or any additives contained in the coating composition at room temperature.
  • the hydrophilic character of the silicone oils is typically obtained by including pendant and/or terminal polyoxyalkylene chains as will be described in more detail in the following.
  • the non- reactive polyoxyalkylene-modified silicone oils are silicone oils carrying polyoxyalkylene chains.
  • the polyoxyalkylene chains are typically selected from poly(ethylene glycol) chains, poly(propylene glycol) chains and poly(ethylene glycol-co-propylene glycol) chains).
  • Examples of the latter are poly(ethylene glycol)-block-poly(propylene glycol), poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol), poly(propylene glycol)- block-poly(ethylene glycol), poly(propylene glycol)-block-poly(ethylene glycol)-block- poly(propylene glycol), and poly(ethylene glycol-ranatom-propylene glycol).
  • particularly interesting polyoxyalkylene-modified silicone oils typically have a HLB value (as determined as described in the Examples section) in the range of 4 to 19.5, in particular 5 to 19, or 6 to 19, or 7 to 19, such as more preferably in the range of 9 to 18, e.g. 11-17.
  • polyoxyalkylene chains are selected from poly(ethylene glycol) chains and poly(ethylene glycol-co-propylene glycol) chains wherein the weight ratio between ethylene glycol (PEG) and propylene glycol (PPG) is more than 25: 75, such as in the range of 95: 5 to 25 : 75, e.g. 90: 10 to 30: 70, preferably 75: 25 to 35: 65, more preferably 60:40 to 40: 60.
  • the polyoxyalkylene-modified silicone oil is a silicone having grafted thereto polyoxyalkylene chains.
  • polyoxyalkylene-modified silicone oils is formula (A) :
  • each R 1 is independently selected from Ci_ 5 -alkyl (including linear or branched hydrocarbon groups) and aryl (e.g. phenyl (-C 6 H 5 )), in particular methyl;
  • each R 2 is independently selected from -H, Ci- 4 -alkyl (e.g . -CH 3 , -CH 2 CH 3 , -
  • each R 3 is independently selected from -CH 2 CH 2 - and -CH 2 CH(CH 3 )-;
  • each R 4 is selected from -(CH 2 ) 2 _ 6 -;
  • x is 0-2500, y is 1- 100 and x+y is 1-2000;
  • n 0-50, m is 0-50 and m+ n is 1-70.
  • n+ m includes 3 to 60 repeating units, such as 3 to 50 repeating units, such as 3 to 30 or even 4 to 20 repeating units. In yet another interesting embodiment n+ m includes 6 to 40 repeating units, such as 8 to 30 or 10 to 25 repeating units.
  • x+y is less than 25 such as less than 20, or less than 15.
  • x+y includes 3 to 30 repeating units, such as 3 to 20 repeating units, such as 3 to 15 or even 4 to 12 repeating units.
  • x+y includes 6 to 20 repeating units, such as 8 to 15 repeating units.
  • the polyoxyalkylene-rmodified silicone oil is a silicone having terminal polyoxyalkylene chains. An illustrative example of the structure of such
  • polyoxyalkylene-rmodified silicone oils is formula (B) :
  • each R 1 is independently selected from Ci_ 5 -alkyl (including linear or branched hydrocarbon groups) and aryl (e.g. phenyl (-C 6 H 5 )), in particular methyl;
  • each R 4 is selected from -(CH 2 ) 2 -6-;
  • x is 1-2500
  • n+ m includes 3 to 60 repeating units, such as 3 to 50 repeating units, such as 3 to 30 or even 4 to 20 repeating units. In yet another interesting embodiment n+ m includes 6 to 40 repeating units, such as 8 to 30 or 10-25 repeating units.
  • x includes 3 to 1,000 repeating units, such as 3 to 200, or 5 to 150, or 5 to 100, repeating units, e.g. 1 to 50 repeating units. In another interesting embodiment x includes 3 to 30 repeating units, such as 3 to 20 repeating units, such as 3 to 15, or even 4 to 12, repeating units. In yet another interesting embodiment x includes 6 to 20 repeating units, such as 8 to 15 repeating units.
  • n+ m+x includes 3 to 120 repeating units, such as 3 to 100 repeating units, such as 3 to 80, or even 4 to 50, repeating units.
  • n+ m+x includes 6 to 40 repeating units, e.g. 8 to 35 repeating units, such as 8 to 30 repeating units.
  • the polyoxyalkylene-modified silicone oil is a silicone having terminal polyoxyalkylene chains and having grafted thereto polyoxyalkylene chains.
  • An illustrative example of the structure of such polyoxyalkylene-modified silicone oils is formula (C) :
  • each R 1 is independently selected from Ci_ 5 -alkyl (including linear or branched hydrocarbon groups) and aryl (e.g. phenyl (-C 6 H 5 )), in particular methyl;
  • each R 2 is independently selected from -H, Ci-4-alkyl (e.g. -CH 3 , -CH 2 CH 3 , -
  • each R 3 is independently selected from -CH 2 CH 2 - and -CH 2 CH(CH 3 )-;
  • each R 4 is selected from -(CH 2 ) 2 -6- ;
  • x is 0-2500, y is 1- 100 and x+y is 1-2000;
  • k is 0-50, I is 0-50 and k+ l is 1-50;
  • n + m includes 3 to 60 repeating units, such as 3 to 50 repeating units, such as 3 to 30 or even 4 to 20 repeating units. In yet another interesting embodiment n+ m includes 6 to 40 repeating units, such as 8 to 30 or 10-25 repeating units. In an embodiment of formula (C) herein above, k+l includes 3 to 60 repeating units, such as 3 to 50 repeating units, such as 3 to 30 or even 4 to 20 repeating units. In yet another interesting embodiment k+ l includes 6 to 40 repeating units, such as 8 to 30 or 10-25 repeating units.
  • x includes 3 to 1,000 repeating units, such as 3 to 200, or 5 to 150, or 5 to 100 repeating units, e.g. 1 to 50 repeating units. In another interesting embodiment x includes 3 to 30 repeating units, such as 3 to 20 repeating units, such as 3 to 15, or even 4 to 12, repeating units. In yet another interesting embodiment x includes 6 to 20 repeating units, such as 8 to 15 repeating units. In an embodiment of formula (C) herein above, y includes 3 to 1,000 repeating units, such as 3 to 200, or 5 to 150, or 5 to 100 repeating units, e.g. 1 to 50 repeating units.
  • y includes 3 to 30 repeating units, such as 3 to 20 repeating units, such as 3 to 15, or even 4 to 12, repeating units. In yet another interesting embodiment y includes 6 to 20 repeating units, such as 8 to 15 repeating units.
  • the group -CH 2 CH(CH 3 )- may be present in any of the two possible orientations.
  • the segments present x and y times typically are randomly distributed, or distributed as blocks, within the silicone structure.
  • groups present I and k, and m and n, times typically are distributed as blocks, but may be randomly distributed.
  • the polyoxyalkylene chains are preferably selected from poly(ethylene glycol) and poly(ethylene glycol-co-propylene glycol).
  • each R 3 linking two oxygen atoms is selected from -CH 2 CH 2 - and -CH 2 CH(CH 3 )-.
  • the one or more non-reactive polyoxyalkylene-modified silicone oils may be of different types, e.g. two or more of the types described above.
  • each of the above-mentioned polyoxyalkylene chains includes at least 3 repeating units, such as at least 5 repeating units.
  • the above-mentioned polyoxyalkylene chains includes at least 3 repeating units, such as at least 5 repeating units.
  • polyoxyalkylene chains include 3-200 repeating units, such as 3- 150, or 5-100, or 5-80 repeating units. In another interesting embodiment the polyoxyalkylene chains include 3-30 repeating units, such as 3-20 repeating units, such as 3 to 15 or even 4 to 12 repeating units. In yet another interesting embodiment the polyoxyalkylene chains include 6 to 20 repeating units, such as 8 to 15 repeating units. In some preferred embodiments, the polyoxyalkylene chains have a number average molecular weight (M n ) in the range of 100-20,000 g/mol, such as in the range of 100-15,000 g/mol, in particular in the range of 200- 10,000 g/mol, or in the range of 200-8,000 g/mol.
  • M n number average molecular weight
  • the polyoxyalkylene chains have a number average molecular weight (M n ) in the range of 50-2,000 g/mol, such as 50-700 g/mol or even 100- 700 g/mol.
  • polyoxyalkylene-modified silicone oils in which the relative weight of the polyoxyalkylene chains is 1% or more of the total weight (e.g. 1-90%), such as 5% or more (e.g. 5-80%), in particular 10% or more (e.g. 10-70%) of the total weight of the polyoxyalkylene-modified silicone oil.
  • the relative weight of the polyoxyalkylene chains is in the range of 25-60 % such as 30-50 % of the total weight of the polyoxyalkylene-modified silicone oil.
  • the polyoxyalkylene-modified silicone oil has a number average molecular weight (M n ) in the range of 200-100,000 g/mol, such as in the range of 250- 75,000 g/mol, in particular in the range of 500-50,000 g/mol.
  • M n number average molecular weight
  • the polyoxyalkylene-modified silicone oil has a number average molecular weight (M n ) in the range of 500-20,000 g/mol, such as 1,000-10,000 g/mol or 1,000-7,500 g/mol or even 1,500-5,000 g/mol.
  • M n number average molecular weight
  • the polyoxyalkylene-modified silicone oils have a viscosity in the range of 10-20,000 mPa ⁇ s, such as in the range of 20-10,000 mPa ⁇ s, in particular in the range of 40-5,000 mPa ⁇ s.
  • Non-reactive polyoxyalkylene-modified silicone oils are, OFX-5103, OFX-190, OFX-5103, OFX QC2-5211, OFX-Q2-5097, OFX-Q4-3669, OFX-Q4-3667, OFX-2-86, and OFX- 193 (all from Xiameter), BYK-331 from BYK, DBE-621, CMS-222 from Gelest, CoatOSil 3501, SilSurf Di 1010, Silwet 7280, CoatOSil 7210, CoatOSil 7200, CoatOSil 7602, CoatOSil 1220 (all from Momentive), TEGO Glide 410 from Evonik industries, Pluronic L64 from BASF, KF945 from Shin-Etsu, and MB30X-8 from Sekisui Plastics.
  • the one or more non-reactive polyoxyalkylene-modified silicone oils are included in the coating composition (and in the final coat) in an amount of 0.05-10 %, by dry weight.
  • the one or more non-reactive polyoxyalkylene-modified silicone oils constitutes 0.05-10 % by dry weight, 0.05-7 % by dry weight, e.g. 0.1-6 % by dry weight, in particular 0.15-5 % by dry weight, or 0.15-4 %, or 0.2-3.5 %, or 0.1-3.2 %, of the coating composition/final coat.
  • the one or more non-reactive polyoxyalkylene-modified silicone oils constitutes 1-10 % by dry weight, e.g.
  • the one or more non-reactive polyoxyalkylene-modified silicone oils are typically included in the coating composition (and in the final coat) in an amount of 0.01-40 %, e.g. 0.05-30 %, by solids volume.
  • the one or more non-reactive polyoxyalkylene- modified silicone oils constitutes 0.05-25 % by solids volume, e.g. 0.1-20 % by solids volume, in particular 0.15-15 % by solids volume, or 0.15-14 %, or 0.2-12 %, or 0.5-10 %, of the coating composition/final coat.
  • the one or more non- reactive polyoxyalkylene-modified silicone oils constitutes 0.05-25 % by solids volume, e.g.
  • the coating compositions may further comprise solvents and additives.
  • the coating compositions described herein are solvent-borne, hence comprises a solvent or a mixture of solvents.
  • the solvents are of non-aqueous.
  • solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, methyl isobutyl ketone (MIBK), toluene, xylene and naphtha solvent, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; octamethyltrisiloxane, and mixtures thereof.
  • MIBK methyl isobutyl ketone
  • the solvents are selected from aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate;
  • octamethyltrisiloxane and mixtures thereof, preferably those solvents having a boiling point of 110 °C or more.
  • the solvent(s) typically constitute(s) 2-50 % by volume of the coating composition, such as 3-40 %, or 4-30 %, or 5-25 % by volume of the coating composition.
  • additives are:
  • non-reactive fluids such as organopolysiloxanes; for example polydimethylsiloxane, methylphenyl polysiloxane; petroleum oils and combinations thereof;
  • surfactants such as derivatives of propylene oxide or ethylene oxide such as alkylphenol- ethylene oxide condensates (alkylphenol ethoxylates); ethoxylated monoethanolamides of unsaturated fatty acids such as ethoxylated monoethanolamides of linoleic acid; sodium dodecyl sulfate; and soya lecithin;
  • thickeners and anti-settling agents e.g. thixotropic agents
  • thixotropic agents such as colloidal silica, hydrated aluminium silicate (bentonite), aluminium tristearate, aluminium monostearate, xanthan gum, chrysotile, pyrogenic silica, hydrogenated castor oil, organo-modified clays, polyamide waxes and polyethylene waxes;
  • dyes such as l,4-bis(butylamino)anthraquinone and other anthraquinone derivatives; toluidine dyes, etc. ;
  • antioxidants such as bis(tert-butyl) hydroquinone, 2,6-bis(tert-butyl) phenol, resorcinol, 4-tert-butyl catechol, tris(2,4-di-tert-butylphenyl)phosphite, pentaerythritol tetrakis(3-(3,5- di-tert-butyl-4-hydroxyphenyl)propionate), bis(2,2,6,6,-tetramethyl-4-piperidyl)sebacate, etc.
  • the coating composition comprises one or more thickeners and/or anti-settling agents (e.g. thixotropic agents), preferably in an amount of 0.2-10 %, such as 0.5-5 %, e.g. 0.6-4 %, by dry weight of the coating composition.
  • thickeners and/or anti-settling agents e.g. thixotropic agents
  • the coating composition used for forming the coat may comprise pigments and fillers.
  • Pigments and fillers are in the present context viewed in conjunction as constituents that may be added to the coating composition with only limited implications on the adhesion properties. "Pigments” are normally characterised in that they render the final paint coating non-transparent and non-translucent, whereas “fillers” normally are characterised in that they do not render the paint non-translucent and therefore do not contribute significantly to hide any material below the coating.
  • pigments are grades of titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminium sulfosilicates, quinacridones, phthalocyanine blue, phthalocyanine green, black iron oxide, indanthrone blue, cobalt aluminium oxide, carbazole dioxazine, chromium oxide, isoindoline orange, bis-acetoacet-o-tolidiole, benzimidazolon, quinaphtalone yellow, isoindoline yellow, tetrachloroisoindolinone, quinophthalone yellow.
  • fillers examples include calcium carbonate such as calcite, dolomite, talc, mica, feldspar, barium sulfate, kaolin, nephelin, silica, perlite, magnesium oxide, and quartz flour, etc. Fillers (and pigments) may also be added in the form of nanotubes or fibres, thus, apart from the before-mentioned examples of fillers, the coating composition may also comprise fibres, e.g. those generally and specifically described in WO 00/77102 which is hereby incorporated by reference.
  • Any pigments and/or fillers typically constitute 0-60 %, such as 0-50 %, preferably 5-45 %, such as 5-40 %, or 5-35 %, or 0.5-25 %, or 1-20 %, by dry weight of the coating composition. Taking into account the density of any pigments and/or fillers, such constituents typically constitute 0.2-20 %, such as 0.5-15 % by solids volume of the coating composition
  • the coating composition typically has a viscosity in the range of 25-25,000 mPa ⁇ s, such as in the range of 150-15,000 mPa ⁇ s, in particular in the range of 200-4,000 mPa ⁇ s.
  • the invention provides a solvent-borne antifouling coating composition comprising 18-40 % by dry weight of an erodible non-silicone based binder system, 20-55 % by dry weight of one or more metal-containing biocides and 0.2-5 % by dry weight of one or more non-reactive polyoxyalkylene-modified silicone oils.
  • the invention provides a solvent-borne antifouling coating composition
  • a solvent-borne antifouling coating composition comprising 18-40 % by dry weight of an erodible non-silicone based binder system, 20-55 % by dry weight of one or more metal-containing biocides and 0.2-5 % by dry weight of one or more non-reactive polyoxyalkylene-modified silicone oils, where the polyoxyalkylene chains poly(ethylene glycol-co-propylene glycol) chains wherein the weight ratio between ethylene glycol (PEG) and propylene glycol (PPG) is more than 25: 75, such as in the range of 95: 5 to 25: 75, e.g.
  • Preferred binder systems to be used in combination with the above embodiments are, rosin based binder systems, silyl acrylate binder systems, non-aqueous dispersion based binder systems, and metal-acrylate based binder systems.
  • a further aspect of the present invention is an antifouling coat (occasionally referred to as a "paint coat” or a “coating”) comprising an erodible non-silicone based binder matrix, one or more metal-containing biocides, and one or more non-reactive polyoxyalkylene-modified silicone oils.
  • a paint coat or a “coating”
  • the constituents are as defined further above for the paint composition, and any descriptions, preferences and variants also apply for the coat which simply represents the coating composition when allowed to dry.
  • the antifouling coat is such that it comprises 1-40, such as 2-30, in particular 3- 20 g/m 2 of said one or more non-reactive polyoxyalkylene-modified silicone oils and 10-500, such as 15-350, such as 20-250, such as 30-200, in particular 50-150 g/m 2 of said one or more metal-containing biocides.
  • the antifouling coating composition is used to prepare a corresponding antifouling coat.
  • the coating compositions may be prepared by any suitable technique that is commonly used within the field of paint production.
  • the various constituents may be mixed together utilizing a mixer, a high speed disperser, a ball mill, a pearl mill, a grinder, a three-roll mill etc.
  • the coating compositions are typically prepared and shipped as one or two- component systems that should be combined and thoroughly mixed immediately prior to use.
  • the paints according to the invention may be filtrated using bag filters, patron filters, wire gap filters, wedge wire filters, metal edge filters, EGLM turnoclean filters (ex. Cuno), DELTA strain filters (ex. Cuno), and Jenag Strainer filters (ex. Jenag), or by vibration filtration.
  • An example of a suitable preparation method is described in the Examples.
  • the present invention also relates to an antifouling coating system comprising at least a first coat and a second coat, a) said first coat comprising an erodible non-silicone based binder system, said first coat further comprising one or more non-reactive polyoxyalkylene-modified silicone oils; and b) said second coat comprising an erodible non-silicone based binder system, said second coat further comprising one or more metal-containing biocides.
  • the antifouling coat is such that it comprises 1-40, such as 2-30, in particular 3-20 g/m 2 of said one or more non-reactive polyoxyalkylene-modified silicone oils and 10-500, such as 15-350, such as 20-250, such as 30-200, in particular 50-150 g/m 2 of said one or more metal-containing biocides.
  • first coat as well as the second coat are prepared on a substrate in such a way that the second coat is prepared on top of the first coat.
  • first coat may be prepared on an already existing coating layer, e.g. an anti-corrosive coating layer, or an aged antifouling or fouling-release coat, etc., or directly on a native substrate (see further below in the section "Application of coating compositions".
  • second coat is preferably the outermost layer, the second coat may in principle be over-coated with a further coating layer (e.g. a top-coat).
  • outermost coat i.e. the second coat
  • first coat the underlying layer
  • silicone oil polyoxyalkylene-modified silicone oil
  • the antifouling coating system comprises at least a first coat and a second coat.
  • first coat as well as in the second coat (except that the binder system is not necessarily identical) is described in the above sections, "The binder system”, “Non-reactive
  • first coat is described in the section "The first coat ..” below, whereas the specific features of the second coat is further described in the section “The second coat ..” further below. It should be understood that although the first coat and the second coat typically are of the same or similar type (or even identical) with respect to the binder system, the first coat and the second coat are not identical.
  • the first coat and the second coat at least differs with respect to at least one of i) the content and/or type of metal-containing biocide(s), and ii) the content and/or type of the polyoxyalkylene-modified silicone oil(s).
  • the first coat of the coating system is the first coat of the coating system
  • the coating composition used for establishing the first coat of the coating system is essentially as described above for the antifouling coating in the section "The solvent-borne antifouling coating composition", except that the first coat does not have - as a mandatory constituent - included a metal-containing biocide. Otherwise, the first coat is a described above, mutatis mutandis.
  • the first coat comprises: 18-40 % by dry weight of an erodible non-silicone based binder system
  • the first coat further comprises one or more metal-containing biocides or other biocides, in particular of the types and in the amounts specified further above in the section "Metal-containing biocides”.
  • the coating composition used for establishing the second coat of the coating system is essentially as described above for the antifouling coating in the section "The solvent-borne antifouling coating composition", except that the first coat does not have - as a mandatory constituent - included a polyoxyalkylene-modified silicone oil. Otherwise, the first coat is a described above, mutatis mutandis.
  • the second coat comprises: 18-40 % by dry weight of an erodible non-silicone based binder system
  • the second coat further comprises one or more non-reactive polyoxyalkylene-modified silicone oils, in particular of the types and in the amounts specified further above in the section "Non-reactive polyoxyalkylene-modified silicone oils ".
  • the coating composition of the invention is typically applied to at least a part of the surface of a substrate.
  • applying is used in its normal meaning within the paint industry.
  • “applying” is conducted by means of any conventional means, e.g. by brush, by roller, by spraying, by dipping, etc.
  • the commercially most interesting way of “applying” the coating composition is by spraying.
  • the coating composition is preferably sprayable. Spraying is effected by means of conventional spraying equipment known to the person skilled in the art.
  • the coating is typically applied in a dry film thickness of 50-600 pm, such as 50-500 ⁇ , e.g. 75- 400 pm, or 20-150 pm, or 30-100 pm.
  • the coating composition is preferably such with respect to sag resistance cf. ASTM D 4400-99 (i.e. relating to its ability to be applied in a suitable film thickness to a vertical surface without sagging) that it exhibits sag resistance for a wet film thickness up to at least 70 pm, such as up to at least 200 pm, e.g. up to at least 300 pm, preferably up to at least 400 pm, and in particular up to at least 600 pm.
  • ASTM D 4400-99 i.e. relating to its ability to be applied in a suitable film thickness to a vertical surface without sagging
  • the term "at least a part of the surface of a substrate” refers to the fact that the coating composition may be applied to any fraction of the surface.
  • the coating composition is at least applied to the part of the substrate (e.g. a vessel) where the surface (e.g. the ship's hull) may come in contact with water, e.g. sea-water.
  • the term "substrate” is intended to mean a solid material onto which the coating composition is applied.
  • the substrate typically comprises a metal such as steel, iron, aluminium, or glass- fibre reinforced polyester.
  • the substrate is a metal substrate, in particular a steel substrate.
  • the substrate is a glass-fibre reinforced polyester substrate.
  • the substrate is at least a part of the outermost surface of a marine structure.
  • surface is used in its normal sense, and refers to the exterior boundary of an object.
  • Particular examples of such surfaces are the surface of marine structures, such as vessels (including but not limited to boats, 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, floatation devices, water-power installations and structures, underwater oil well structures, nets and other aquatic culture installations, cooling plants, and buoys, etc., and is especially applicable to the hulls of ships and boats and to pipes.
  • vessels including but not limited to boats, 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, floatation devices, water-power installations
  • the surface of the substrate may either be the "native" surface (e.g. the steel surface).
  • the substrate is typically coated, e.g. with an anticorrosive coating and/or a tie coat, so that the surface of the substrate is constituted by such a coating.
  • the (anticorrosive and/or tie) coating is typically applied in a total dry film thickness of 100-600 pm, such as 150-450 pm, e.g. 200-400 pm.
  • the substrate may carry a paint coat, e.g. a worn-out antifouling paint coat, or similar.
  • the substrate is a metal substrate (e.g. a steel substrate) coated with an anticorrosive coating such as an anticorrosive epoxy-based coating, e.g. cured epoxy-based coating, or a shop-primer, e.g. a zinc-rich shop-primer.
  • an anticorrosive coating such as an anticorrosive epoxy-based coating, e.g. cured epoxy-based coating, or a shop-primer, e.g. a zinc-rich shop-primer.
  • the substrate is a glass-fiber reinforced polyester substrate coated with an epoxy primer coating.
  • the coat of the main aspect of the invention is typically applied as the outermost coat (a. k.a. a top-coat), i.e. the coat being exposed to the environment, e.g. an aquatic environment.
  • the coat of the main aspect of the invention alternatively may be applied as a layered system where the coat described in the main aspect of this invention will be coated with one or more layer(s) of one or more other coating compositions in order to obtain an improve control of the leaching rate of the leachable components in the coat.
  • a coating composition Prior to the application of a coating composition to a marine structure, the marine structure may first be coated with a primer-system which may comprise several layers and may be any of the conventional primer systems used in connection with application of coating
  • the primer system may include an anti-corrosive primer optionally followed by a layer of an adhesion-promoting primer.
  • the invention also relates to a method of establishing an antifouling coating system on a surface of a substrate, comprising the sequential steps of: a) applying one or more layers of a primer composition onto the surface of said substrate, thereby forming a primed substrate, b) applying one or more layers of a solvent-borne antifouling coating composition onto the surface of said primed surface, and allowing said layer(s) to dry/cure, thereby forming a antifouling coat as defined hereinabove (main aspect).
  • the antifouling coat may be further coated with a top-coat.
  • the invention also relates to a method of establishing an antifouling coating system on a surface of a substrate (according to the first alternative aspect), comprising the sequential steps of: a) applying one or more layers of a solvent-borne antifouling coating composition onto the surface of said substrate, e.g.
  • the invention also relates to a method of establishing an antifouling coating system on a surface of a substrate (according to the first alternative aspect), comprising the sequential steps of: a) applying one or more layers of a primer composition onto the surface of said substrate, and allowing said layer(s) to dry/cure, thereby forming a primed substrate, b) applying one or more layers of a solvent-borne antifouling coating composition onto the surface of said primed substrate, and allowing said layer(s) to dry/cure, thereby forming a first coat as defined hereinabove for the first alternative aspect, and c) applying one or more layers of a solvent-borne antifouling coating composition onto the surface of said first coat, and allowing said layer(s) to dry/cure, thereby forming a second coat as defined hereinabove for the first alternative aspect.
  • the invention further relates to a method of establishing an antifouling coating system on a surface of an aged antifouling coating system, comprising the sequential steps of: a) applying one or more layers of a sealer/link-coat composition onto the surface of said substrate, allowing said layer(s) to dry/cure, thereby forming a sealed substrate, b) applying one or more layers of a solvent-borne antifouling coating composition onto the surface of said primed substrate, and allowing said layer(s) to dry/cure, thereby forming a first coat as defined hereinabove for the first alternative aspect, and c) applying one or more layers of a solvent-borne antifouling coating composition onto the surface of said first coat, and allowing said layer(s) to dry/cure, thereby forming a second coat as defined hereinabove for the first alternative aspect.
  • the invention further relates to a method of establishing an antifouling coating system on a surface of an aged antifouling coating system, comprising the sequential steps of: a) applying one or more layers of a solvent-borne antifouling coating composition onto the surface of said aged antifouling coating system, and allowing said layer(s) to dry/cure, thereby forming a first coat as defined hereinabove for the first alternative aspect, and b) applying one or more layers of a solvent-borne antifouling coating composition onto the surface of said first coat, and allowing said layer(s) to dry/cure, thereby forming a second coat as defined hereinabove for the first alternative aspect.
  • the present invention further provides a marine structure comprising on at least a part of the outer surface thereof an outermost antifouling coat as defined hereinabove under the section "Antifouling coat".
  • a marine structure comprising on at least a part of the outer surface thereof an outermost antifouling coat as defined hereinabove under the section "Antifouling coat”.
  • at least as part of the outer surface carrying the outermost coating is a submerged part of said structure.
  • the present invention also provides a marine structure comprising on at least a part of the outer surface thereof an outermost antifouling coating system as defined hereinabove under the section "First alternative aspect of the invention".
  • at least as part of the outer surface carrying the outermost coating is a submerged part of said structure.
  • the antifouling coating system of the marine structure may consist of an anticorrosive layer and the antifouling coating system as described herein.
  • the antifouling coating composition is applied on top of a used antifouling coating system, e.g. on top of a used antifouling coat.
  • the anticorrosive layer has a total dry film thickness of 100-600 pm, such as 150-450 pm, e.g. 200-400 pm; and the antifouling coating has a total dry film thickness of 20-500 pm, such as 20-400 pm, e.g. 50- 300 pm.
  • a further embodiment of the marine structure is that where at least a part of the outermost surface of said structure is coated with an antifouling coating system comprising a total dry film thickness of 150-400 pm of an anticorrosive layer of an epoxy-based coating established by application of 1-4, such as 2-4, layers; and
  • a further embodiment of the marine structure is that where at least a part of the outermost surface of said structure is coated with an antifouling coating system (first alternative aspect) comprising a total dry film thickness of 150-400 pm of an anticorrosive layer of an epoxy-based coating established by application of 1-4, such as 2-4, layers;
  • an antifouling coating system (first alternative aspect) comprising a total dry film thickness of 150-400 pm of an anticorrosive layer of an epoxy-based coating established by application of 1-4, such as 2-4, layers;
  • a further aspect of the invention relates to the use of the combination of one or more non- reactive polyoxyalkylene-modified silicone oils and one or more metal-containing biocides, for improving the antifouling properties of a coating composition comprising an erodible non- silicone based binder system.
  • the coating compositions defined herein may comprise one, two or more types of the individual constituents.
  • the total amount of the respective constituent should correspond to the amount defined above for the individual constituent.
  • the "(s)" in the expressions: compound(s), silicones(s), agent(s), etc. indicates that one, two or more types of the individual constituents may be present.
  • % dry weight means the percentage of the respective component based on the dry weight of the coat or of the coating composition, as the case may be. For most practical purposes (hence, unless otherwise stated), the “% dry weight” when referring the final coat is identical to the “% dry weight” of the coating composition.
  • Plasticizer 45 wt.% solution in xylene
  • Oil 1, non-reactive polyether modified silicone oil, HLB 10.5, PEG/PPG ratio 50/50
  • Oil 2 non-reactive polyether modified silicone oil, HLB 17.0, PEG/PPG ratio 50/50
  • Oil 3 non-reactive polyether modified silicone oil, HLB 13.0, PEG/PPG ratio 60/40
  • Oil 4 non-reactive polyether modified silicone oil, HLB 18.6, PEG/PPG ratio 30/70
  • Oil 5 non-reactive polyether modified silicone oil, HLB 15.1, PEG/PPG ratio 80/20
  • Oil 6 non-reactive polyether modified silicone oil, HLB 15.4, PEG/PPG ratio 30/70
  • Reference oil 1 Wacker AK 1000, ex Wacker Chemie (Germany), non-reactive silicone oil, HLB (not applicable), PEG/PPG ratio (not applicable)
  • Reference oil 2 Pluronic L-35, ex Sigma-Aldrich (), Poly(ethylene glycol)-block- poly(propylene glycol)-block-poly(ethylene glycol), non-reactive polyether oil, HLB (not applicable), PEG/PPG ratio 50/50
  • Reference oil 3 Pluronic L-64, ex BASF (Germany), Poly(ethylene glycol)-block- poly(propylene glycol)-block-poly(ethylene glycol), non-reactive polyether oil, HLB (not applicable), PEG/PPG ratio 40/60
  • Reference oil 4 BlueSil FLD 550, ex Bluestar Silicones (Spain), non-reactive silicone oil, HLB (not applicable), PEG/PPG ratio (not applicable)
  • Reference oil 5 BlueSil 510V100, ex Bluestar Silicones (Spain), non-reactive silicone oil, HLB (not applicable), PEG/PPG ratio (not applicable)
  • Reference oil 6 OFX-5211 (chemically equivalent to DC Q2-5211), ex Xiameter (USA), non- reactive polyether modified silicone oil, HLB 12.9, PEG/PPG ratio 100/0
  • Reference oil 7 KF-945, ex Shin-Etsu (Japan), non-reactive polyether modified silicone oil, HLB 3.9, PEG/PPG ratio 100/0
  • the set-up consists of a rotary rig, which has two concentric cylinders with the inner cylinder (rotor, diameter of 0.3 m and height 0.17 m) capable of rotation.
  • the cylinder pair is immersed in a tank containing about 400-500 litres of Artificial Seawater (cf. Table 1).
  • the tank is fitted with baffles to break the liquid flow, which enhances turbulence and enables faster mixing of the species released from the paints and enhance heat transfer from a thermostating system.
  • baffles to break the liquid flow, which enhances turbulence and enables faster mixing of the species released from the paints and enhance heat transfer from a thermostating system.
  • the purpose of using two cylinders is to create a close approximation to couette flow (flow between two parallel walls, where one wall moves at a constant velocity).
  • the rotor is operated at 20 knots at 25 °C (unless otherwise specified), and the pH is adjusted frequently to 8.2 using 1 M sodium hydroxide or 1 M hydrochloric acid.
  • Samples are prepared using overhead transparencies (3M PP2410) that are primed using two-component paint (Hempadur 4518 ex Hempel's Marine Paints A/S) applied using a Doctor Blade applicator with a gap size of 200 pm. Coating samples are applied adjacent to each other using a Doctor Blade applicator with a gap of 250 pm. After drying for 1 day, the coated transparency is cut in strips of 2 cm resulting in eight samples of 1.5 x 2 cm 2 on a long (21 cm) strip. The strips are mounted on the rotor, and left to dry for a week.
  • 3M PP2410 that are primed using two-component paint (Hempadur 4518 ex Hempel's Marine Paints A/S) applied using a Doctor Blade applicator with a gap size of 200 pm. Coating samples are applied adjacent to each other using a Doctor Blade applicator with a gap of 250 pm. After drying for 1 day, the coated transparency is cut in strips of 2 cm resulting in eight samples of 1.5 x 2 cm 2 on
  • test After one week, the test is initiated, and during the experiment, samples are removed after 35, 65 and 140 days in order to inspect the polishing and leaching depths.
  • the samples are dried for three days at ambient conditions, after which they are cut in half and cast in paraffin.
  • the internal front of the sample is planed off before total film thickness and leached layer thickness is established using light microscopy (coating cross-section inspection).
  • a stainless steel test panel (13.5 x 7 cm) with a curvature corresponding to that of a cylindrical drum with a diameter of 1 m is first coated with 40-50 pm (DFT) of an epoxy primer (Hempadur 15553 ex Hempel A/S). After 24 hours, the panel is coated with 80 pm (DFT) of a commercial epoxy tie coat (HEMPADUR 47182 ex Hempel A/S) applied by air spraying.
  • DFT an epoxy primer
  • HEMPADUR 47182 ex Hempel A/S commercial epoxy tie coat
  • test paint After minimum 24 hours drying in the laboratory at room temperature the test paint is applied by air spraying in a DFT of approximately 150-200 pm. The panel is dried for at least 1 week in the laboratory at room temperature before testing. The initial thickness of the paint system is measured using a coating thickness tester (Isoscope, Fischer).
  • test panel is fixed onto the convex surface of a cylindrical drum of 1 m in diameter and is rotated in sea water with a salinity in the range of 37-38 parts per thousand at an average temperature of 17-18°C at a test site in Vilanova i la Geltrii in Northeastern Spain, which is situated at latitude 41.13 North and longitude 1.43 East.
  • An acrylic test panel (15 x 20 cm 2 ), sandblasted on one side to facilitate adhesion of the coating, is first coated with 80 pm (DFT) of a commercial vinyl tar primer (Hempanyl 16280 ex Hempel's Marine Paints A/S) applied by air spraying. After a minimum drying time of 24 hours in the laboratory at room temperature the test paint is applied with a Doctor Blade type applicator, with four gap sizes with a film width of 80 mm. One coat was applied in a DFT of 90-100 pm. After at least 72 hours drying the test panels are fixed on a rack and immersed in sea water.
  • DFT commercial vinyl tar primer
  • HLB hydrophilic-lipophilic balance
  • HLB value 20 * M h /M wherein M h is the weight of the hydrophilic (polyoxyalkylene) group(s) in the molecule, and wherein M is the weight of the whole molecule.
  • the coating compositions are prepared following the standard procedure. An initial dispersion of the binder(s) in organic solvent, followed by addition of part or all the additives such as thixotropic agents, etc., and eventually the addition of part or all the pigments such as zinc oxide, fibres, etc. are mixed on a Diaf dissolver equipped with an impeller disc. Further, the rest of the pigments such as cuprous oxide, zinc-ethylenebis(dithiocarbamate) (Zineb) is added, and a temperature activation of any component that may require it (e.g. thixotropic agent) is initiated. The coating compositions are finally let down with the remaining additives and binders, and its rheology adjusted with final addition of remaining organic solvent. Typically, the solid components of the coating composition are mixed and ground.
  • the polyoxyalkylene-modified siloxanes oils may alternatively be added in initial or later additive addition step.
  • the coating composition may be prepared as a one component paint or by mixing two or more components e.g. two pre-mixtures, one pre-mixture comprising the one or more resins and one pre-mixture comprising the one or more curing agents.
  • % dry weight means the percentage of the respective component based on the dry weight of the coat or of the coating composition, as the case may be. For most practical purposes (hence, unless otherwise stated), the “% dry weight” when referring the cured coat is identical to the “% dry weight” of the coating composition.
  • Example 1 Example 2
  • Example 3 (ref) (3% Cu 2 0 + oil) (3% Cu 2 0 + oil) (3% Cu 2 0 (blank))
  • Zinc oxide 4 2 4 1.5 5 2
  • Titanium oxide 5 2.5 4.5 2.5 5 3
  • Example 4 Example 5
  • Example 6 (ref) (5.5% Cu 2 0 + oil) (5.5% Cu 2 0 + oil) (5.5% Cu 2 0 (blank))
  • Titanium oxide 4.5 3 4.5 3 5 3
  • Example 7 Example 8
  • Example 9 (ref) (9% Cu 2 0 + oil) (9% Cu 2 0 + oil) (9% Cu 2 0 (blank))
  • Zinc oxide 4 2 4 1.5 4 2
  • Examples 1-9 show the effect of the addition of a polyoxyalkylene-modified silicone oil at different levels of biocide.
  • Examples 1-3, examples 4-6 and examples 7-9 each show that the addition of a polyoxyalkylene-modified silicone oil provides a better performance to the coating composition than the coating compositions without a polyoxyalkylene-modified silicone oil.
  • Examples 10-16 show the effect of the addition of a small amount (0.5-2.5 wt-%) of a polyoxyalkylene-modified silicone oil to a binder of rosin and acrylate. Even the small addition of the polyoxyalkylene-modified silicone oil provides a better performance than compositions without the polyoxyalkylene-modified silicone oil.
  • Example 14 is 2 wt-% short of biocides, but show the same performance as reference example 13.
  • Examples 17-18 show the effect of the addition of a small amount (2.5 wt-%) of a polyoxyalkylene-modified silicone oil to a binder of rosin and silylated acrylate. Even the small addition of the polyoxyalkylene-modified silicone oil provides a better performance than compositions without the polyoxyalkylene-modified silicone oil.
  • Examples 19-20 show the effect of the addition of a small amount (1-2.5 wt-%) of a polyoxyalkylene-modified silicone oil to a binder of rosin and silylated acrylate. Even the small addition of the polyoxyalkylene-modified silicone oil provides a better performance than compositions without the polyoxyalkylene-modified silicone oil.
  • Examples 22-30 show the effect of the addition of 5 wt-% of a polyoxyalkylene-modified silicone oil to various binder systems: Rosin-based, nanoacrylate based and silyl acrylate based.
  • the addition of the polyoxyalkylene-modified silicone oil provides a better
  • Examples 31-37 show the effect of the polyoxyalkylene-modified silicone oil at different levels of the oil. Both in Spain and Singapore, there is a positive effect of the oil at different levels.
  • Examples 40-52 show that polyoxyalkylene-modified silicone oils (oil 1-6) perform better than non-modified silicone oils (Reference oils 1, 4 and 5) and polyoxyalkylene oils without silicone (Reference oils 2 and 3).
  • Reference oils 6 and 7 are polyoxyalkylene-modified silicone oils with 100% PEG-chain.
  • Model paints proving the effect of polyoxyalkylene-modified silicone oils in two-layer systems The model paint used in example 38 is used as base paint in examples 53-55, with or without the addition of a polyoxyalkylene-modified silicone oil.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne une composition de revêtement anticontamination à base de solvant comprenant un système de liant non à base de silicone érodable, un ou plusieurs biocides contenant un métal (tels que l'oxyde cuivreux, la pyrithione de cuivre (cuivre-omadine), la pyrithione de zinc (cuivre-omadine) et l'éthylènebis(dithiocarbamate) de zinc (Zineb)), et une ou plusieurs huiles silicone modifiées par polyoxyalkylène non réactives, en particulier des huiles de silicone modifiées par PEG/PPG, telles que celles ayant un bilan hydrophile-lipophile (HLB), par exemple de 9-18. L'invention concerne en outre une structure marine comprenant, sur au moins une partie de sa surface externe, une couche ou un système de revêtement extérieur anticontamination autopolissant.
PCT/DK2017/050204 2016-06-22 2017-06-22 Composition de revêtement anticontamination à libération contrôlée par interaction biocide WO2017220097A1 (fr)

Priority Applications (4)

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CN201780045298.XA CN109803533A (zh) 2016-06-22 2017-06-22 通过生物杀灭剂相互作用控释的防污涂料组合物
KR1020187038024A KR20190021273A (ko) 2016-06-22 2017-06-22 살생물제 상호반응을 통한 조절 방출형 방오 코팅 조성물
EP17814790.6A EP3474668A4 (fr) 2016-06-22 2017-06-22 Composition de revêtement anticontamination à libération contrôlée par interaction biocide
SG11201811257SA SG11201811257SA (en) 2016-06-22 2017-06-22 Controlled release antifouling coating composition via biocide interaction

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WO2023036923A1 (fr) 2021-09-10 2023-03-16 Hempel A/S Composition de revêtement d'acrylate pour former un revêtement antisalissure

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WO2021113564A1 (fr) * 2019-12-06 2021-06-10 Lonza Solutions Ag Compositions de protection antisalissure
KR102360904B1 (ko) * 2021-06-18 2022-02-08 방봉문 해양생물 부착 방지용 수용성 방오페인트

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023036923A1 (fr) 2021-09-10 2023-03-16 Hempel A/S Composition de revêtement d'acrylate pour former un revêtement antisalissure

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KR20190021273A (ko) 2019-03-05

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