WO2023232825A1

WO2023232825A1 - Waterborne antifouling composition

Info

Publication number: WO2023232825A1
Application number: PCT/EP2023/064460
Authority: WO
Inventors: Aslan M. ESMURZIEV; Kjartan Tobias Boman
Original assignee: Jotun A/S
Priority date: 2022-05-31
Filing date: 2023-05-30
Publication date: 2023-12-07

Abstract

The invention provides a waterborne antifouling coating composition comprising: (a) a polymeric binder comprising a structural unit derived from an ethylenically unsaturated monomer; and (b) at least 1.0 wt%, based on dry weight of the total coating composition, of a rosin ester, wherein said rosin ester has a glass transition temperature (Tg) of less than 0 °C; wherein the coating composition comprises at least 5 wt% water relative to the total weight of the composition as a whole.

Description

Waterborne Antifouling Composition

Field of the Invention

The present invention relates to antifouling coating compositions, more specifically to waterborne antifouling coating compositions comprising a polymeric binder and a rosin ester. The invention further relates to a process of protecting objects from fouling, and to objects coated with the antifouling composition of the invention.

Background of invention

Surfaces that are submerged in seawater are subjected to fouling by marine organisms such as green and brown algae, barnacles, mussels, tube worms and the like. On marine constructions such as vessels, oil platforms, buoys, etc. such fouling is undesired and has economic consequences. The fouling may lead to biological degradation of the surface, increased load and accelerated corrosion. On vessels the fouling will increase the frictional resistance which will cause reduced speed and/or increased fuel consumption.

To prevent settlement and growth of marine organisms antifouling paints are used. These paints generally comprise a film-forming binder, together with different components such as pigments, fillers, additives and solvents together with biologically active substances (biocides). Biocides can be broadly divided into those active against soft fouling, such as green and brown algae, grass, slime and those active against hard fouling, such as barnacles, mussels, tube worms etc.

Commercial vessels (e.g. container ships, bulk carriers, tankers, passenger ships) often operate in different waters, in different trade, with different activity, including idle periods. The antifouling coating should provide good fouling protection under all those conditions. Typical service intervals for commercial vessels are from 30 to 90 months. Maintenance of submerged objects is costly, so the applied antifouling coatings should be effective for the specified service interval. It requires a controlled degradation of the coating film giving constant release of biocides to protect the object through the full service interval and under various sailing conditions.

That can best be obtained by using a self-polishing antifouling coating having a controlled polishing rate. Too fast polishing will lead to a rapid consumption of the coating film, resulting in an unprotected surface. Too slow polishing will lead to insufficient release of the biocide, which is vital for effective protection from fouling. A controlled degradation over the life time of the coating will give a constant release of biocides and thereby excellent fouling protection.

In addition to these demands, the coating industry is constantly faced with stricter VOC regulations, which limits the amount of organic solvents that can be used in antifouling paints. The most common application methods for antifouling coatings are airless spray, brush or roller. It is important that the paint can be applied by standard techniques which in turn means coating compositions and paints having a certain viscosity level, whilst minimising their VOC content and still achieving satisfactory application properties. The VOC limits may be exceeded if additional solvent must be added to reduce the viscosity at the point of application.

It is a challenge to find coating compositions which comply with the ever tightening VOC regulations and which also have controlled polishing properties, good mechanical properties and exhibit good fouling protection.

One solution for achieving VOC compliant and more sustainable antifouling paints is to use waterborne technology. The waterborne market will likely increase to offer more sustainable coatings to meet VOC/HAP regulations. Water-based paints have gained popularity in the interior market due to low odour, easier cleanup, faster drying and that it is healthier for staff. The advances in newer technology lead to performance and durability of waterborne coatings being closer to solvent- borne coatings for most applications.

Waterborne coatings are described in, for example, US 2021/0301153, US 4052354 and WO 2012/084758. These include coatings based on (meth)acrylic binders.

JP 2007204687 aqueous release agent which is obtained by emulsifying a blend of a long-chain alkyl-based release agent and a rosin-based resin. The aqueous release agent is intended for use in adhesive tape as a back-surface-treated layer of a base material such as paper.

WO 2019/096928 describes an antifouling coating composition for use on underwater surfaces to prevent fouling by marine organisms. Said composition is non aqueous and comprises (i) an acrylic binder polymer and (ii) rosin.

There is, however, a constant demand in the industry for the development of new and improved coatings.

The present inventors have unexpectedly found that if, in addition to a polymeric binder comprising a structural unit derived from an ethylenically unsaturated monomer, a specific class of rosin ester is included in the coating composition, more controlled polishing and improved mechanical properties are observed. A more controlled polishing will give a more controlled release of the biocides and thereby improved long-term antifouling performance.

The waterborne antifouling coating compositions developed show controlled polishing properties. In addition, they exhibit good mechanical properties (e.g., resistance to cracking, film-forming behaviour).

Summary of invention

In one aspect, the invention relates to a waterborne antifouling coating composition comprising:

(a) a polymeric binder comprising a structural unit derived from an ethylenically unsaturated monomer; and

(b) at least 1.0 wt%, based on dry weight of the total coating composition, of a rosin ester, wherein said rosin ester has a glass transition temperature (Tg) of less than 0 °C; wherein the coating composition comprises at least 5 wt% water relative to the total weight of the composition as a whole.

In another aspect, the invention provides a process for applying a waterborne antifouling coating composition to a substrate comprising applying, e.g. by spraying, a waterborne antifouling coating composition as hereinbefore defined to a substrate and allowing the coating composition to dry. In a further aspect, the invention provides a process for protecting an object from fouling, said process comprising coating at least a part of said object which is subject to fouling with an antifouling coating composition as hereinbefore defined.

In another aspect, the invention provides a substrate coated with a waterborne antifouling coating composition as hereinbefore defined, wherein said coating composition has been allowed to dry.

In yet another aspect, the invention provides the use of a rosin ester with a glass transition temperature (Tg) of less than 0 °C to increase the polishing rate of a waterborne antifouling coating composition, preferably an antifouling coating compositing comprising polymeric binder comprising a structural unit derived from an ethylenically unsaturated monomer, more preferably an antifouling coating composition comprising a polymeric binder comprising (meth)acrylic acid and/or (meth)acrylic acid ester monomers.

Definitions

The terms “marine antifouling coating composition”, “antifouling coating composition” or simply “coating composition” refer to a composition that, when applied to a surface, prevents or minimises growth of marine organisms on the surface.

As used herein, the term “waterborne composition” refers to a composition which comprises water as the main solvent. Typically, water forms at least 70 wt% of the solvent used, preferably more than 80 wt%, particularly preferred more than 90 wt%.

As used herein the term “paint” refers to a composition comprising the antifouling coating composition as herein described and optionally solvent which is ready for use, e.g. for spraying. Thus, the antifouling coating composition may itself be a paint or the antifouling coating composition may be a concentrate to which solvent is added to produce a paint.

The term “(meth)acrylate” means a methacrylate or acrylate. The term “hydrocarbyl group” refers to any group containing C atoms and H atoms only and therefore covers alkyl, alkenyl, aryl, cycloalkyl, arylalkyl groups and so on.

As used herein the term “resin acid” and “rosin acid” refers to a mixture of carboxylic acids present in resins.

The term “binder system” defines the part of the composition which includes the polymeric binder and any other polymers, resins or components which together form a matrix giving substance and strength to the composition. The rosin esters of the present invention are regarded as part of the binder system.

The term “Tg” means glass transition temperature, obtained by Differential Scanning Calorimetry (DSC) measurements.

Where a wt% of a given monomer is given, the wt% is relative to the total (weight) of each monomer present in the copolymer.

The term “wt% based on the total weight of the composition” refers to the wt% of a component present in the final, ready to use, composition, unless otherwise specified.

The term “wt% based on the total dry weight of the composition” refers to the wt% of a component present in the composition relative to the total weight of the components in the composition not including the solvents.

As used herein the term “dispersion” refers to a fine dispersion of particles or droplets dispersed in a continuous liquid phase. Typically, the continuous liquid phase is water. Thus, the dispersions employed in the present invention may also be termed “aqueous dispersions”, meaning that they are dispersions wherein the continuous phase (i.e. the solvent) is water.

Droplets dispersed in water can be referred to as an emulsion. As used herein, the term emulsion refers to a fine dispersion of droplets of one liquid in another in which it is not soluble or miscible. In the present invention the term “dispersion” refers to both particles and droplets (emulsions) dispersed in water.

As used herein the term “volatile organic compound (VOC)” refers to an organic compound having a boiling point of 250 °C or less at 101.3 kPa.

As used herein “antifouling agent” or “biocide” refers to a biologically active compound or mixture of biologically active compounds that prevents the settlement of marine organisms on a surface, and/or prevents the growth or marine organisms on a surface and/or encourages the dislodgement of marine organisms on a surface. These terms are used interchangeably. A biocide is defined by the European biocidal products regulation (BPR) as 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.

Detailed description of invention

The invention relates to a new waterborne antifouling coating composition comprising (a) a polymeric binder comprising a structural unit derived from an ethylenically unsaturated monomer and (b) a rosin ester.

Polymeric binder

The coating composition of the present invention comprises a polymeric binder comprising a structural unit derived from an ethylenically unsaturated monomer. The polymeric binder as defined above will herein be referred to as the “polymeric binder”.

Examples of suitable ethylenically unsaturated monomers are (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylic acid amide, vinyl chloride, vinyl ester, vinyl acetate, vinyl propionatemaleic acid, itaconic acid, vinyl alcohol, styrene, α- m ethyl styrene, alkyl vinyl ether, vinyl pyrrolidone, N-vinyl caprolactame, N- methyl-N-vinylacetamide and (meth)acrylonitrile.

Preferably the ethylenically unsaturated monomer is selected from (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylic acid amide and vinyl ester such as vinyl acetate and vinyl neodecanoate.

In a particularly preferred embodiment, the ethylenically unsaturated monomer is selected from (meth)acrylic acid and (meth)acrylic acid esters.

Examples of the (meth)acrylic acid ester monomers include: alkylate or cycloalkyl ester of (meth)acrylic acid having 1 to 18 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and cyclohexyl (meth)acrylate; alkoxy alkyl ester of (meth)acrylic acid having 2 to 18 carbon atoms such as methoxybutyl (meth)acrylate, methoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, and ethoxybutyl (meth)acrylate; dialkylaminoalkyl ester of (meth)acrylic acid such as dimethylaminoethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2-(diisopropylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, 4-dimethylaminobutyl (meth)acrylate and dimethylaminopropyl (meth)acrylate; hydroxy alkyl ester of (meth)acrylic acid such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3 -hydroxypropyl (meth)acrylate, 2- hydroxy-1 -methylethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and hydroxyisobutyl (meth)acrylate; glycidyl (meth)acrylate, (2,2-dimethyl-l,3-dioxolan-4-yl)methyl (meth)acrylate;

(meth)acrylic acid ester monomers comprising cyclic amines such as (meth)acryloyl-2-pyrrolidone;

(meth)acrylic acid ester monomers comprising polysiloxane groups such as monomethacryloxypropyl terminated polydimethylsiloxane, such as α- methacryloyloxypropyl-o-butyl polydimethylsiloxane, α-methacryloyloxypropyl-o- trimethyl silyl polydimethylsiloxane, α-methacryloyloxyethyl-o-trimethylsilyl polydimethylsiloxane, α-acryloyloxypropyl-o-butyl polydimethylsiloxane, α- acryloyloxypropyl-o-trimethylsilyl polydimethylsiloxane, α-acryloyloxyethyl-o- trimethyl silyl polydimethylsiloxane. Representative examples of commercially available monomers comprising polysiloxane groups include X-22-174ASX, X22- 174BX, KF-2012, X-22-2426 and X-22-2404 from Shin-Etsu, Silaplane FM-0711, Silaplane FM-0721, Silaplane FM-0725 from JNC Corporation, PS560 from United Chemical Technologies and MCR-M07, MCR-M11, MCR-M17, MCR-M22 and MCR-V41 from Gelest; (meth)acrylic acid momomers comprising polyether groups such as polyethylene glycol)methyl ether (meth)acrylate, poly(propylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) ethyl ether (meth)acrylate, polypropylene glycol) ethyl ether (meth)acrylate, poly(ethylene glycol) (meth)acrylate, polypropylene glycol) (meth)acrylate. Representative examples of commercially available monomers include Visiomer MPEG 750 MA W, Visiomer MPEG 1005 MA W, Visiomer MPEG 2005 MA W, Visiomer MPEG 5005 MA W from Evonik, Bisomer PPA6, Bisomer PEA6, Bisomer PEM6, Bisomer PPM5, Bisomer PEM63P, Bisomer MPEG350MA, Bisomer MPEG550MA, Bisomer SIOW, BisomerS20W from Geo Speciality Chemicals, SR550 MPEG350MA, SR552 MPEG500MA from Sartomer and RPEG 750 from Ineos Oxide;

(meth)acrylic acid ester monomers that are hydrolysable such as silyl (meth)acrylate monomers and metal ester (meth)acrylic monomers. Examples of such monomers are trialkyl silyl monomers such as triisopropyl silyl (meth)acrylate, zinc (meth)acrylate and zinc acetate (meth)acrylate, copper (meth)acrylate and copper acetate (meth)acrylate.

In one particularly preferred embodiment, the polymeric binder comprises a residue of at least one, and preferably at least two, monomers of formula (I)

wherein R¹ is H or CH3;

R² is H or optionally a linear, branched or cyclic substituted C1-18 alkyl, wherein said substituents are selected from OH, OR³ and N(R⁴)2; and

R³ is selected from C_1-8 alkyl and C_3-8 cycloalkyl.

Each R⁴ is independently selected from H, C1-8 alkyl and C_3-8 cycloalkyl

It is to be understood that the polymeric binder of the present invention may be a co-polymer comprising several of the monomers described above. The polymeric binder of the present invention preferably comprises at least 50 wt% of the structural unit derived from an ethylenically unsaturated monomer, preferably at least 70 wt%, more preferred at least 80 wt% relative to the total weight of the polymeric binder. In one preferred embodiment the polymeric binder of the present invention comprises at least 95 wt% of the structural units derived from ethylenically unsaturated monomers, preferably 100 wt%.

The polymeric binder of the present invention preferably comprises a (meth)acrylic acid and/or a (meth)acrylic acid ester monomer. Preferably the polymeric binder of the present invention comprises at least 15 wt%, relative to the total weight of the polymeric binder of (meth)acrylic acid and/or (meth)acrylic acid ester monomers, preferably at least 20 wt%, more preferably at least 40 wt%, still more preferably at least 55 wt%. In general, the (meth)acrylic acid and/or (meth)acrylic acid ester monomer is present in an amount of 99.9 wt% or less, more preferably 99.5 wt% or less, relative to the total weight of the polymeric binder.

The amount of each structural unit can be determined by, for example, nuclear magnetic resonance spectroscopy (NMR) or pyrolysis gas chromatography mass spectrometry (Pyro-GC/MS). Information about the wt.% (meth)acrylic acid and/or (meth)acrylic acid ester parts in a commercially available polymeric binder is also often easily obtainable from the supplier.

The polymeric binder of the invention may be produced by methods known in the art. In general, this involves appropriately selecting one or more ethylenically unsaturated monomers, in amounts in consideration of, for example, the structural unit and weight average molecular weight, and then using a known method, for example, emulsion polymerization to polymerise said monomers.

The amount of polymeric binder in the coating composition is preferably 1.0 to 40 wt%, more preferred 2.0 to 35 wt%, further preferred 2.5 to 25 wt% of the total dry weight of the coating composition.

The glass transition temperature (Tg) of the polymeric binder is not particularly limited and can be, for example, less than 50°C.

In a particularly preferred embodiment, the polymeric binder of the present invention is in the form of a dispersion. The polymeric binder is typically present in the dispersion in the form of particles or droplets with an average size of 4 to 1000 nm, preferably 25 to 400 nm, more preferably 50 to 350 nm, such as 100 to 300 nm. The “average size” referred to in this context is the Z-average size, which will be understood to be the intensity weighted average hydrodynamic diameter as described in ISO22412:2017. It will be understood that in this context the polymeric binder particles form the dispersed phase of the dispersion.

The polymeric binder droplets or particles preferably form 10 to 80 wt% of the dispersion, relative to the total weight of the dispersion as a whole. Typical wt% ranges may be 35 to 60 wt%, such as 40 to 55 wt%, relative to the total weight of the dispersion as a whole.

In addition to the polymeric binder droplets or particles, the dispersion comprises an aqueous solvent (i.e. the continuous phase). It will be understood that an aqueous solvent is one comprising (preferably consisting of) water. The dispersion referred to herein may thus be termed an aqueous dispersion. The aqueous dispersion of the polymeric binder is a dispersion in which the polymeric binder is dispersed in a dispersion medium including water (hereinafter, also referred to as “aqueous medium”).

The aqueous medium is not particularly limited as long as it includes water; however, the content of water in the aqueous medium is preferably 50 to 100 wt%, and more preferably 60 to 90 wt% relative to the total weight of the aqueous medium. In one preferred embodiment the content of water in the aqueous medium is 100 wt%, e.g. the aqueous medium consists of water. The aqueous medium may include a medium other than water, and examples of such a medium include acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-methoxy ethanol, 2-ethoxy ethanol, 2-butoxyethanol, 1- methoxy-2-propanol, l-ethoxy-2-propanol, diacetone alcohol, dioxane, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol monomethyl ether (Dowanol DPM), ethylene glycol monopropyl ether, and ethylene glycol monohexyl ether. One or more of these can be used.

The solvent (preferably water) forms 10 to 70 % of the volume of the dispersion, relative to the total volume of the dispersion as a whole. Typical volume% ranges may be 20 to 65 %, such as 30 to 60 %, relative to the total volume of the dispersion as a whole.

The dispersion may be prepared by any suitable known method in the art.

The dispersion may comprise a surfactant. The surfactant may be non-ionic, anionic, cationic or amphoteric.

Examples of non-ionic surfactants are alkyl phenoxy ethers, polyalkylene glycols, polyoxyalkylene sorbitan monooleates, polyvinyl alcohols, polyvinyl esters, polyether siloxanes, fatty alcohol ethoxylates and sorbitan stearates. Preferred non- ionic emulsifying agents are polyalkylene glycols such as polyoxyethylenepolyoxypropylene co-polymers and fatty alcohol ethoxylates.

Examples of anionic surfactants are alkyl-, aryl-, alkaryl- sulphates, sulphonates, phosphates, sulpho-succinates, sulphosuccinamates, sulphoacetates and amino acid derivatives.

Particularly preferred anionic surfactants are alkylsulfate salts, polyoxyethylene alkyl ether sulfate salts, unsaturated aliphatic sulfonate salts, and hydroxylated aliphatic sulfonate salts. The alkyl group referenced here can be exemplified by medium and higher alkyl groups such as decyl, undecyl, dodecyl, tridecyl, tetradecyl, cetyl, stearyl, and so forth. The unsaturated aliphatic group can be exemplified by oleyl, nonenyl, and octynyl. The counterion can be exemplified by sodium ion, potassium ion, lithium ion, and ammonium ion, with the sodium ion being typically used among these.

The cationic surfactant can be exemplified by quaternary ammonium salttype surfactants such as alkyltrimethylammonium salts, e.g., octadecyltrimethylammonium chloride and hexadecyltrimethylammonium chloride, and dialkyldimethylammonium salts, e.g., dioctadecyldimethylammonium chloride, dihexadecyldimethylammonium chloride and didecyldimethylammonium chloride.

The amphoteric surfactant can be exemplified by alkylbetaines and alkylimidazolines.

The dispersions may also comprise crosslinkers, curing catalysts, antifoaming agents, rheology modifiers and pH adjusting agents. Suitable antifoaming agents, rheology modifiers and pH adjusting agents are described further under additives. From the viewpoint of the stability of the dispersion, the volume solid is preferably 30 % or more, more preferably 40 wt% or more, relative to the total volume of the dispersion. Typically, the volume solid is 80 % or less, preferably 70 % or less, relative to the total volume solid of the dispersion as a whole.

Example of suitable commercially available dispersions include PRIMAL™ AC-337, PRIMAL™ SF-021 and MAINCOTE™ 1071 from Dow Chemical company.

An aqueous dispersion of the polymeric binder can be prepared by dispersing the polymeric binder with a surfactant to form a dispersion. In addition, a dispersion can be directly prepared by emulsion polymerisation of the monomers forming the polymeric binder. The surfactant is not particularly limited, and can be appropriately selected from a cationic surfactant, an anionic surfactant, and a nonionic surfactant as described above.

The dispersion of the polymeric binder preferably forms 2 to 45 wt% of the antifouling coating composition, relative to the total weight of the composition as a whole. Typical wt% ranges may be 3 to 40 wt%, such as 5 to 35 wt%, relative to the total weight of the composition as a whole.

Rosin Ester

The antifouling coating composition of the invention further comprises a rosin ester. It is to be understood that the rosin ester of the invention is also considered to be part of the binder system.

Rosin esters are made from rosin acids by converting the carboxylic acid group of the rosin acids to an ester group by for example reacting the carboxylic acid with an alcohol.

Rosin acids are also referred to as resin acids. It will be appreciated that the rosin acids are derived from natural sources and as such they typically exist as a mixture of acids. Examples of rosin acids are abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, pimaric acid, levopimaric acid, isopimaric and sandaracopimaric acid. Representative examples of sources of rosin acids are gum rosin, wood rosin and tall oil rosin. Rosin acid derivatives such as hydrogenated rosin acid, partially hydrogenated rosin acid, dimerized rosin acids and modified rosin acids (such as maleic and fumaric modified rosin acids) can also be used to make rosin esters.

The molecular weight and functionality of the alcohol will determine the Tg of the resulting rosin ester after the reaction with the rosin acid.

The rosin ester of the present invention has a glass transition temperature (Tg) of less than 0°C. The Tg is obtained by Differential Scanning Calorimetry (DSC) measurements. Typically, the measurement is performed by running a heat- cool-heat procedure, within a temperature range from -80°C to 150°C, with a heating rate of 10°C/min and cooling rate of 10°C/min and using an empty pan as reference. The inflection point of the glass transition range, as defined in ASTM E1356-08, of the second heating is reported as the Tg of the rosin ester.

In practice, a Tg of less than 0 °C, generally means that the rosin ester is in a liquid state at room temperature (i.e. temperatures in the range of 18 to 25 °C). In preferable embodiments, the rosin ester has a Tg of less than -5 °C, such as less than -10 °C.

Without wishing to be bound by theory, it is considered that rosin esters which have Tg less than 0 °C (and thus which are typically in a liquid state at room temperature) will give a plasticizing effect leading to less cracking and increase the polishing rate of the coating, while rosin esters with Tg higher than this (and which are typically in a solid state at room temperature) will not have a positive effect on the polishing rate and can reduce the polishing significantly compared to coating compositions where the binder system comprises only the polymeric binder.

Reaction of rosin acids with mono-functional and di-functional alcohols will typically give rosin esters with Tg less than 0 °C. Examples of suitable alcohols are methanol, ethanol and triethylene glycol.

Reaction of rosin acids with tri and tetrafunctional alcohols such as glycerol and pentaerytritol will typically give rosin esters with Tg higher than 0 °C.

Preferably the rosin esters of the present invention are made from rosin acids or rosin acid derivatives and a mono or di-fimctional alcohol. Any rosin ester may be employed which satisfies the above mentioned Tg requirement. Preferred rosin esters include the methyl ester or triethyleneglycol ester of rosin acid.

Examples of suitable rosin esters commercially available are Granolite TEG (triethylene glycol ester of rosin, supplied by DRT, Viscosity 600DPa.s @20°C, acid number 12-15 mg KOH/g, Gardner colour of 6 (50 resin/50toluene)), Granolite M (methyl ester of rosin, supplied by DRT, viscosity 3500 mPa.s @30°C, acid number maximum 9 mg KOH/g, Gardner colour of maximum 6 (50 resin/50 toluene)), Abalyn® (methyl ester of wood rosin, supplied by DRT, liquid, Gardner colour of 6, acid number maximum 8 mgKOH/g), Liquid rosin ester LRE-1 (supplied by Resin Chemicals, polyol esterified gum rosin, viscosity 20-40 mPa.s @30°C, acid number 20 mg KOH/g, Gardner colour of 8), Abalyn™ D-E (methyl ester of rosin, supplied by Eastman, viscous liquid, acid number 5 mgKOH/g, Gardner colour of 4), Dertoline DEG 2 (diethylene glycol-esterified rosin, supplied by DRT, liquid, acid number 13 mgKOH/g, Gardner color 2.5, Tg -7, softening point 37), Hercolyn ® D (methyl ester of partially hydrogenated rosin, supplied by DRT, liquid, Tg -30, Gardener colour 2, acid number 6 mgKOH/g), Neutac liquid rosin esters (Neutac supplied by Newport resins, several liquid rosin esters available, e.g., Neutac 14277, Neutac MER-L and MEHR-L).

A single rosin ester as defined above may be employed, or a mixture of two or more such rosin esters. The rosin ester(s) can be used in combination with one or more rosin acid(s).

To ensure sufficient polishing and mechanical properties, the amount of rosin ester should be at least 1.0 wt%, relative to the total dry weight of the coating composition. Typical wt% ranges for the rosin ester(s) are 1.0 to 30 wt%, such as 1.2 to 25 wt%, more preferably 1.5 to 20 wt%, relative to the total dry weight of the coating composition. Where the coating composition comprises more than one rosin ester, these wt% ranges will be understood to corresponds to the total for all rosin esters present.

Preferably the ratio between the rosin ester and the polymeric binder is more than 5:95, such as 10:90 or more. In a particularly preferred embodiment, the rosin ester is in the form of a dispersion.

The rosin ester is typically present in the dispersion in the form of droplets or particles with an average size of 50 to 1500 nm, preferably 100 to 1200 nm, more preferably 150 to 1000 nm. The “average size” referred to in this context is the Z- average size, which will be understood to be the intensity weighted average hydrodynamic diameter as described in ISO22412:2017.

It will be understood that in this context the rosin ester droplets or particles form the dispersed phase of the dispersion.

The rosin ester droplets or particles preferably form 30 to 90 wt% of the dispersion, relative to the total weight of the dispersion as a whole. Typical wt% ranges may be 35 to 80 wt%, such as 40 to 70 wt%, relative to the total weight of the dispersion as a whole.

In addition to the rosin ester droplets or particles, the dispersion comprises aqueous solvent (i.e. the continuous phase). It will be understood that an aqueous solvent is one comprising (preferably consisting of) water. The dispersion referred to herein may thus be termed an aqueous dispersion. The aqueous dispersion of the rosin ester is a dispersion in which the rosin ester is dispersed in a dispersion medium including water (hereinafter, also referred to as “aqueous medium”).

The aqueous medium is as defined above for the dispersions of the polymeric binder.

The solvent (preferably water) forms 10 to 70 wt% of the dispersion, relative to the total weight of the dispersion as a whole. Typical wt% ranges may be 20 to 65 wt%, such as 30 to 60 wt%, relative to the total weight of the dispersion as a whole. The dispersion may be prepared by any suitable known method in the art.

The dispersion may comprise surfactants, such as those hereinbefore defined for the dispersions of the polymeric binder. The dispersion may also comprise antifoaming agents, preservatives, pH adjusting agents and rheology modifiers. Suitable antifoaming agents, rheology modifiers, preservatives and pH adjusting agents are described further under additives.

From the viewpoint of the stability of the dispersion, the solid is preferably 30 wt% or more, more preferably 40 wt% or more, even more preferably 50 wt% or more, relative to the total weight of the dispersion or emulsion. Typically, the solid content is 80 wt% or less, preferably 70 wt% or less, relative to the total weight of the dispersion as a whole.

The dispersion of the rosin ester preferably forms 0.5 to 30 wt% of the antifouling coating composition, relative to the total weight of the composition as a whole. Typical wt% ranges may be 1.0 to 25 wt%, such as 2.0 to 20 wt%, relative to the total weight of the composition as a whole.

Rosin acid and rosin acid derivatives

In addition to the polymeric binder and the rosin ester described above the coating composition of the present invention may optionally comprise a rosin acid and/or a rosin acid derivative. The rosin acid might be used to increase the polishing rate of the coating composition. It is to be understood that, when present, the rosin acid and/or rosin acid derivative is also considered to be a part of the binder system.

Rosin acids are also referred to as resin acids. It will be appreciated that the rosin acids are derived from natural sources and as such they typically exist as a mixture of acids. Examples of rosin acids are abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, pimaric acid, levopimaric acid, isopimaric and sandaracopimaric acid. Representative examples of sources of rosin acids are gum rosin, wood rosin and tall oil rosin. Gum rosin, also referred to as colophony and colophonium, is particularly preferred. Preferred rosin acids are those comprising more than 85 % rosin acids and still more preferably more than 90 % rosin acids.

Commercial grades of rosin acids are often classified according to its colour by designation of letters on a colour scale XC (lightest), XB, XA, X, WW, WG, N, M, K, I, H, G, F, E, D (darkest) as specified in ASTM D509. Preferred colour grades for the compositions of the invention are X, WW, WG, N, M, K, I, and still more preferably WW. Commercial grades of rosin acids typically have an acid value from 155 to 180 mg KOH/g as specified in ASTM D465. Preferred rosin for the compositions of the invention has an acid value from 155 to 180 mg KOH/g, more preferred 160 to 175 mg KOH/g, even more preferred 160 to 170 mg KOH/g. Commercial grades of rosin typically have a softening point (Ring & Ball) of 70 °C to 80 °C as specified in ASTM E28. Preferred rosin for the compositions of the invention has a softening point of 70 °C to 80 °C, more preferred 75 °C to 80 °C.

In one preferred embodiment the coating composition of the present invention comprises rosin acid. Typical amounts for the rosin acid, when present, are 0.1 to 15 wt%, such as 0.5 to 10 wt%, relative to the dry weight of the total composition.

If present, the ratio between rosin ester and rosin acid can be, for example, 3: 1, 2: 1, 1 : 1, 1 :2 or 1 :3

If present, the ratio between polymeric binder, rosin ester and rosin acid can be, for example, 2: 1 : 1, or 1 :2: 1, 1 : 1 :2.

The rosin acid is preferably dispersed in water as described for the rosin ester above.

When present, the rosin acid is typically present in the dispersion in the form of droplets or particles with an average size of 50 to 1500 nm, preferably 100 to 1200 nm, more preferably 150 to 1000 nm. The “average size” referred to in this context is the Z-average size, which will be understood to be the intensity weighted average hydrodynamic diameter as described in ISO22412:2017.

It will be understood that in this context the rosin acid droplets or particles form the dispersed phase of the dispersion.

The rosin acid droplets or particles preferably form 30 to 90 wt% of the dispersion, relative to the total weight of the dispersion as a whole. Typical wt% ranges may be 35 to 80 wt%, such as 40 to 70 wt%, relative to the total weight of the dispersion as a whole.

In addition to the rosin acid droplets or particles, the dispersion comprises aqueous solvent (i.e. the continuous phase). It will be understood that an aqueous solvent is one comprising (preferably consisting of) water. The dispersion referred to herein may thus be termed an aqueous dispersion. The aqueous dispersion of the rosin acid is a dispersion in which the rosin acid is dispersed in a dispersion medium including water (hereinafter, also referred to as “aqueous medium”).

The aqueous medium is as defined above for the dispersions of the polymeric binder. The solvent (preferably water) forms 10 to 70 wt% of the dispersion, relative to the total weight of the dispersion as a whole. Typical wt% ranges may be 20 to 65 wt%, such as 30 to 60 wt%, relative to the total weight of the dispersion as a whole. The dispersion may be prepared by any suitable known method in the art.

The dispersion of the rosin acid may also comprise surfactants, antifoaming agents, rheology modifiers and pH adjusting agents. Suitable antifoaming agents, rheology modifiers and pH adjusting agents are described further under additives. Suitable surfactants are as described for the polymeric binder above.

Rosin acid derivatives such as hydrogenated rosin acid, partially hydrogenated rosin acid, dimerized rosin acids and modified rosin acids (such as maleic and fumaric modified rosin acids) may also be present in the coating composition of the present invention. When present the rosin acid derivatives are preferably dispersed in water as described for the rosin acid above.

Typical amounts for the rosin acid derivatives, when present, are 0.1 to 15 wt%, such as 0.5 to 10 wt%, relative to the dry weight of the total composition.

Metal carboxylate salts of rosin acid and rosin acid derivatives may also be present in the antifouling coating composition of the present invention. Examples of metal carboxylate salts include alkali metal salts such as sodium and potassium carboxylate salt, alkaline earth metal carboxylate salt such as magnesium carboxylate salt and calcium carboxylate salt or transition metal carboxylate salt such as copper carboxylate salt and zinc carboxylate salt. Transition metal carboxylate salts are preferred such as rosin acid zinc salts (zinc rosinate) and rosin acid copper salts (copper rosinate). The metal carboxylate salts may be added directly to the antifouling coating composition or be generated in situ in the antifouling coating composition.

Other Binder components

In addition to the polymeric binder, rosin ester and optionally rosin acid described above, additional binder(s) can be used to adjust the properties of the antifouling coating composition. Examples of binders that can be used include: polyethylene glycol) copolymers; saturated aliphatic polyesters, such as poly(lactic acid), poly(glycolic acid), poly(2-hydroxybutyric acid), poly (3 -hydroxybutyric acid), poly(4-hydroxy valeric acid), polycaprolactone and aliphatic polyester copolymer containing two or more of the units selected from the above mentioned units; and polymeric plasticizers from any of the polymer groups specified above.

Additional examples of other binder components that may be present in the antifouling coating composition of the invention include:

Polyurethane-based binder systems;

Hydrocarbon resins, such as hydrocarbon resin formed only from the polymerisation of at least one monomer selected from a C₅ aliphatic monomer, a C₉ aromatic monomer, an indene coumarone monomer, or a terpene or mixtures thereof; and monocarboxylic acids other than the rosin acids described above.

Examples of suitable monocarboxylic acids are C₆-C₂₀ cyclic monocarboxylic acid, C₅-C₂₄ acyclic aliphatic monocarboxylic acid, C₇-C₂₀ aromatic monocarboxylic acid, a derivative of any of the monocarboxylic acids, and mixtures thereof.

Derivatives of monocarboxylic acid include metal salts of monocarboxylic acid, such as alkali metal carboxylate, alkaline earth metal carboxylate (e.g. calcium carboxylate, magnesium carboxylate) and transition metal carboxylate (e.g. zinc carboxylate, copper carboxylate). Preferably the metal carboxylate is a transition metal carboxylate, particularly preferably the metal carboxylate is a zinc carboxylate or copper carboxylate. The metal carboxylate may be added directly to the antifouling coating composition or be generated in situ in the antifouling coating composition.

Representative examples of C₆-C₂₀ cyclic monocarboxylic acids include naphthenic acid, 1 ,4-dimethy 1 -5-(3 -methy 1 -2-buteny 1 )-3 -cyclohexen- 1 -yl- carboxylic acid, 1 , 3 -dimethy 1 -2-(3 -methy 1 -2-buteny 1 )-3 -cyclohexen- 1 -yl- carboxylic acid, 1,2,3- trimethyl-5-(l-methyl-2-propenyl)-3-cyclohexen-l-yl- carboxylic acid, l,4,5-trimethyl-2-(2-methyl-2-propenyl)-3-cyclohexen-l-yl- carboxylic acid, 1 ,4, 5-trimethy 1 -2-(2-methyl-l-propeny 1 )-3 -cyclohexen- 1 -yl- carboxylic acid, 1,5, 6-trimethy 1-3 -(2-methy 1-1 -property 1 )-4-cyclohexen- 1 -yl- carboxylic acid, 1 -methyl-4-(4-methyl-3 -penteny 1 )-4-cyclohexen- 1 -yl-carboxylic acid, 1 -methyl -3 -(4-methyl-3 -penteny l)-3 -cycloh exen-l-yl-carboxylic acid, 2- methoxycarbony 1 -3-(2-methy 1 - 1 -propeny l)-5, 6-dimethyl-4-cyclohexen- 1 -y 1 - carboxylic acid, l-isopropyl-4-methylbicyclo[2,2,2]2-octen-5-yl-carboxylic acid, 1- isopropyl-4-methyl-bicyclo[2,2,2]2-octen-6-yl-carboxylic acid, 6-isopropyl-3- methyl-bicyclo[2,2,2]2-octen-8-yl-carboxylic acid and 6-isopropyl-3-methyl- bicyclo[2,2,2]2-octen-7-yl-carboxylic acid.

Representative examples of C₅-C₂₄ acyclic aliphatic monocarboxylic acids include versatic acids, neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4- dimethyl-2-isopropylpentanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, 2,2- dimethyloctanoic acid, 2,2-diethylhexanoic acid, pivalic acid, 2,2-dimethylpropionic acid, trimethylacetic acid, neopentanoic acid, 2-ethylhexanoic acid, isononanoic acid, 3,5,5-trimethylhexanoic acid, isopalmitic acid, isostearic acid, 16- methylheptadecanoic acid and 12,15-dimethylhexadecanoic acid. The acyclic aliphatic monocarboxylic acid is preferably selected from liquid, acyclic C₁₀-C₂₄ monocarboxylic acids or liquid, branched C₁₀-C₂₄ monocarboxylic acids. It will be appreciated that many of the acyclic C₁₀-C₂₄ monocarboxylic acids may be derived from natural sources, in which case in isolated form they typically exist as a mixture of acids of differing chain lengths with varying degree of branching.

Preferably the monocarboxylic acid is acyclic C₁₀-C₂₄ monocarboxylic acids, C₆-C₂₀ cyclic monocarboxylic acids or mixtures thereof.

Additives

The antifouling coating composition of the present invention optionally comprises one or more additives. Examples of additives that may be present in the coating composition of the invention include, rheology modifiers, antifoaming agents, pH adjusting agents, dispersing agents, wetting agents, coalescing agents and plasticizers. The coating composition of the invention preferably comprises a rheology modifier. A mixture of two or more rheology modifiers may be employed. The presence of a rheology modifier in the compositions of the invention advantageously improves the storage stability, the body of the coating composition and the application properties of the coating.

Examples of suitable rheology modifiers are polysaccharide rheology modifiers, associative rheology modifiers, clays, cellulosic rheology modifiers, fumed silica or a mixture thereof.

Exemplary polysaccharide rheology modifiers for use in the coating compositions include alginin, guar gum, locust bean gum and xanthan gum.

Exemplary clay rheology modifiers for use in the coating compositions of the invention include kaolin clay, smectite clay, illite clay, chlorite clay, synthetic clay or organically modified clay. Preferred clay rheology modifiers are synthetic clay or an organically modified clay.

Exemplary associative rheology modifiers for use in the coating compositions include non-ionic synthetic associative rheology modifier (niSAT), hydrophobically modified alkoxylated urethanes such as hydrophobically modified ethoxylated urethanes (HEUR), hydrophobically modified alkali-swellable emulsions (HASE), and styrene-maleic anhydride terpolymers (SMAT). Acidic acrylate copolymers (cross-linked) of ethyl acrylate and methacrylic acid, and acrylic terpolymers (cross-linked) of ethyl acrylate, methacrylic acid, and non-ionic urethane surfactant monomer may also be used as associative rheology modifiers. Particularly preferred associative rheology modifiers present in the coating compositions of the invention are hydrophobically modified ethoxylated urethanes (HEUR).

Preferably rheology modifiers are present in the composition of the invention in an amount of 0-10 wt%, more preferably 0.1-6 wt% and still more preferably 0.1- 2.0 wt%, based on the total dry weight of the composition.

The coating composition of the present invention may comprise an antifoaming agent. Antifoaming agents are sometimes also referred to as foam control agents or defoamers. A wide range of antifoaming agents are commercially available, and may be used in the coating compositions of the invention. Representative examples of suitable antifoaming agents include organic siloxanes, polyethers, polyether-modified silicones, mineral oils and combinations thereof. Preferred coating compositions of the invention comprise 0-2.0 wt% antifoaming agent based on the total weight of the coating composition.

The coating composition of the present invention may comprise a pH adjusting agent such as ammonia, 2-aminopropanol, sodium hydroxide (NaOH), sodium carbonate (Na₂CO₃) and sodium bicarbonate (NaHCO₃).

Coalescing agents may optionally be included. In a waterborne paint composition, the applied wet product is inhomogeneous, as opposed to a solventborne composition which will be homogenous when applied. In order to form a film the polymeric binder droplets or particles must coalesce. Coalescing agents aid this process in the water phase. Examples of suitable coalescing agents are ester alcohol, benzyl alcohol, propylene glycol monomethyl ether (PM), propylene glycol propyl ether (PnP), dipropylene glycol n-butyl ether (DPnB), propylene glycol phenyl ether (PPh), tripropylene glycol n-butyl ether (TPnB), ethylene glycol propyl ether (EP), ethylene glycol butyl ether (EB), diacetone alcohol (DAA) and dipropylene glycol methyl ether (DPM).

In order to improve or facilitate dispersion of the pigments, fillers and biocides it may be desirable to incorporate wetting/dispersion additives that are compatible with a water-borne coating composition. A wide range of dispersing agents is commercially available, and may be used in the coating compositions of the invention. Suitable dispersing agents include conventional anionic, cationic, non- ionic and amphoteric dispersing agents as well as combinations thereof.

Examples of suitable dispersing agents are polyalkylene glycol, polyacrylamide, polyethercarboxylate, polycarboxylates and sodium salts of acrylic polymers.

A plasticizer may be added to the coating composition of the present invention. Examples of suitable plasticizers are silicone oils (non-reactive polydimethylsiloxanes), chlorinated paraffins, phthalates, phosphate esters, sulphonamides, adipates, epoxidised vegetable oils and sucrose acetate isobutyrate.

Solvent The antifouling coating composition of the present invention is a waterborne composition, i.e. one comprising water as the main solvent.

The antifouling coating composition of the present invention preferably comprises water as the main solvent.

Low amounts of organic co-solvents may be present such as ketones, alcohols, glycol ethers or other oxygen-containing solvents that are soluble or miscible with water.

Preferably the coating composition comprises less than 10 wt% of an organic solvent, further preferred less than 5 wt% or an organic solvent relative to the total weight of the composition as a whole.

The coating compositions comprise at least 5 wt% water, relative to the total weight of the composition as a whole. Preferably the coating compositions comprise at least 10 wt% water relative to the total weight of the composition as a whole. Preferably, the compositions comprise 5 to 60 wt% water, more preferably 10 to 50 wt%, such as 15 to 40 wt%, relative to the total weight of the composition as a whole.

Biocide

The antifouling coating composition of the invention preferably additionally comprises a compound capable of preventing settlement or growth of marine fouling on a surface. The terms antifouling agent, antifoulant, biocide, active compounds, toxicant are used in the industry to describe known compounds that act to prevent marine fouling on a surface. The antifouling agents of the invention are marine antifouling agents.

The antifouling agent may be inorganic, organometallic or organic. Suitable antifouling agents are commercially available.

Examples of inorganic antifouling agents include copper and copper compounds such as copper oxides, e.g. cuprous oxide and cupric oxide, copper thiocyanate and copper sulfide, copper powder and copper flakes. Examples of organometallic marine antifouling agents include zinc pyrithione, copper pyrithione, zinc bis(dimethyldithiocarbamate) [ziram] and zinc ethyl enebi s( di t hi ocarb am ate) [zineb ] .

Examples of organic marine antifouling agents include heterocyclic compounds such as 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-l,3,5- triazine [cybutryne], 4,5-dichloro-2-w-octyl-4-isothiazolin-3-one [DCOIT], 1,2- benzisothiazolin-3-one, 3 -(3, 4-di chlorophenyl)- 1,1 -dimethylurea [diuron], N- dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide [dichlofluanid], N- dichlorofluoromethylthio-N',N'-dimethyl-N-p-tolylsulfamide [tolylfluanid], N- (2,4,6-trichlorophenyl)maleimide, triphenylborane pyridine [TPBP], 3-iodo-2- propynyl N-butylcarbamate [IPBC], 2,4,5,6-tetrachloroisophthalonitrile [chlorothalonil], /?-((diiodomethyl)sulphonyl)toluene, 4-bromo-2-(4-chlorophenyl)- 5-(trifluoromethyl)-lH-pyrrole-3-carbonitrile [tralopyril], 4-[l-(2,3-dimethylphenyl)ethyl]-lH-imidazole [medetomidine].

Other examples of marine antifouling agents may be tetraalkylphosphonium halogenides, quaternary ammonium salts, guanidine derivatives such as dodecylguanidine monohydrochloride; macrocyclic lactones including avermectins and derivatives thereof such as ivermectine; spinosyns and derivatives such as spinosad; capsaicin and derivatives such as phenylcapsaicin; and enzymes such as oxidase, proteolytically, hemicellulolytically, cellulolytically, lipolytically and amylolytically active enzymes. Complexes such as copper di(ethyl-4,4,4- trifluoroacetoacetate (Cu(ETFAA)2 as described in EP3860349 and WO2021113564 may also be used in the antifouling formulation.

Copper based antifouling coating compositions contain inorganic copper biocides such as metallic copper, cuprous oxide, copper thiocyanate and the like to prevent hard fouling.

The cuprous oxide material has a typical particle diameter distribution of 0.1- 70 pm and an average particle size (d50) of 1-25 pm. The cuprous oxide material may contain a stabilizing agent to prevent surface oxidation and caking. Examples of commercially available cuprous oxide paint grades include Nordox Cuprous Oxide Red Paint Grade and Nordox XLT, Cuprous oxide orange from Nordox AS, Furukawa Cuprous oxide from Furukawa Chemicals Co., Ltd.; Red Copp 97, Purple Copp 97, LoLo Tint LM, LoLo Tint NP, LoLo Tint LM B/B, from American Chemet Corporation; Cuprous Oxide Red from Cosaco; Cuprous oxide Roast, Cuprous oxide Electrolytic from Taixing Smelting Plant Co., Ltd.

Another example of commercially available grades of inorganic copper is e.g., Cuprous thiocyanate from Bardyke Chemicals Ltd.

The copper pyrithione material (needle shaped powder) has a typical average particle size (d50) of 2-7 pm and may contain surfactants for stabilisation. Examples of commercially available material is Copper Omadine from Arxada (Arch Chemicals B.V.); CleanBio from Kolon Life Science.

Trade names for some suitable antifouling agents are Econea (tralopyril, from Janssen and Kolon Life Science); Selektope (Medetomidine from LTech); SeaNine 21 IN (DCOIT from DuPont Microbial Control), SeaNine Ultra (encapsulated DCOIT from DuPont Microbial Control); UmiGard Pro and UmiGard SynPro (from Arxada), Perozine Marine (Zineb from Agria S. A.); Zineb Nautec (Zineb from United Phosphorus).

Antifouling coating compositions without inorganic copper biocides typically use a series of organic biocides such as 4-[l-(2,3-dimethylphenyl)ethyl]- IH-imidazole [medetomidine] and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)- lH-pyrrole-3-carbonitrile [tralopyril] to prevent hard fouling. Any known biocide can be used in the invention.

Preferred biocides are cuprous oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate) [zineb], 2-(/c/7-butylamino)-4- (cyclopropylamino)-6-(methylthio)-l,3,5-triazine [cubutryne], 4,5-dichloro-2-n- octyl-4-isothiazolin-3-one [DCOIT], N-dichlorofluoromethylthio-N',N'-dimethyl-N- phenylsulfamide [dichlorofluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-N-p- tolylsulfamide [tolylfluanid], triphenylborane pyridine [TPBP] and 4-bromo-2-(4- chlorophenyl)-5-(trifluoromethyl)-lH-pyrrole-3-carbonitrile [tralopyril], 4-[l-(2,3- dimethylphenyl)ethyl]-lH-imidazole [medetomidine] and phenylcapsaicin.

A mixture of biocides can be used as is known in the art as different biocides operate against different marine fouling organisms. Mixtures of antifouling agents are generally preferred. In one embodiment the antifouling coating composition comprises cuprous oxide and/or copper thiocyanate and one or more agents selected from copper pyrithione, zineb, 4,5-dichloro-2-octyl-4-isothiazolin-3-one, tralopyril and medetomidine.

In an alternative embodiment the antifouling coating is free of an inorganic copper biocide. In this embodiment, a preferred biocide combination involves a combination of tralopyril and one or more selected from zinc pyrithione, copper pyrithione, zineb, 4,5-dichloro-2-octyl-4-isothiazolin-3-one and medetomidine.

Where present, the combined amount of biocides may form up to 60 wt% of the coating composition, such as 0.1 to 50 wt%, e.g. 5 to 45 wt%, relative to the total weight of the coating composition. Where inorganic copper compounds are present, a suitable amount of biocide might be 5 to 60 wt% relative to the total weight of the coating composition. Where inorganic copper compounds are avoided, lower amounts might be used such as 0.1 to 25 wt%, e.g. 0.2 to 10 wt% relative to the total weight of the coating composition.

Where present the combined amount of biocides may form up to 70 wt% of the coating composition, such as 0.1 - 60 wt%, e.g 10 - 60 wt% relative to the total dry weight of the coating composition.

It will be appreciated that the amount of biocide will vary depending on the end use and the biocide used.

Some biocides may be encapsulated or adsorbed on an inert carrier or bonded to other materials for controlled release. Some biocide may be surface treated to improve stability, dispersibility and/or controlled release. These percentages refer to the amount of active biocide present and not therefore to any carrier used.

Pigments, extenders and fillers

In addition to the polymeric binder, rosin ester, biocides (including cuprous oxide) and any of the optional components described above, the antifouling coating composition according to the present invention may optionally further comprise one or more components selected among inorganic or organic pigments, extenders and fillers.

The pigments may be inorganic pigments, organic pigments or a mixture thereof. Inorganic pigments are preferred. Examples of inorganic pigments include titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, zinc oxide, zinc sulfide, lithopone and graphite. Examples of organic pigments include carbon black, phthalocyanine blue, phthalocyanine green, naphthol red and diketopyrrolopyrrole red. Pigments may optionally be surface treated to be more easily dispersed in the paint composition. The titanium dioxide may be surface treated with silicone, zinc, zirconium or aluminium.

Examples of extenders and fillers are minerals such as dolomite, plastorite, calcite, quartz, baryte, magnesite, aragonite, silica, nepheline syenite, wollastonite, talc, chlorite, mica, kaolin, pyrophyllite, perlite, silica and feldspar; synthetic inorganic compounds such as calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zinc phosphate and silica (colloidal, precipitated, fumed, etc.); polymeric and inorganic microspheres such as uncoated or coated hollow and solid glass beads, uncoated or coated hollow and solid ceramic beads, porous and compact beads of polymeric materials.

Preferably the total amount of extender, filler and/or pigment present in the compositions of the invention is 2-60 wt%, more preferably 5-50 wt% and still more preferably 7-45 wt%, based on the total weight of the composition.

Preferably the total amount of extender, filler and/or pigment present in the compositions of the invention is 2 - 80 wt.%, preferably 5 - 70 wt.%, more preferably 10 - 65 wt.% of the total dry weight of the coating composition

The skilled person will appreciate that the extender, filler and pigment content will vary depending on the particle size distribution, the particle shape, the surface morphology, the particle surface-resin affinity, the other components present and the end use of the coating composition.

Examples of reinforcing fillers are flakes and fibres. Fibres include natural and synthetic inorganic fibres and natural and synthetic organic fibres e.g. as described in WO 00/77102. Representative examples of fibres include mineral-glass fibres, wollastonite fibres, montmorillonite fibres, tobermorite fibres, atapulgite fibres, calcined bauxite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, and processed mineral fibres from mineral wool. Preferably, the fibres have an average length of 25 to 2,000 pm and an average thickness of 1 to 50 pm with a ratio between the average length and the average thickness of at least 5. Preferably reinforcing fillers are present in the compositions of the invention in an amount of 0- 20 wt%, more preferably 0.5-15 wt% and still more preferably 1-10 wt%, based on the total weight of the composition.

Examples of flaky fillers are mica, glass flakes and micronized iron oxide (MiO).

The antifouling coating composition of the invention should preferably have solids content above 35 vol%, e.g. above 40 vol%, such as above 42 vol%.

More preferably the antifouling coating composition should have a content of volatile organic compounds (VOC) of less than 200 g/L, preferably less than 150 g/L, more preferably less than 100 g/L, e.g. less than 70 g/L. VOC content can be calculated as described in e.g. ASTM D5201-01 or IED 2010/75/EU or measured, e.g. as described in US EPA Method 24 or ISO 11890-2.

The antifouling coating composition of the invention ideally has a pigment volume concentration (PVC) of less than 80%, more preferably less than 60%, further preferred less than 55%. Pigment Volume Concentration (PVC) is defined as the ratio of pigment volume to the total dry film volume.

Applications

The antifouling coating composition of the invention can be applied to a whole or part of any object surface which is subject to fouling. The surface may be permanently or intermittently underwater (e.g. through tide movement, different cargo loading or swell). The object surface will typically be the hull of a vessel or surface of a fixed marine object such as an oil platform or buoy. The surface of the substrate may be the "native" surface (e.g. the steel surface) or a surface which already has an organic primer layer coated thereon.

Application of the coating composition can be accomplished by any convenient means, e.g. via painting (e.g. with brush or roller) or spraying the coating onto the object. Typically, the surface will need to be separated from the seawater to allow coating. The application of the coating can be achieved as conventionally known in the art.

When applying the antifouling coating to an object (e.g. a ship hull) the surface of the object is preferably not protected solely by a single coat of antifouling coating composition. Depending on the nature of the surface, the antifouling coating can be applied directly to an existing coating system. Such a coating system may comprise several layers of paint of different generic types (e.g. epoxy, polyester, vinyl or acrylic or mixtures thereof). Starting with an uncoated surface (e.g. steel, aluminium, plastic, composite, glass fiber or carbon fiber) the full coating system will typically comprise one or two layers of a primer such as an anticorrosive coating (e.g. curable epoxy coating or curable modified epoxy coating), one layer of tie-coat (e.g. curable modified epoxy coating or physical drying vinyl coating) and one or two layers of antifouling paint. In exceptional cases further layers of antifouling paint may be applied. If the surface is a clean and intact antifouling coating from a previous application, the new antifouling paint can be applied directly, typically as one or two coats with more in exceptional cases. When two or more coats of antifouling coating composition is applied, the different coats can be antifouling coatings of different compositions. If different compositions are used in consecutive layers, the difference may e.g. be in type of biocide or level of biocide.

The coating composition of the present invention may be applied on anticorrosive primers, tie-coat and antifouling coating films prepared from water borne, solvent borne and solvent free coating compositions. Application on an epoxy primer layer is preferred.

The invention will now be defined with reference to the following nonlimiting examples.

Examples

Materials and methods

Table 1: List of materials

5794-1. Table2: Overview of polymer dispersions

Polymer dispersion D-5 and D6: Synthesis and preparation described below.

Table 3: Overview of rosin esters

Rosin ester R-l : Methyl ester of rosin (Granolite M from DRT); Rosin ester R-2: Triethyleneglycol (TEG) ester of rosin (Granolite TEG from DRT); Rosin ester R-3 :

Glycerol ester of rosin (Granolite SG from DRT)

Table 4: Overview of rosin acid and rosin ester dispersions¹

¹ Amount of raw materials in parts by weight.

²E-1 : Rosin acid dispersion (Dermulsene A 7510 from DRT, softening point 75°C, viscosity 600 mPa.s @20°C, pH 7.8 @ 20°C).

VOC calculations

Calculated VOC (in g/L) given as Mat. VOC (VOC of Material, actual VOC, based on total coating formulation) in Table to 10

Table . Calculated VOC for regulatory VOC and Material VOC (less water and exempt) can be calculated from the standard ASTM D5201-05a.

Determination of glass transition temperature of the rosin esters

The glass transition temperature (Tg) was obtained by Differential Scanning Calorimetry (DSC) measurements. The DSC measurements were performed on a TA Instruments DSC Q200. The measurement was performed by running a heat- cool-heat procedure, within a temperature range from -80°C to 150°C, with a heating rate of 10°C/min and cooling rate of 10°C/min and using an empty pan as reference. The data were processed using Universal Analysis software from TA Instruments. The inflection point of the glass transition range, as defined in ASTM E1356-08, of the second heating is reported as the Tg of the polymers. Approx. 10 mg of the material was transferred to an aluminum pan. The pan was sealed with a non-hermetic lid.

Determination of glass transition temperature of the (meth)acrylic binder The glass transition temperature (Tg) was obtained by Differential Scanning Calorimetry (DSC) measurements. The DSC measurements were performed on a TA Instruments DSC Q200. The measurement was performed by running a heat- cool-heat procedure, within a temperature range from -80°C to 150°C or -50 °C- 150 °C with a heating rate of 10°C/min and cooling rate of 10°C/min and using an empty pan as reference. The data were processed using Universal Analysis software from TA Instruments. The inflection point of the glass transition range, as defined in ASTM E1356-08, of the second heating is reported as the Tg of the polymers. The samples were prepared by applying a film of the polymer dispersion on a glass panel using a frame applicator with 100 pm gap size and allowing it to dry for at least 24 h at 23 °C. Approx. 10 mg of the dried polymeric material was transferred to an open aluminum pan.

Determination of viscosity of rosin esters

The viscosity of the liquid rosin esters was determined in accordance with ASTM D2196 Test Method A using a Brookfield DV-I Prime digital viscometer at a rotational speed of 12 rpm and with a LV-4 spindle. The samples were tempered to 23.0°C ± 0.5°C before the measurements.

Particle size measurement

The average particle size was determined by dynamic light scattering (DLS) using a Malvern Zetasizer Nano S particle size analyser at a wavelength of 633 nm with a constant angle of 173°. The measurements were performed at 25°C. Before measurement, 0.1 mL sample was diluted with 0.1 L deionized water. Measurement duration, measurement position and attenuator were set automatically by the instrument software. Each sample was measured 3 times, and the results are reported as the mean of the Z-average particle size.

Preparation of (meth)acrylic dispersions

(Meth)acrylic dispersions D-l to D-4 are commercially available, while (meth)acrylic dispersions D-5 and D-6 where prepared following the described procedure.

In a reaction vessel fitted with stirrer, condenser and inlets for nitrogen gas, monomer feed and initiator feed, the surfactant solution was heated to 70°C under nitrogen gas. Monomer charge 1 and initiator solution 1 were added. The mixture was then stirred for 30 minutes while the temperature was maintained at 70°C. The temperature was then increased to 80°C. While stirred at 80°C, monomer charge 2 and initiator solution 2 were added slowly to the vessel at a constant rate over 3 hours. When the addition was completed, the mixture was stirred at 80°C for 2 hours before the finished polymer dispersion was cooled and filtered through a 100 pm nylon filter bag to remove larger particles.

Table 5: Preparation of (meth)acrylic dispersions in parts per weight

Preparation of rosin and rosin ester dispersions Dispersion E-l was acquired commercially.

Dispersions E-2 and E-3 were made according to the following procedure. A solution of water and additives was heated in a beaker to 75°C. Rosin ester, heated to 75°C, was slowly added under stirring with an Ultra Turrax rotor-stator mixer. The mixture was then dispersed at 25 000 rpm for 2 minutes.

Dispersion E-4 was made according to the following procedure. A solution of water and additives was heated in a beaker to 75°C. Rosin ester dissolved in xylene was heated to 75°C. The rosin ester solution was slowly added to the aqueous solution under stirring with an Ultra Turrax rotor-stator mixer. The mixture was then dispersed at 25 000 rpm for 2 minutes. Xylene and water were then partially removed using a rotary evaporator.

Preparation of paint

Pigments, extenders and fillers, biocides, additives and water were mixed and grinded at high shear using a dissolver with impeller blade until the mill base had fineness of grind below 40 pm. Then the stirring rate was reduced, and the binder ingredients were added slowly. More additives were post-added when/if needed.

Testing of mechanical properties

Accelerated cracking testing of coating films

PVC panels were coated with Safeguard Plus (two-component polyamide cured vinyl epoxy-based coating, manufactured by Chokwang Jotun Ltd., Korea) using airless spray. In example 25 PVC panels were also coated with Jotacoat Universal N10 (two component polyamine cured epoxy-based coating from Jotun AS). The antifouling coatings were applied on the panels using a film applicator with gap size of 800 pm. The panels were dried for 72 h at 52°C before immersion in seawater at 40°C. At regular intervals, the panels were taken out and evaluated after drying at ambient conditions for 24 h and drying at 52°C for 24 h. The panels were assessed for cracking visually and under 10 x magnifications and rated as described in ISO 4628-4:2005. The panels were then re-immersed.

The rating after drying at 52°C is reported in Tables 7 to 10 following the rating evaluation given in Table 6. The values for “size” and “quantity” of defects were multiplied and given as an integer value, e.g., cracking quantity 3 with size 3 means 9.

Table 6: Evaluation of cracking or blistering after immersion testing in saltwater and freshwater, respectively.

A rating of 0 - 5 (excellent - good) is considered acceptable.

Accelerated blistering testing of coating films

A similar procedure as for cracking testing is performed, except panels are submerged in fresh water at 30°C for blistering testing. The panels were assessed for blistering visually and under 10 x magnifications and rated as described in ISO 4628-2:2016. The rating after freshwater immersion is reported in Tables 7 to 10, following the rating evaluation given in Table 6. The values for “size” and “quantity” of defects were multiplied and given as an integer value, e.g., blisters quantity 3 with size 3 means 9. Determination of the polishing rates of antifouling coating films on rotating disc in seawater

The polishing rate is determined by measuring the reduction in film thickness of a coating film over time. For this test PVC discs are used. The coating compositions are applied as radial stripes on the PVC disc using a film applicator with 300 pm gap size. The thickness of the dry coating films is measured by an optical surface profiler (TaiCaan laser profilometer). The PVC discs are mounted on a shaft and rotated in a container in which seawater is flowing through. The speed of the rotated shaft is giving an average simulated speed of 16 knots on the disc. Natural seawater which has been filtered and temperature-adjusted to 25°C ± 2°C is used. The PVC discs are taken out at regular intervals for measuring the film thickness. The discs are rinsed and allowed to dry overnight at room temperature before measuring the film thickness. Desired polishing is 10-60 pm after 28 weeks.

Table 7: Paint examples 1-15 with dispersion D-l

able 8: Comparative examples using dispersion D-l

Table 9: Paint examples with dispersions D-2 to D-6

Table 10: Comparative paint examples with dispersions D-2 to D-6

Table 11: Test of different primers

Observations from the experiments using (meth)acrylic dispersion D-l (Tg 17.9°C), Table 7 (Examples) and Table 8 (Comparative examples)

- Examples 1 and 2, binder D-l and rosin methyl ester is used in different amounts. The polishing results show that polishing increases with increasing amount of rosin methyl ester. No cracking or blistering is observed.

- Comparative example 1, is directly comparable to Ex. 1 and 2 and show that without the rosin Me ester the polishing is low (< 10 pm).

- Example 3 and 4, binder D-l and Rosin TEG ester is used in different amounts. The results show that polishing increases with increasing amount of the rosin TEG ester. No cracking is observed after salt water immersion. Fresh water immersion was not tested.

- Comparative examples 2 and 3, D-l is used as a binder and rosin acid used instead of rosin ester. The results show good polishing, but high degree of cracking and blistering in the film after immersion in salt and fresh water.

- Comparative examples 4 and 5, D-l and a solid glycerol ester of rosin having a Tg < 0 is used in different amounts. The results show that when a rosin ester that is solid at room temperature (Tg < 0) is used there is little or no polishing. No cracking or blistering is observed.

- Example 5 show that binder D-l and a mix of rosin methyl ester and rosin acid can be used. The polishing rate is high and there are no cracks or blisters. The ratio of rosin esterrosin acid is 1 : 1.5.

- Example 6, binder D-l and a ratio of rosin ester to rosin acid of 1 : 1 is used.

The polishing rate was good and there are no cracks or blisters. - Example 7, binder D-l and lower amount of rosin methyl ester is used, D-

1 : rosin methyl ester ratio of 9: 1. The polishing is still good and there are no cracks or blistering.

- Comparative example 8 shows that 0.05 wt% of the rosin methyl ester and a ratio of D-l and rosin methyl ester of 95:5 is not a sufficient amount of rosin methyl ester to obtain good polishing.

- Example 8, D-l is used as binder and rosin methyl ester and rosin acid are used in a 1 :0.5 ratio. Good polishing and no cracking or blistering observed.

- Example 9, D-l is used as binder and rosin TEG ester and rosin acid are used in a 1 :2: 1 ratio. Good polishing and no cracking or blistering observed.

- Examples 10 and 11, D-l and rosin methyl ester in different amounts are used in a formulation with another Cuprous oxide grade (LoLoTint) and copper pyrithione as biocides. Results show good polishing and no cracks or blisters. Comparative examples 6 and 7 are directly comparable with examples 10 and 11. Comparative example 6, only (meth)acrylic dispersion D-l and no rosin ester or rosin acid, shows low polishing, no cracks or blisters. Comparative example 7 includes rosin acid and results show good polishing but blistering after freshwater immersion.

- Examples 12 and 13, D-l and rosin methyl ester in different amounts are used in a copper-free formulation, Zinc pyrithione and Tralopyril are used as biocides. The results show good polishing and no cracking and blistering after immersion in saltwater and freshwater.

- Examples 14 and 15, D-l and rosin methyl ester in different amounts are used in combination with Copper pyrithione and Tralopyril as biocides. The results show good polishing and no cracking and blistering after immersion in salt and fresh water.

Observations from the experiments using (meth)acrylic dispersions D-2 to D-6, Table 9 (Examples) and Table 10 (Comparative examples).

- Examples 16 and 17, (meth)acrylic dispersion D-2 (Tg 1.7°C) is used in combination with different amounts of rosin methyl ester. The polishing rate is good, and no cracks or blisters observed. These results show that a (meth)acrylic binder with a lower Tg can also be used.

- Example 18, (meth)acrylic dispersion D-2 is used as a binder and a mixture of rosin methyl ester and rosin acid in a 1 :2.5 ratio is used. The polishing is good and there are no cracks or blisters.

- Comparative example 9, (meth)acrylic dispersion D-2 and a quite high amount of rosin acid is used. The polishing rate is high but there are also a high amount of crack and blisters observed.

- Examples 19 and 20, (meth)acrylic dispersion D-3 (Tg 38.4°C) that has a higher Tg than binder D-l is used. Rosin methyl ester in different amount is used. Polishing is good, no cracking after salt water immersion and low degree of blistering after freshwater immersion. These results show that (meth)acrylic binders with higher Tg can also be used.

- Comparative examples 10 and 11, (meth)acrylic dispersion D-3 is used in combination with rosin acid or alone. With rosin acid present, the polishing is good, while cracking and blistering is seen after sea and freshwater immersion, respectively. D-3 alone, without rosin acid, shows no cracking or blistering after salt and fresh water immersion, but the polishing is low.

- Example 21, D-3 and a mix of rosin methyl ester and rosin acid is used in ratio

1 : 1.5. Results show good polishing, low degree of cracking after saltwater immersion and no blistering after freshwater immersion.

- Example 22, (meth)acrylic dispersion D-4 (18.5°C) is used together with a combination of rosin methyl ester and rosin acid in a ratio of 1 : 1.5. Decent polishing rate, low degree of cracking and blistering after immersion in saltwater and freshwater, respectively.

- Comparative examples 12 and 13, D-4 is used alone or in combination with rosin acid. There is no polishing without rosin acid or rosin ester present, while mechanical properties are good. When D-4 is used with rosin acid, polishing has increased somewhat, but is still low. Mechanical properties are poor, high degree of cracking and blistering observed. - Example 23, (meth)acrylic dispersion D-5 (Tg -33°C) having the lowest Tg of the (meth)acrylic dispersions, is used together with rosin methyl ester. Results show decent polishing and neither cracking nor blistering.

- Comparative example 14 shows that (meth)acrylic dispersion D-5 without added rosin Me ester does not give sufficient polishing. Mechanical properties are however good, no cracks or blisters observed.

- Example 24, (meth)acrylic dispersion D-6 (Tg -18.3°C) is used together with rosin methyl ester. Example 24 show decent polishing and good mechanical properties, no cracks or blisters are observed.

- Comparative example 15, D-6 is used without rosin ester or acid. Cracking is observed after exposure in salt or freshwater. The polishing rate is not sufficient.

Observations from tests of different primers

- The tests in example 25 show that the coating compositions of the invention can be applied to different primers while still maintaining good performance.

Claims

1. A waterborne antifouling coating composition comprising:

2. The waterborne antifouling coating composition as claimed in claim 1, wherein said composition has a volatile organic compound (VOC) content of less than 200 g/L, preferably less than 150 g/L, more preferably less than 100 g/L, even more preferably less than 70 g/L.

3. The waterborne antifouling coating composition as claimed in claim 1 or 2, wherein said composition has a pigment volume concentration (PVC) of less than 80%.

4. The waterborne antifouling coating composition as claimed in any of clams 1 to 3, wherein said polymeric binder is in the form of a dispersion.

5. The waterborne antifouling coating composition as claimed in any of claims 1 to 4 wherein said polymeric binder comprises a monomer selected from (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylic acid amide, vinyl chloride, vinyl propionatemaleic acid, itaconic acid, styrene, α-methyl styrene, alkyl vinyl ether, vinyl pyrrolidone, N-vinyl caprolactame, N-methyl-N- vinylacetamide or (meth)acrylonitrile. The waterborne antifouling coating composition as claimed in any of claims 1 to 5, wherein said polymeric binder comprises (meth)acrylic acid and/or (meth)acrylic acid ester monomers, preferably wherein the polymeric binder comprises at least 15 wt%, relative to the total weight of the polymeric binder of (meth)acrylic acid and/or (meth)acrylic acid ester monomers. The waterborne antifouling coating composition as claimed in any of claims 1 to 6, wherein said polymeric binder comprises a residue of at least one, and preferably at least two, monomers of formula (I)

wherein R¹ is H or CH₃;

R² is H or optionally a linear, branched or cyclic substituted C_1-18 alkyl, wherein said substituents are selected from OH, OR³ and N(R⁴)₂;

R³ is selected from C_1-8 alkyl and C_3-8 cycloalkyl; and each R⁴ is independently selected from H, C_1-8 alkyl and C_3-8 cycloalkyl. The waterborne antifouling coating composition as claimed in any of claims 1 to 7, wherein said composition further comprises a rosin acid and/or rosin acid derivative. The waterborne antifouling coating composition as claimed in any of claims 1 to 8, wherein said composition further comprises one or more biocides. The waterborne antifouling coating composition as claimed in any of claims 1 to 9, wherein said composition comprises 1.0 to 40 wt% of the polymeric binder, based on the weight of the total dry weight of the composition.

11. The waterborne antifouling coating composition as claimed in any of claims 1 to 10, wherein said composition comprises 1.0 to 30 wt% of the rosin ester, based on the dry weight of the total composition.

12. A process for applying a waterborne antifouling coating composition to a substrate comprising applying, e.g. by spraying, a waterborne antifouling coating composition as defined in any of claims 1 to 11 to a substrate and allowing the coating composition to dry.

13. A process for protecting an object from fouling, said process comprising coating at least a part of said object which is subject to fouling with an antifouling coating composition as claimed in any of claims 1 to 11.

14. A substrate coated with a waterborne antifouling coating composition as claimed in any of claims 1 to 11, wherein said coating composition has been allowed to dry.

15. The substrate as claimed in claim 14, wherein said substrate is the surface of a marine structure, preferably a marine structure which is submerged when in use.

16. Use of a rosin ester with a glass transition temperature (Tg) of less than 0 °C to increase the polishing rate of a waterborne antifouling coating composition, preferably an antifouling coating compositing comprising polymeric binder comprising a structural unit derived from an ethylenically unsaturated monomer, more preferably an antifouling coating composition comprising a polymeric binder comprising (meth)acrylic acid and/or (meth)acrylic acid ester monomers.