DE102018128727A1 - Antifouling composition - Google Patents

Abstract

A binder for an antifouling coating composition, comprising: (i) a hydrophilic copolymer having a glass transition temperature of at least 0 ° C, comprising at least 10% by weight of at least one monomer of formula (I) where R is H or C str and C 3 to C 18 pure Is a substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or is a pure poly (alkylene glycol) chain; and at least one monomer of the formula (II) wherein R is H or CH, and R is C 1 -C 20 hydrocarbon radical; hydrophilic copolymer comprises less than 15% by weight of other comonomers than those of formula (I) or (II); (ii) a cyclic monocarboxylic acid such as rosin or a derivative thereof (iii) a silyl ester copolymer comprising at least 15% by weight; % of a silyl ester monomer and / or a non-hydrophilic (meth) acrylic polymer comprising less than 10% by weight of a monomer of formula (I).

Description

Field of the invention

The present invention relates to a binder for a marine antifouling coating composition, in particular for marine antifouling coating compositions comprising a three-component binder based on a hydrophilic (meth) acrylate copolymer, a cyclic monocarboxylic acid and a silyl ester or (meth) acrylic polymer. The invention further relates to a method of protecting objects from fouling and to articles coated with the antifouling composition of the invention.

State of the art

Surfaces immersed in seawater are subject to fouling by marine organisms such as green and brown algae, barnacles, bivalves, tube worms and the like. On marine structures such as vehicles, oil rigs, buoys, etc., such fouling is undesirable and has economic consequences. Fouling can lead to biological degradation of the surface, an increase in weight and accelerated corrosion. In vehicles, fouling increases frictional resistance, resulting in lower speed and / or increased fuel consumption. It can also lead to reduced maneuverability.

Antifouling paints are used to prevent colonization and growth of marine organisms. These paints generally comprise a film-forming binder together with various ingredients such as pigments, fillers, solvents and biologically active substances.

Today, the most successful self-polishing antifouling systems on the market are based on (meth) acrylic copolymers with silylester functions. Silyl ester functional (meth) acrylic copolymers are often used in conjunction with other binders such as acrylates and rosin or rosin derivatives to tailor the self-polishing properties as well as the mechanical properties of the antifouling coating films.

While marine antifouling paints have been developed to work in seawater, it is also important that these coatings work in fresh water. In particular, it is important that the coatings in fresh water do not suffer from excessive water absorption.

It may not be directly apparent why water uptake in fresh water is important for coatings of ships operating on seas. However, many ships remain in fresh water for extended periods of time. For example, the Panama Canal contains fresh water. In addition, many new buildings are being fitted in freshwater rivers in China. In these cases, excessive water absorption can lead to excessive swelling and, in the worst case, collapse of the paint layer.

The ability to withstand water intake in fresh water is also an important indicator of seawater operation. It is a good indicator that the coatings will have long term stability. In seawater, paint layers receive water, but the speed and amount are lower due to the lower osmotic pressure. Excessive water absorption in fresh water indicates that water absorption in seawater will increase in the long term.

Antifouling coatings are designed to last up to 7.5 years of service. Maintaining minimal water uptake during this period is an important factor in controlling the release of active components from the coating. For any given type of antifouling technology, there is a clear link between long-term reliable performance and water absorption. Excessive water uptake results in higher release rates of active ingredients than desired and a decrease in performance over the life of the coating. Depending on the type of binder system used, increasing water uptake may result in faster hydrolysis and excessive erosion or accelerated leaching of active ingredients, resulting in the formation of a thicker depleted layer (leached layer) on the surface of the coating. In any case, the control of water absorption is an important Parameters in the development of high-performance antifouling coatings, such as those for new buildings and stays in dry dock.

The inventors have found that the use of a particular binder in an antifouling paint surprisingly reduces water absorption in fresh water. The binder is one comprising three components, namely a hydrophilic (meth) acrylate copolymer comprising certain hydrophilic monomers, a cyclic monocarboxylic acid component and an acrylic / silyl ester copolymer component. When used together in an antifouling coating composition, the binder reduces the amount of water absorbed by the film. Antifouling coatings comprising the binder according to the invention therefore allow longer maintenance intervals.

The literature contains numerous disclosures of binder polymers for antifouling coatings. In particular, silyl ester copolymers and acrylate-based polymers are well known. However, there are only a few disclosures of binders comprising a mixture of three binder components as required by the present invention.

In EP 2128208 For example, antifouling coating compositions comprising silyl ester copolymers, a rosin component and a very low glass transition temperature softening resin are prepared. As we noted in the examples, when the hydrophilic (meth) acrylate polymer has a low Tg, the binder suffers from high water uptake.

WO 03070832 describes a coating composition comprising copolymer A (silyl copolymer), polymer B (which is incompatible with copolymer A and may comprise a hydrophilic comonomer) and optionally polymer C (often a non-hydrophobic copolymer). None of the paint examples uses a cyclic monocarboxylic acid. The use of such an acid is advantageous as it reduces the viscosity of the coating composition and therefore makes it possible to produce low VOC coating compositions.

WO 2014175246 describes an antifouling coating composition comprising a binder based on a styrene and glycidyl (meth) acrylate based copolymer and a silyl ester copolymer. Example 15 uses rosin, but there is no disclosure of a copolymer (i) as required by the present invention because there is a large excess of styrene. Copolymers such as A-13 have a Tg of significantly less than 0 ° C.

WO 97/44401 describes the use of rosin or rosin equivalents, fibers and a polymeric plasticizer in an antifouling coating composition. There are no paint examples comprising two types of (meth) acrylic copolymers.

EP 1288234 describes a film-forming polymer made from binders having a low content of hydrolyzable monomers. The only hydrophilic comonomers exemplified are vinyl pyrrolidone and methacrylic acid, and no example is based on a combination of acrylic copolymers.

WO 2005/005516 describes low Mw silylester copolymers and their use in antifouling coatings. Example 7 describes a coating composition containing a binder based on an unidentified silyl ester copolymer, rosin, and Degalan LP 64/12 (a non-hydrophilic BMA / MMA copolymer). None of the disclosed silyl copolymers has a hydrophilic monomer content of more than 10% by weight, that is, the hydrophilic binder component of the present invention is absent.

WO 2011/131721 describes a coating composition made by adding various ingredients in a particular order (eg, desiccant). In the examples rosin is used together with Neocryl B725 (a non-hydrophilic BMA / MMA copolymer) and Polyace NSP-100 (silyl acrylate). Neocryl B725 does not use hydrophilic comonomers.

WO 2014/175140 describes a silyl copolymer with certain end groups.

EP 3078715 comprises an antifouling coating composition comprising a silyl ester copolymer, tralopyril and a stabilizer. In the examples, a triisopropylsilyl methacrylate copolymer, balsam resin and an acrylic polymer are used. The monomer composition or polymer properties of the acrylic copolymer are not specified.

The patent WO 2009/149919 covers the use of caprolactone-modified comonomers in a silyl copolymer. No additional acrylic polymer is used.

EP 2489710 describes antifouling coatings by way of example and gives by way of example two acrylic acid copolymers T3 and T4. These are combined with rosin and a vinyl chloride-isobutyl vinyl ether copolymer.

In EP 2161316 and the relative US 2011/0166253 For example, the binder is based on a rosin component and a silyl ester component, ie, the third binder component of the present invention is absent.

The combination of ingredients required in the claims is novel and provides remarkable results.

Brief description of the invention

1. (i) ein hydrophiles Copolymer mit einer Glasübergangstemperatur von mindestens 0 °C, umfassend mindestens 10 Gew.-% von mindestens einem Monomer der Formel (I)
   
   wobei R¹ H oder CH₃ ist und R² ein C3-C18-Substituent mit mindestens einem Sauerstoff- oder Stickstoffatom, vorzugsweise mindestens einem Sauerstoffatom ist oder R² eine Poly(alkylenglykol)-Kette ist; und mindestens ein Monomer der Formel (II),
   
   wobei R¹' H oder CH₃ ist, und R²' ein C1-C20-Kohlenwasserstoffrest ist; wobei das hydrophile Copolymer weniger als 15 Gew.-% anderer Comonomere als die der Formeln (I) und (II) umfasst;
2. (ii) eine cyclische Monocarbonsäure wie etwa Kolophonium oder ein Derivat davon (wie etwa ein Salz davon); und
3. (iii) ein Silylester-Copolymer, umfassend mindestens 15 Gew.-% eines Silylester-Monomers und/oder eines nicht hydrophilen (Meth)acrylpolymers, das weniger als 10 Gew.-% eines Monomers der Formel (I), vorzugsweise weniger als 5 Gew.-%, mehr bevorzugt 0 Gew.-% der Monomere der Formel (I) umfasst.

In a first aspect, the invention provides a binder for an antifouling coating composition comprising:

1. (i) a hydrophilic copolymer having a glass transition temperature of at least 0 ° C, comprising at least 10% by weight of at least one monomer of the formula (I)
   
   wherein R ^{1 is} H or CH ₃ and R ^{2 is} a C 3 -C 18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ^{2 is} a poly (alkylene glycol) chain; and at least one monomer of the formula (II),
   
   wherein R ¹ 'is H or CH ₃ , and R ² ' is a C ¹ -C 20 hydrocarbon radical; wherein the hydrophilic copolymer comprises less than 15% by weight of other comonomers than those of formulas (I) and (II);
2. (ii) a cyclic monocarboxylic acid such as rosin or a derivative thereof (such as a salt thereof); and
3. (iii) a silyl ester copolymer comprising at least 15% by weight of a silyl ester monomer and / or a non-hydrophilic (meth) acrylic polymer containing less than 10% by weight of a monomer of formula (I), preferably less than 5 Wt .-%, more preferably 0 wt .-% of the monomers of the formula (I).

The amount of the component (i) in the binder is preferably in the range of 20 to 60% by weight (dry substance). The amount of the component (ii) in the binder is preferably in the range of 10 to 70% by weight (dry substance). The amount of the component (iii) in the binder is preferably in the range of 5 to 70% by weight (dry substance).

The invention also provides an antifouling coating composition comprising a binder as described herein, preferably dispersed in a solvent. The antifouling coating may further comprise an antifouling agent, preferably cuprous oxide, zinc ethylene bis (dithiocarbamate) and / or copper pyrithione.

The invention also provides a method of protecting an article from fouling, which process comprises coating at least a portion of this article subject to fouling with an antifouling coating composition as defined herein.

The invention also relates to articles coated with the antifouling coating composition as herein defined or the use of the antifouling composition of the present invention to protect a marine surface from fouling.

definitions

The term "marine antifouling coating composition", "antifouling coating composition" or simply "coating composition" refers to a composition suitable for use in a marine environment. The antifouling coating composition preferably contains an antifouling agent, e.g. A biocide.

The term hydrocarbon group refers to any group containing only C atoms and H atoms and therefore covers alkyl, alkenyl, aryl, cycloalkyl, arylalkyl groups and so on.

The term "(meth) acrylate" means a methacrylate or acrylate.

The term "poly (alkylene oxide)" refers to a compound comprising repeating - [alkylene-O] units. Typically, the alkylene is ethylene or propylene.

The term "rosin" as used herein is used to cover "rosin or derivatives thereof".

The term "binder" defines a portion of the composition comprising the copolymers and the cyclic monocarboxylic acid and any other ingredients which together form a matrix which imparts substance and strength to the composition. The "binder" includes the polymer components (i) and (iii) together with the cyclic monocarboxylic acid (ii).

The term non-hydrophilic (meth) acrylic polymer defines a polymer comprising at least one (meth) acrylic acid monomer and at least one (meth) acrylate monomer (or optionally both) but less than 10% by weight of monomers of formula (I), preferably less as 5% by weight, most preferably 0% by weight of a monomer of formula (I). If less than 10% by weight of monomers of formula (I) are present, this is considered not to be hydrophilic.

When wt% of a given monomer is given, wt% refers to the total (weight) of each monomer present in the copolymer. Thus, when 2-methoxyethyl acrylate (MEA) and methyl methacrylate (MMA) are the only monomers in the copolymer component (i), wt% of MEA is calculated as (MEA (wt) / (MEA (wt) + MMA ( Weight))) x 100%.

Detailed description of the invention

This invention relates to a novel binder for a marine antifouling coating composition which exhibits remarkably low water absorption in fresh water. These compositions therefore offer a prolonged service life. The antifouling coating composition of the present invention comprises a binder containing at least three components.

The copolymer component (i)

wobei R¹ H oder CH₃ ist und R ² ein C3-C18-Substituent, der mindestens ein Sauerstoff- oder Stickstoffatom, vorzugsweise mindestens ein Sauerstoffatom enthält, oder R² eine Poly(alkylenglykol)-Gruppe darstellt. Wie hier verwendet, definiert diese Struktur „hydrophile“ (Meth)acrylat-Monomere.The invention requires the use of certain hydrophilic (meth) acrylate-based copolymers. The term hydrophilic is used herein to indicate the presence of at least 10% by weight of at least one monomer of formula (I). The copolymer component (i) therefore comprises at least one monomer of the formula (I):

wherein R ^{1 is} H or CH ₃ and R ^{2 is} a C 3 -C 18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ^{2 is} a poly (alkylene glycol) group. As used herein, this structure defines "hydrophilic" (meth) acrylate monomers.

As indicated in the formula above, the term "hydrophilic (meth) acrylate" requires that the R ² group in formula (I) contains at least one oxygen or nitrogen atom, preferably at least one oxygen atom. As explained more fully below, additional non-hydrophilic (meth) acrylate monomers may also be present in component (i) of the binder as monomers of formula (II) wherein the R ² 'moiety is comprised of C and H atoms only consists.

In one embodiment, the copolymer component (i) of the binder contains at least one monomer of the above-mentioned formula (I) in which the R ² group has the formula (CH ₂ CH ₂ O) _n -R ³ wherein R ^{3 is} a C 1 -C 10 hydrocarbon substituent, preferably a C 1 -C 10 alkyl or C 6 -C 10 aryl substituent, and n is an integer in the range of 1 to 5, preferably 1 to 3. Preferably, R ^{2 has} the formula (CH ₂ CH ₂ O) _n -R ³ wherein R ^{3 is} a C ¹ -C 10 alkyl substituent, preferably CH ₃ or CH ₂ CH ₃ , and n is an integer in the range of 1 to 3 , preferably 1 to 2. Such a monomer may include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, 2- [2- (2 -Methoxyethoxy) ethoxy] ethyl acrylate, 2- [2- (2-ethoxyethoxy) ethoxy] ethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate , 2- (2-butoxyethoxy) ethyl methacrylate, 2- [2- (2-methoxyethoxy) ethoxy] ethyl methacrylate, 2- [2- (2-ethoxyethoxy) ethoxy] ethyl methacrylate.

In one embodiment, the copolymer component (i) includes one or more of 2-methoxyethyl acrylate (MEA), 2-methoxyethyl methacrylate (MEMA), 2-ethoxyethyl methacrylate (EEMA), 2- (2-ethoxyethoxy) ethyl acrylate (EDEGA), or 2- (2-ethoxyethoxy) ethyl methacrylate (EDEGMA).

In another embodiment, the copolymer component (i) contains at least one monomer of the above formula (I) in which the R ² group is a poly (alkylene glycol) group such as a poly (ethylene glycol) group. Such a group may have a formula (CH ₂ CH ₂ O) _m -R ¹³ or (CH ₂ CH (CH ₃ ) O) _m -R ¹³ where R ^{13 is} a C 1 -C 10 hydrocarbon substituent, preferably a C 1 -C 10 hydrocarbon substituent. C10 alkyl or C6 C10 aryl substituent and m is an integer in the range of 5 to 100, preferably 5 to 20. Such a monomer may be poly (ethylene glycol) methyl ether acrylate, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) methyl ether methacrylate, poly (ethylene glycol) ethyl ether methacrylate. Preferably, such a monomer has a number average molecular weight (Mn) of 300-4,000, more preferably 300-1,000.

In one embodiment, the copolymer component (i) contains at least one monomer of the above-mentioned formula (I) in which the R ² group is a saturated cyclic group containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom. More preferably, R ^{2 is} a group WR ¹⁰ wherein R ^{10 is} a cyclic ether (such as oxolane, oxane, dioxolane, dioxane, optionally alkyl-substituted) and W is a C 1 -C 4 alkylene. Such a monomer may be furfuryl acrylate, tetrahydrofurfuryl acrylate, (1,3-dioxolan-4-yl) methyl acrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, (2,2-dimethyl-1,3-dioxolan-4-yl) methyl methacrylate. Preferred cyclic ethers should contain at least 4 atoms in the ring. Most preferably, the compound of formula (I) in this embodiment is tetrahydrofurfuryl acrylate (THFA) and tetrahydrofurfuryl methacrylate (THFMA).

In one embodiment, the hydrophilic copolymer component (i) does not contain a glycidyl group.

Monomers of the formula (I) preferably form at least 15% by weight of the copolymer (I). Particularly preferable amounts of the hydrophilic (meth) acrylate monomer of the formula (I) in the binder component (i) are 15 to 65% by weight, preferably 18 to 62% by weight, such as 20 to 50% by weight. If a mixture of monomers of the formula (I) is present, these amounts relate to the combined weight fraction of the monomers of the formula (I) in the copolymer.

The monomer of formula (I) is preferably 2-methoxyethyl acrylate (MEA), 2-methoxyethyl methacrylate (MEMA), 2-ethoxyethyl methacrylate (EEMA), tetrahydrofurfuryl acrylate (THFA), tetrahydrofurfuryl methacrylate (THFMA), 2- (2-ethoxyethoxy) ethyl acrylate (EDEGA ) or 2- (2-ethoxyethoxy) ethyl methacrylate (EDEGMA).

Non-hydrophilic (meth) acrylate monomer (s)

wobei R^1' H oder CH₃ ist und R^2' ein C1-C20-Kohlenwasserstoff-Substituent, vorzugsweise ein C1-8-Alkyl-Substituent und am meisten bevorzugt Methyl, Ethyl, n-Propyl, n-Butyl oder 2-Ethylhexyl ist. Monomere gemäß Formel (II) werden hier als „nicht hydrophile“ Monomere bezeichnet.The copolymer component (i) according to the invention also includes one or more non-hydrophilic (meth) acrylate monomers of the formula (II)

wherein R ^{1 'is} H or CH ₃ and R ^{2' is} a C 1 -C 20 hydrocarbon substituent, preferably a C 1-8 alkyl substituent, and most preferably methyl, ethyl, n-propyl, n-butyl or 2-ethylhexyl is. Monomers according to formula (II) are referred to herein as "non-hydrophilic" monomers.

In all embodiments of the invention, the copolymer component (i) includes at least one non-hydrophilic methacrylate and / or one non-hydrophilic acrylate monomer (II) together with at least one monomer of the formula (I). Monomers of formula (II) preferably form at most 85% by weight of ingredient (i), preferably 35 to 85% by weight, such as 38 to 82% by weight, such as in the range of 40 to 80% by weight. %. If a mixture of monomers of the formula (II) is present, these preferred amounts relate to the combined weight fraction of the monomers of the formula (II) in the copolymer.

In a preferred embodiment, the copolymer component (i) consists only of monomers of the formula (I) and (II).

In a preferred embodiment, more monomer of formula (II) than formula (I) is present by weight.

Preferred options for monomers of the formula (II) include methyl methacrylate (MMA), n-butyl acrylate (n-BA), n-butyl methacrylate (n-BMA), 2-ethylhexyl acrylate (2-EHA) or 2-ethylhexyl methacrylate (2-EHMA) , In all of the embodiments of the present invention, it is preferable that methyl methacrylate (MMA) or n-butyl acrylate (n-BA) is contained in the copolymer component (i).

In one embodiment, the copolymer includes one or more of the hydrophilic monomers MEA, EDEGA, EEMA,
Poly (ethylene glycol) methyl ether methyl methacrylate or THFA and at least one non-hydrophilic (meth) acrylate MMA or n-BA.

The copolymer component (i) contains less than 15% by weight of any monomer other than the above-mentioned monomers of the formula (I) and (II). It is therefore necessary that the copolymer component (i) contain less than 15% by weight of any silyl ester monomers of the formula (III) defined below, preferably less than 10% by weight of any silyl ester monomers of the formula defined below ( III). In some embodiments, component (i) may consist only of monomers of formulas (I) and (II).

The copolymer component (i) is preferably free of any (meth) acrylic acid comonomers.

The copolymer component (i) is preferably free of any metal ion-containing comonomers.

1. (i) 15 bis 65 Gew.-% mindestens eines Monomers der Formel (I)
   
   wobei R¹ H oder CH₃ ist und R ² ein C3-C18-Substituent mit mindestens einem Sauerstoff- oder Stickstoffatom, vorzugsweise mindestens einem Sauerstoffatom ist oder R² eine Poly(alkylenglykol)-Kette ist; und 35 bis 85 Gew.-% mindestens eines Monomers der Formel (II),
   
   wobei R^1' H oder CH₃ ist, und R^2' ein C1-C20-Kohlenwasserstoffrest ist; wobei das hydrophile Copolymer weniger als 15 Gew.-% andere Comonomere als die der Formel (I) oder (II) umfasst.

In a preferred embodiment, the hydrophilic copolymer comprises (i)

1. (i) from 15 to 65% by weight of at least one monomer of the formula (I)
   
   wherein R ^{1 is} H or CH ₃ and R ^{2 is} a C 3 -C 18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ^{2 is} a poly (alkylene glycol) chain; and 35 to 85% by weight of at least one monomer of the formula (II),
   
   wherein R ^{1 'is} H or CH ₃ , and R ^{2' is} a C ¹ -C 20 hydrocarbon radical; wherein the hydrophilic copolymer comprises less than 15% by weight of other comonomers than those of formula (I) or (II).

Properties of Copolymer Component (i)

The copolymer preferably has a weight average molecular weight (Mw) of 5,000 to 70,000, preferably 10,000 to 60,000, more preferably 15,000 to 40,000. Mw is measured as described in the example section.

The copolymer preferably has a polydispersity index (PDI) of 1.5 to 5.0.

The copolymer component (i) preferably has a glass transition temperature (Tg) of at least 0 ° C. The copolymer preferably has a glass transition temperature (Tg) of at least 5 ° C, preferably at least 10 ° C, such as at least 15 ° C, all values being measured according to the Tg test described in the Examples section. Values of less than 80 ° C are preferred, such as less than 75 ° C, e.g. B. less than 50 ° C. Without wishing to be limited by theory, we believe that the higher Tg contributes to the reduction in water uptake observed in the examples. If the Tg is below 0 ° C, the water absorption is higher.

The copolymer component (i) is preferably partially or completely incompatible with the mixture of the other binder components. By incompatible is meant that the binder components are incompatible according to the test procedure explained below in the Example section.

The amount of copolymer component (i) in the binder is preferably in the range of 20 to 60% by weight, such as 30 to 50% by weight (dry substance).

The finished antifouling coating composition of the present invention preferably comprises 0.5 to 45% by weight (dry matter) of copolymer component (i), such as 1.0 to 30% by weight, more preferably 5.0 to 25% by weight.

An antifouling coating composition according to the invention may optionally comprise a mixture of the copolymer constituents (i) according to the invention.

The polymer component (iii)

The binder according to the invention additionally comprises a polymer component (iii). This ingredient is different from ingredient (i). The component (iii) may be based on a non-hydrophilic (meth) acrylic acid polymer, a non-hydrophilic (meth) acrylate polymer (iii-2) or a silylester copolymer comprising at least 15% by weight of silylester monomer (iii-1) , Component (iii) may be a non-hydrophilic (meth) acrylic polymer (referred to herein as (iii-2)). Component (iii) may also be a mixture of copolymer (iii-1) and polymer (iii-2). Component (iii) therefore differs from component (i).

Silyl Ester Copolymer Component (iii-1)

wobei
R⁴ H oder CH₃ ist;
R⁵ jeweils unabhängig aus linearen oder verzweigten C_1-4-Alkylgruppen ausgewählt ist;
R⁶ jeweils unabhängig aus der Gruppe bestehend aus linearen oder verzweigten C1-C20-Alkylgruppen, C3-C12-Cycloalkylgruppen, gegebenenfalls substituierten C6-C20-Arylgruppen und -OSi(R⁷)₃-Gruppen ausgewählt ist;
jedes R⁷ unabhängig eine lineare oder verzweigte C1-C4-Alkylgruppe ist, p eine ganze Zahl von 0 bis 5 ist.Component (iii-1) comprises at least one silyl (meth) acrylate monomer. Suitable silyl (meth) acrylate monomers for use in component (iii) preferably have formula (III)

in which
R ^{4 is} H or CH ₃ ;
Each R ⁵ is independently selected from linear or branched C _1-4 alkyl groups;
Each R ⁶ is independently selected from the group consisting of linear or branched C 1 -C 20 alkyl groups, C ₃ -C 12 cycloalkyl groups, optionally substituted C 6 -C 20 aryl groups and -OSi (R ⁷ ) ₃ groups;
each R ^{7 is} independently a linear or branched C 1 -C 4 alkyl group, p is an integer from 0 to 5.

The term "alkyl" is intended to include both linear and branched alkyl groups such as methyl, ethyl, isopropyl, propyl, butyl and tert-butyl. Particularly preferred cycloalkyl groups include cyclohexyl and substituted cyclohexyl.

Examples of substituted aryl groups include aryl groups substituted with at least one substituent selected from halogens, alkyl groups having from 1 to about 8 carbon atoms, acyl groups or a nitro group. Particularly preferred aryl groups include substituted and unsubstituted phenyl, benzyl, phenalkyl or naphthyl.

Ideally, preferred silyl ester monomers are based on compounds of formula (III) in which p is 0.

wobei R⁴ H oder CH₃ ist, und
R⁶ jeweils unabhängig aus der Gruppe bestehend aus linearen oder verzweigten C1-C10-Alkylgruppen ausgewählt ist.More preferably, silyl ester monomers have the formula (IV)

wherein R ^{4 is} H or CH ₃ , and
Each R ⁶ is independently selected from the group consisting of linear or branched C ¹ -C 10 alkyl groups.

Examples of monomers containing a silyl ester functionality are well known. Monomers as defined by the general formula (III) include:

Silyl ester monomers of acrylic acid and methacrylic acid, such as tri-n-propylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tert-butyldimethylsilyl (meth) acrylate, Thexyldimethylsilyl (meth) acrylate, tert-butyldiphenylsilyl (meth) acrylate, Nonamethyltetrasiloxanyl (meth) acrylate, bis (trimethylsiloxy) methylsilyl (meth) acrylate and tris (trimethylsiloxy) silyl (meth) acrylate.

The use of triisopropylsilyl acrylate (TISA) or triisopropylsilyl methacrylate (TISMA) is preferred.

Preferably, component (iii-1) comprises at least 15% by weight of the silyl ester monomer, preferably 15 to 65% by weight, especially 35 to 60% by weight.

Preferably, the silyl ester copolymer component (iii-1) comprises, in addition to the silyl ester monomer (s), a second comonomer other than a silyl ester monomer. The second comonomer preferably has the formula (I) or (II) as defined hereinbefore. The silyl ester copolymer component (iii-1) may also comprise a monomer of the formula (I) and a monomer of the formula (II) as hereinbefore described.

Preferred monomers of formula (I) for use in the silyl ester copolymer component (iii) are EDEGA, THFA, MEA and MEMA, especially EDEGA and THFA. Preferred hydrophobic comonomers include MMA, n-BA, n-BMA and 2-EHA.

The silyl ester copolymer preferably includes at least the monomers triisopropylsilyl (meth) acrylate, a monomer of the formula (I) and a monomer of the formula (II). Preferred options of the above-mentioned formula (I) and (II) are independent of the embodiment of the component (iii). Preferred options for monomers of the formula (II) include methyl methacrylate (MMA), n-butyl acrylate (n-BA), n-butyl methacrylate (n-BMA), 2-ethylhexyl acrylate (2-EHA) or 2-ethylhexyl methacrylate (2-EHMA) , In all of the embodiments of the present invention, it is preferable that methyl methacrylate (MMA) or butyl acrylate (n-BA) is contained in the copolymer component (iii).

Preferably, the silyl ester copolymer component (iii) comprises at least 15% by weight of the monomer of the component of formula (II), especially 15 to 65% by weight.

Preferably, the silyl ester copolymer component (iii) comprises 5 to 30% by weight of the monomer of formula (I).

The silyl ester copolymer preferably has a glass transition temperature (Tg) of at least 15 ° C, preferably at least 20 ° C, such as at least 25 ° C, all values being measured according to the Tg test described in the Examples section. Values of less than 80 ° C are preferred, such as less than 75 ° C, e.g. B. less than 50 ° C.

The silyl ester copolymer component (iii) preferably has a weight-average molecular weight of 5,000 to 70,000, preferably 10,000 to 60,000, more preferably 20,000 to 50,000. Mw is measured as described in the example section.

The silyl ester copolymer preferably has a PDI of 2 to 6.

The amount of silyl ester component (iii) in the binder is preferably in the range of 10 to 60% by weight, preferably 15 to 50% by weight (dry substance).

The (meth) acrylic polymer component (iii-2)

Alternatively or additionally, component (iii) comprises a non-hydrophilic (meth) acrylic polymer comprising at least one (meth) acrylic acid monomer or at least one (meth) acrylate monomer (or both), such as one of formula (II). Component (iii-2) may be a homopolymer or a copolymer, preferably a copolymer. In particular, when a (meth) acrylic acid monomer is present, it is preferable that a second monomer is present to thereby form a copolymer. The second monomer in this embodiment is preferably a monomer of the formula (II) as defined herein.

The non-hydrophilic (meth) acrylic polymer comprises less than 10% by weight of any of the monomers of formula (I) and is preferably free of any monomers of formula (I). It is also preferably free of any silyl ester monomers.

Preferably, (meth) acrylic acid is present in the non-hydrophilic (meth) acrylic polymer component (iii-2). Preferably, (meth) acrylic acid is present in a non-hydrophilic (meth) acrylic copolymer component (iii-2), especially with a second comonomer of formula (II).

Preferred options for combination with (meth) acrylic acid include a monomer of formula (II) such as MMA, n-BMA and n-BA.

The (meth) acrylic acid content within the copolymer component (iii-2) is preferably in the range of 0.5 to 10% by weight. Monomers of formula (II) preferably constitute at least 50% by weight of the (meth) acrylic acid copolymer, such as at least 75% by weight, especially 90 to 99.5% by weight.

Alternatively, the non-hydrophilic (meth) acrylic polymer component (iii-2) may comprise one or more monomers of formula (II). Thus, in one embodiment, the non-hydrophilic (meth) acrylic polymer component (iii-2) is a (meth) acrylate homopolymer, e.g. B. a monomer of the formula (II).

Monomers of the formula (II) in this embodiment preferably constitute at least 50% by weight of the (meth) acrylic polymer, such as at least 75% by weight, especially 90 to 100% by weight. Preferred options for the formula (II) are those mentioned above in connection with component (i), such as methyl methacrylate (MMA), n-butyl acrylate (n-BA), n-butyl methacrylate (n-BMA), 2-ethylhexyl acrylate (2 -EHA) or 2-ethylhexyl methacrylate (2-EHMA).

In all of the embodiments of the present invention, it is preferable that methyl methacrylate (MM A) or n-butyl acrylate (n-BA) is contained in the polymer component (iii-2).

The (meth) acrylic polymer component (iii-2) preferably has a glass transition temperature (Tg) of less than 0 ° C, preferably less than -20 ° C, such as less than -22 ° C, all values being in accordance with the Example Tg test described. Values greater than -60 ° C are preferred, e.g. B. more than -50 ° C.

The (meth) acrylic polymer component (iii-2) preferably has a weight-average molecular weight of 5,000 to 70,000, preferably 10,000 to 60,000, more preferably 15,000 to 35,000. Mw is measured as described in the example section.

The (meth) acrylic polymer component (iii-2) preferably has a PDI of 1.5 to 5.0.

The binder composition of the present invention preferably comprises 0.5 to 25% by weight (dry substance) of (meth) acrylic polymer component (iii-2), such as 1.0 to 22% by weight, especially 2.0 to 18% by weight. %.

In general, the amount of component (iii) (combined amounts of (iii-1) + (iii-2)) in the binder is preferably in the range of 5 to 70% by weight, preferably 10 to 60% by weight. preferably 10 to 50 wt .-%, in particular 15 to 50 wt .-% (dry matter).

It is preferable that the (meth) acrylic polymer component (iii-2) is present. When a silyl ester copolymer component (iii-1) is present, it is also preferable that a (meth) acrylic polymer component (iii-2) is present. The weight ratio of these components may be 95 to 50:50 to 5, preferably 90 to 60:40 to 10 part (iii-1) to (iii-2). Thus, when both (iii-1) and (iii-2) are present, it is preferred that an excess of component (iii-1) is present.

The antifouling coating compositions of the invention preferably comprise at least 0.5% by weight (dry matter) of component (iii), such as at least 1% by weight. The upper limit of component (iii) may be 20% by weight, such as 15% by weight.

Preparation of copolymer component (i) and polymer component (iii)

The polymers can be prepared using polymerization reactions known in the art. Acrylic polymers are preferably made using addition polymerization or chain growth polymerization. Examples of suitable addition polymerization techniques include free radical polymerization, anionic polymerization, and adequately controlled polymerization techniques. The polymer can be obtained, for example, by polymerizing a monomer mixture in the presence of a polymerization initiator and optionally a chain transfer agent by any of various methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization in a conventional manner or by controlled polymerization techniques. In the preparation of a coating composition using this Polymer, the polymer is preferably diluted with an organic solvent to yield a polymer solution having a suitable viscosity. Therefore, it is desirable to use solution polymerization.

Examples of polymerization initiators for free radical polymerization include azo compounds such as dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (isobutyronitrile) and 1 , 1'-azobis (cyanocyclohexane) and peroxides such as tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy diethyl acetate, tert-butyl peroxy isobutyrate, di-tert-butyl peroxide, tert-butyl peroxybenozate and tert-butyl peroxy isopropyl carbonate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, 1,1-di (tert-amylperoxy) cyclohexane and dibenzoyl peroxide. These compounds are used alone or as a mixture of two or more thereof.

Examples of the organic solvent include aromatic hydrocarbons such as xylene, toluene or mesitylene; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone or cyclohexanone; Esters such as butyl acetate, tert-butyl acetate, amyl acetate, ethylene glycol methyl ether acetate, butyl propionate or isobutyl isobutyrate; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane or tetrahydrofuran, alcohols such as n-butanol, isobutanol or benzyl alcohol; Ether alcohols such as butoxyethanol or 1-methoxy-2-propanol; cyclic terpenes such as d-limonene; aliphatic hydrocarbons such as benzene and optionally a mixture of two or more solvents. These compounds are used alone or as a mixture of two or more thereof. The copolymer components (i) or (iii) are preferably random copolymers.

The cyclic monocarboxylic acid component (ii)

The binder according to the invention comprises at least one cyclic monocarboxylic acid. The cyclic monocarboxylic acid contains a single functional carboxyl group (which may be in its salt form). The cyclic monocarboxylic acid may contain one or more cyclic rings. In particular, such rings may be condensed rings. The cyclic monocarboxylic acid is preferably selected from rosin acids, a derivative of rosin acids, C6-20 cyclic carboxylic acids, and mixtures thereof. Suitable monocarboxylic acids include rosin acids such as abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, palustric acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, cinnamic acid; Naphthenic acids, methylisohexenylcyclohexenecarboxylic acids, such as 1-methyl-3- (4-methyl-3-pentenyl) -3-cyclohexen-1-yl-carboxylic acid, 1-methyl-4- (4-methyl-3-pentenyl) -4- cyclohexen-1-yl-carboxylic acid, trimethylisobutenylcyclohexenecarboxylic acids such as 1,4,5-trimethyl-2- (2-methyl-1-propenyl) -3-cyclohexen-1-yl-carboxylic acid and 1,5,6-trimethyl-3 - (2-methyl-1-propenyl) -4-cyclohexene-1-yl-carboxylic acid and mixtures thereof. Ideally, the cyclic monocarboxylic acid is a rosin or a derivative thereof.

The monocarboxylic acid can be used to adjust the self-polishing properties and mechanical properties of the antifouling coating film. The amount of the component (ii) in the binder is preferably in the range of 10 to 70% by weight (dry matter), preferably 20 to 50% by weight.

The rosin used in the invention may be a rosin or a derivative thereof, such as a salt thereof, e.g. B. as described below. Examples of rosin materials include root resin, tall resin and gum rosin; Rosin derivatives such as hydrogenated and partially hydrogenated rosin, disproportionated rosin, rosin modified with maleic acid, rosin modified with fumaric acid, metal salts of rosin and rosin derivatives such as copper rosinate, zinc resinate, calcium resinate, magnesium resinate, and others as described in U.S. Pat WO 97/44401 described. Preference is given to gum rosin and derivatives of gum rosin.

In the present invention, the antifouling composition preferably comprises 0.5 to 25% by weight, preferably 1 to 20% by weight (dry substance) of a cyclic monocarboxylic acid material, preferably 3 to 15% by weight (dry substance).

• die Menge des Bestandteils (ii) liegt im Bereich von 10 bis 70 Gew.-% des Bindemittels (Trockensubstanz); und
• die Menge des Bestandteils (iii) liegt im Bereich von 10 bis 60 Gew.-% (Trockensubstanz).

In one embodiment of the binder according to the invention, therefore, the amount of component (i) is in the range from 20 to 60% by weight of the binder (dry substance);

• the amount of the component (ii) is in the range of 10 to 70% by weight of the binder (dry substance); and
• the amount of the component (iii) is in the range of 10 to 60% by weight (dry matter).

The properties of the antifouling coating can be adjusted by varying the relative amounts of binder copolymer and rosin ingredients.

Other binder components

• Ester von Kolophonium und hydriertem Kolophonium, wie etwa Methylester, Glycerinester, Poly(ethylenglykol)ester, Pentaerythritester, bevorzugt sind Ester von Balsamharz und hydriertem Balsamharz,
• dimerisiertes Kolophonium und polymerisiertes Kolophonium,
• Polymere mit Säurefunktion, deren Säuregruppe mit zweiwertigen, an einen einwertigen organischen Rest gebundenen Metallen oder zweiwertigen, an einen Hydroxylrest gebundenen Metallen blockiert ist,
• hydrophile Copolymere, zum Beispiel (Meth)acrylat-Copolymere, zum Beispiel Poly(N-vinylpyrrolidon)-Copolymere und Poly(ethylenglykol)-Copolymere,
• Vinyletherpolymere und Copolymere, wie etwa Poly(methylvinylether), Poly(ethylvinylether), Poly(isobutylvinylether), Poly(vinylchlorid-co-isobutylvinylether),
• aliphatische Polyester, wie etwa Poly(milchsäure), Poly(glykolsäure), Poly(2-hydroxybuttersäure), Poly(3-hydroxybuttersäure), Poly(4-hydroxyvaleriansäure), Polycaprolacton und aliphatische Polyestercopolymere, die zwei oder mehr Einheiten enthalten, die aus den oben genannten Einheiten ausgewählt sind, und andere Kondensationspolymere wie etwa Polyoxalate,
• Alkydharze und modifizierte Alkydharze,
• Kohlenwasserstoff-Harz, wie etwa ein Kohlenwasserstoff-Harz, das nur aus der Polymerisation von mindestens einem Monomer ausgewählt aus einem aliphatischen C5-Monomer, einem aromatischen C9-Monomer, einem Inden-Cumaron-Monomer oder einem Terpen oder aus Mischungen davon gebildet wird.

In addition to the above-described components (i) to (iii), an additional binder component may be used to adjust the properties of the antifouling coating film. Examples of binders that can be used include:

• Esters of rosin and hydrogenated rosin, such as methyl esters, glycerol esters, poly (ethylene glycol) esters, pentaerythritol esters, esters of gum rosin and hydrogenated gum rosin are preferred,
• dimerized rosin and polymerized rosin,
• Acid-functional polymers whose acid group is blocked with divalent metals bonded to a monovalent organic radical or divalent hydroxyl-bonded metals,
• hydrophilic copolymers, for example (meth) acrylate copolymers, for example poly (N-vinylpyrrolidone) copolymers and poly (ethylene glycol) copolymers,
• Vinyl ether polymers and copolymers, such as poly (methyl vinyl ether), poly (ethyl vinyl ether), poly (isobutyl vinyl ether), poly (vinyl chloride-co-isobutyl vinyl ether),
• aliphatic polyesters such as poly (lactic acid), poly (glycolic acid), poly (2-hydroxybutyric acid), poly (3-hydroxybutyric acid), poly (4-hydroxyvaleric acid), polycaprolactone, and aliphatic polyester copolymers containing two or more units selected from the above-mentioned units are selected, and other condensation polymers such as polyoxalates,
• Alkyd resins and modified alkyd resins,
• Hydrocarbon resin, such as a hydrocarbon resin, which is formed only from the polymerization of at least one monomer selected from C5 aliphatic monomer, C9 aromatic monomer, indene coumarone monomer or terpene or mixtures thereof.

Acyclic monocarboxylic acid

In one embodiment, the antifouling coatings of the invention may comprise a liquid C 12 -C 24 monocarboxylic acid or a salt thereof, i. that is, an acid containing a single -COOH moiety within the molecule, or its salt. Such acids contain an acidic "head group" and a nonpolar "tail group" which is preferably a branched chain of carbon atoms. The monocarboxylic acid preferably contains only C, H and O atoms.

The use of such a material may allow improved control of leach layer formation (reduced thickness) than a comparable composition that does not contain the acid component. In addition, compositions containing the acid component should exhibit a similar level of polishing while maintaining or even reducing the viscosity of the paint.

This ingredient may comprise one or more monocarboxylic acids selected from monocarboxylic, liquid, acyclic, saturated C12-C24 monocarboxylic acids, or liquid acyclic, branched C12-C24 monocarboxylic acids. The acid should therefore not be a linear, unsaturated carboxylic acid. It is preferred if the acid is saturated.

The monocarboxylic acid ideally has the formula R ₁₁ COOH, wherein R _{11 is} an acyclic branched C 11-23 alkyl or alkenyl group or an acyclic, saturated, linear or branched C 11-23 alkyl group. Preferably, R _{11 is} an acyclic branched C 11-23 alkyl group.

Most preferably, the acyclic monocarboxylic acid is a C12-24 branched fatty acid or mixture thereof.

The acid is preferably liquid at room temperature and pressure (23 ° C and 1 atm).

Preferably, the acid component is branched. A branched acid must contain a tertiary or quaternary carbon atom in its tail group.

It is understood that many of the acids can be derived from natural sources, and in such case are typically present in isolated form as a mixture of acids of different chain lengths and varying degrees of branching. When the acid is used as a mixture of ingredients, the acid may have a degree of branching greater than 50%, preferably greater than 70%, greater than 80%, or even greater than 90%. The percentage is in wt .-%. By way of example, a C18 acid component having a degree of branching of at least 50% contains not more than 50 parts by mass of linear C18 acids (n-stearic acid, n-oleic acid, n-linoleic acid, etc.), the rest consisting of branched C18 acids (generic). Isostearic acid "," isoleic acid "," isolinoleic acid ", etc.).

In a preferred aspect, the acid is an acyclic C 14 -C 20 monocarboxylic acid, preferably an acyclic C 16 -C 20 monocarboxylic acid, in particular an acyclic C 16-18 monocarboxylic acid. Preferably, the carbon chains contain an even number of carbon atoms. In a preferred aspect, the acid has a molecular weight of less than 350 g / mol, preferably less than 320 g / mol, and more preferably less than 300 g / mol.

In a preferred aspect, the acid has an acid number of less than 310, more preferably less than 300, such as less than 290 or even less than 280. "Acid value" is a well-known parameter and is the mass of KOH in milligrams used to neutralize one gram of acid is required (ISO 660: 2009).

In a preferred aspect, the acid has an iodine value of less than 50, more preferably less than 40, less than 30 or less than 20. In some embodiments, the acid may be a saturated acid having an iodine value of zero. "Iodine Number" is a well-known parameter and is the mass of iodine in grams that reacts with 100 grams of the acid (AOCS Tg la-64).

Particularly preferred acids for use include one or more selected from the group consisting of isopalmitic acid or isostearic acid or mixtures thereof. In any case, the acid can be natural or synthetic. A mixture of isopalmitic acid and isostearic acid is available with a suitable degree of branching of oleone under the names Radiacid 0906, Radiacid 0907 and Radiacid 0909. A particularly highly branched isostearic acid is the product Fineoxocol isostearic acid N from Nissan Chemicals.

Particularly preferred acids are isostearic acid and isopalmitic acid, each with a degree of branching greater than 70% and an iodine value of less than 30. Particularly suitable ingredients are the products Fineoxocol isostearic acid N from Nissan Chemicals and Radiacid 0906, Radiacid 0907 or Radiacid 0909 from Oleon.

It is understood that any acid can form a salt when metal ions are present. Although the inventors suggest adding the acid in its acid form, it is also possible to add the acid in its salt form. The acid can also be converted to a salt form in the composition. The% by weight of acid added to the composition should be calculated on the assumption that the acid is in its acid form.

If another binder component is present, it ideally constitutes less than 10% by weight of the binder, ideally less than 5% by weight. In a preferred embodiment, no additional binder component is present and the binder consists only of components (i) to (iii).

In a preferred embodiment of the binder, the weight ratio (dry matter) of copolymer (i): component (ii) may range from 20:80 to 80:20, preferably from 30:70 to 70:30, more preferably from 40:60 until 60:40.

In a preferred embodiment of the binder, the weight ratio (dry matter) of polymers (i) + (iii): component (ii) may range from 35:65 to 85:15, preferably from 40:60 to 80:20, more preferably from 45:55 to 75:25.

In one embodiment, component (i) of the binder is partially or completely incompatible, ie it does not form a homogeneous mixture with the other binder components present as determined according to the method in the experimental section (determination of the incompatibility of the hydrophilic copolymer (i) in binder mixtures of component (i), (ii) and (iii)).

The binder composition of the invention is ideally incorporated into an antifouling coating composition. An antifouling coating composition of the present invention may comprise 15 to 50% by weight of the binder, and more particularly, the antifouling coating composition of the present invention comprises 15 to 50% by weight of the binder components (i) to (iii) as defined in claim 1.

biocide

The antifouling coating preferably additionally comprises a compound that can prevent or remove marine fouling on a surface. The terms anti-fouling agents, inhibitors of growth, biocide, toxins are used in the industry to describe known compounds that cause marine surface fouling on a surface. The antifouling agents according to 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. As copper (I) oxide and copper (II) oxide, copper alloys, eg. As copper-nickel alloys, copper salts, z. As copper (I) thiocyanate and copper sulfide. Examples of organometallic marine antifoulants include zinc 2-pyridinethiol-1-oxide [zinc pyrithione]; Organo copper compounds such as copper 2-pyridinethiol-1-oxide [copper pyrithione], copper acetate, copper naphthenate, copper 8-quinolinonate [oxine-copper], copper nonylphenolsulfonate, copper bis (ethylenediamine) bis (dodecylbenzenesulfonate), and copper bis (pentachlorophenolate) ; Dithiocarbamate compounds such as zinc bis (dimethyldithiocarbamate) [Ziram], zinc ethylene bis (dithiocarbamate) [Zineb], manganese ethylene bis (dithiocarbamate) [Maneb] and manganese ethylene bis (dithiocarbamate) complexed with zinc salt [Mancozeb].

Examples of organic, marine antifouling agents include heterocyclic compounds such as 2- (tert-butylamino) -4- (cyclopropylamino) -6- (methylthio) -1,3,5-triazine [Cybutryn], 4,5-dichloro-2- n -octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one [DCOIT], 2- (thiocyanatomethylthio) -1,3-benzothiazole [benthiazole], 3-benzo [b] thien-2-yl yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide [bethoxazine] and 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine; Urea derivatives such as 3- (3,4-dichlorophenyl) -1,1-dimethylurea [diuron]; Amides and imides of carboxylic acids, sulfonic acids and sulfenic acid such as N- (dichlorofluoromethylthio) phthalimide, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfamide [dichlorofluanide], N-dichlorofluoromethylthio-N', N'-dimethyl-Np tolylsulfamide [tolylfluanid] and N- (2,4,6-trichlorophenyl) maleimide; other organic compounds such as pyridinetriphenylborane, aminetriphenylborane, 3-iodo-2-propynyl-N-butylcarbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile [chlorothalonil], p - ((diiodomethyl) sulfonyl) toluene, and 4-bromo -2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile [tralopyril].

Other examples of marine antifouling agents include tetraalkylphosphonium halides, guanidine derivatives, imidazole containing compounds such as 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine], and derivatives, macrocyclic lactones including avermectins and derivatives thereof such as ivermectin. Spinosyns and derivatives thereof such as spinosad, capsaicin and derivatives such as phenylcapsaicin and enzymes such as oxidase, or proteolytic, hemicellulolytic, cellulolytic, lipolytic and amylolytically active enzymes.

Usually, an antifouling coating composition contains copper biocides such as metallic copper, cuprous oxide, copper thiocyanate, and the like.

The copper (I) oxide material typically has a particle diameter distribution of 0.1-70 μm and an average particle size (d50) of 1-25 μm. The copper (I) oxide material may contain a stabilizing agent to prevent surface oxidation and caking. Examples of commercially available copper (I) oxide include Nordox copper oxide red paint quality, Nordox XLT from Nordox AS, copper oxide from Furukawa Chemicals Co., Ltd., Red Copp 97N, Purple Copp, Lolo Tint 97N, Chemet CDC, Chemet LD from American Chemet Corporation, copper (I) oxide red from Spiess-Urania, copper oxide Roast, copper oxide Electrolytic from Taixing Smelting Plant Co., Ltd.

Instead of copper biocides, a number of organic biocides may be used, such as 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine] and 4-bromo-2- (4-chlorophenyl) - 5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile [tralopyril]. Any known biocide can be used in the invention.

Preferred biocides are copper (I) oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylene bis (dithiocarbamate) [zineb], 2- (tert-butylamino) -4- (cyclopropylamino) -6- (methylthio) -1,3,5 -triazine [cubutryn], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfamide [dichlorofluanide], N- Dichlorofluoromethylthio-N ', N'-dimethyl-N-p-tolylsulfamide [tolylfluanid], 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine], triphenylboranopyridine [TPBP] and 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile [tralopyril].

A mixture of biocides may be used, as known in the art, as various biocides act against different fouling marine organisms. In general, mixtures of antifouling agents are preferred.

In one embodiment, the antifouling coating composition comprises copper (I) oxide and / or copper thiocyanate and one or more biocides selected from copper pyrithione, zinc ethylenebis (dithiocarbamate), 4,5-dichloro-2-octyl-4-isothiazolin-3-one. and medetomidine are selected.

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

If present, the combined amount of biocides may account for up to 70% by weight of the coating composition, such as from 4 to 60% by weight, e.g. B. 5 to 60 wt .-%. When copper is present, an appropriate amount of biocide may be 20 to 60% by weight in the coating composition. When copper is avoided, smaller amounts can be used, such as from 0.1 to 20% by weight, e.g. B. 0.2 to 15 wt .-%. It is understood that the amount of biocide varies depending on the end use and the biocide used.

Some biocides may be encapsulated or adsorbed or bound to other materials for controlled release in an inert carrier. These percentages are based on the amount of active biocide present and therefore not on any vehicle used.

Other ingredients

In addition to the binder and any of the optional ingredients described above, the antifouling coating composition according to the present invention may optionally further comprise one or more ingredients selected from, among others, binders, inorganic or organic pigments, extenders and fillers, additives, solvents and thinners are.

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 and iron oxides. Examples of organic pigments include phthalocyanine compounds, azo pigments and carbon black.

Examples of extenders and fillers are minerals such as dolomite, plastorite, calcite, quartz, barite, magnesite, aragonite, silica, wollastonite, talc, chlorite, mica, kaolin, ground silica and feldspar; synthetic inorganic compounds such as zinc oxide, zinc phosphate, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, ground silica and precipitated silica; Polymeric and inorganic microspheres such as uncoated or coated, hollow and solid glass beads, uncoated or coated, hollow and solid ceramic beads, porous and compact beads of polymeric materials such as poly (methyl methacrylate), poly (methyl methacrylate-co-ethylene glycol dimethacrylate), poly (styrene -coethylene glycol dimethacrylate), poly (styrene-co-divinylbenzene), polystyrene or poly (vinyl chloride).

Preferably, the total amount of diluent, fillers and / or pigment present in the compositions of the invention is based on the total weight of the Composition 0-70 wt .-%, more preferably 1-60 wt .-% and even more preferably 2-50 wt .-%. It will be apparent to those skilled in the art that the extender and pigment content will vary depending on the other constituents present and the end use of the coating composition.

dehydrator

The antifouling coating composition of the present invention optionally comprises a dehydrating agent, also referred to as a water scavenger or desiccant. Preferably, the dehydrating agent is a compound that removes water from the composition in which it is present. Dehydrating agents improve the storage stability of the antifouling coating composition containing water-reactive compounds, e.g. Silylester copolymers, by introducing moisture introduced by raw materials such as pigments and solvents, or by reaction between carboxylic acid compounds and specific compounds, e.g. B. divalent metal oxides, formed water is removed in the antifouling coating composition. The dehydrating agents and drying agents that can be used in the antifouling coating compositions include organic and inorganic compounds.

The dehydrating agents may be hygroscopic materials that absorb water or bind water as water of crystallization and will often be referred to as desiccants. Examples of desiccants include calcium sulfate hemihydrate, anhydrous calcium sulfate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves and zeolites.

The dehydrating agent may be a compound that chemically reacts with water. Examples of dehydrating agents which react with water include orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate and triethyl orthopropionate; ketals; acetals; enolether; Orthoborates such as trimethyl borate, triethyl borate; Tripropyl borate, triisopropyl borate, tributyl borate and tri-tert-butyl borate; Organosilanes such as trimethoxymethylsilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane and ethylpolysilicate.

Preferred dehydrating agents are those which chemically react with water. Particularly preferred dehydrating agents are organosilanes. Preferably, the dehydrating agent in the compositions of the present invention is based on the total weight of the composition in an amount of 0-5 wt%, more preferably 0.5-2.5 wt%, and even more preferably 1.0-2.0 Wt .-% present.

Solvent and thinner

It is highly preferable that the antifouling composition contains a solvent. This solvent is preferably volatile and is preferably organic. Examples of organic solvents and diluents are aromatic hydrocarbons such as xylene, toluene or mesitylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, diisobutyl ketone, methyl propyl ketone, cyclopentanone or cyclohexanone, esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate , Propyl propionate or butyl propionate, isobutyl isobutyrate, ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane or tetrahydrofuran, alcohols such as n-butanol, isobutanol or benzyl alcohol, ether alcohols such as butoxyethanol or 1-methoxy-2-propanol, cyclic terpenes such as Limonene, aliphatic hydrocarbons such as benzene and optionally a mixture of two or more solvents and thinners. Examples of other diluents include water.

Preferred solvents are aromatic solvents and 1-methoxy-2-propanol, especially xylene and mixtures of aromatic hydrocarbons and 1-methoxy-2-propanol.

The amount of solvent is preferably as low as possible. The solvent content can be up to 50% by weight of the composition, preferably up to 45% by weight of the composition, such as up to 40% by weight, but can also be at most 15% by weight or less, e.g. B. 10 wt .-% or less. Again, it will be apparent to those skilled in the art that the solvent content will vary depending on the other ingredients present and the end use of the coating composition.

Alternatively, the coating may be dispersed in an organic nonsolvent for the film-forming ingredients in the coating composition or in an aqueous dispersion.

The antifouling coating composition of the invention should preferably have a solids content of greater than 40% by volume, e.g. B. more than 45 vol .-%, such as more than 50 vol .-%, preferably more than 55 vol .-%.

More preferably, the antifouling coating composition should have a volatile organic content (VOC) of less than 500 g / L, preferably less than 400 g / L, e.g. B. have less than 390 g / L. The VOC content can be calculated (ASTM D5201-01) or measured (US EPA Method 24 or ISO 11890-1 ).

Other additives

Examples of other additives which may be added to an antifouling coating composition are reinforcing agents, thixotropic agents, thickeners, anti-settling agents, wetting and dispersing agents, plasticizers and stabilizers.

Examples of reinforcing agents are flakes and fibers. Fibers include natural and synthetic inorganic fibers such as silicon-containing fibers, carbon fibers, oxide fibers, carbide fibers, nitride fibers, sulfide fibers, phosphate fibers, mineral fibers; metallic fibers; natural and synthetic organic fibers such as cellulose fibers, rubber fibers, acrylic fibers, polyamide fibers, polyimide, polyester fibers, polyhydrazide fibers, polyvinyl chloride fibers, polyethylene fibers, and others as in WO 00/77102 described. Preferably, the fibers have an average length of 25 to 2,000 microns and an average thickness of 1 to 50 microns with a ratio between the average length and the average thickness of at least 5.

Examples of thixotropic agents, thickeners and anti-settling agents are silicas such as fumed silicas, organomodified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil wax, ethyl cellulose, aluminum stearate and mixtures thereof.

Examples of plasticizers are chlorinated paraffins, phthalates, phosphate esters, sulfonamides, adipates and epoxidized vegetable oils.

Examples of stabilizers contributing to the storage stability of the antifouling coating composition are carbodiimide compounds such as bis (2,6-diisopropylphenyl) carbodiimide and poly (1,3,5-triisopropylphenylene-2,4-carbodiimide) and others described in U.S. Pat patent EP 2725073 to be discribed.

In general, each of these optional ingredients may be present in an amount in the range of 0.1 to 20 weight percent, typically 0.5 to 20 weight percent, preferably 0.75 to 15 weight percent of the antifouling composition , It is understood that the amount of these optional ingredients varies depending on the end use.

The antifouling coating composition of the invention may be applied to all or part of a surface of an article which is subject to fouling. The surface may be under water permanently or intermittently (eg due to tidal movement, different cargo load or sea state). The surface of the article is typically the hull of a vehicle or the surface of a solid marine object, such as an oil rig or buoy. The application of the coating composition may be by any convenient means, e.g. As by painting (eg., With a brush or a roller) or spraying the coating on the object. Typically, the surface must be separated from the seawater to allow for coating. The application of the coating can be achieved as conventionally known in the art.

When applying the antifouling coating to an article (e.g., a ship's hull), the surface of the article is typically not protected by a single layer of antifouling agent alone. Depending on the type of surface, the antifouling coating can be applied directly to an existing coating system. Such a coating system may include multiple layers of paints of various types (eg, epoxy, polyester, vinyl or acrylic, or mixtures thereof). If the surface is clean and has an intact antifouling coating from an earlier application, the new antifouling paint can be applied directly, typically with one or two coatings, more in exceptional cases.

Alternatively, the craftsman may start with an uncoated surface (eg, steel, aluminum, plastic, composite, fiberglass, or carbon fiber). To protect such a surface, the complete coating system typically includes one or two layers of a corrosion inhibiting coating, a layer of an adhesion promoter, and one or two layers of antifouling paint. A person skilled in the art is familiar with these coating layers.

In exceptional cases, additional antifouling coating layers may be applied.

In a further embodiment, therefore, the invention provides a substrate coated with a corrosion inhibiting coating layer, such as an epoxy primer, a primer layer, and an antifouling coating composition as defined herein.

The invention will now be defined with reference to the following non-limiting examples.

Materials and procedures

Abbreviations Surname AMBN 2,2'-azobis (2-methylbutyronitrile) BDGMA 2- (2-butoxyethoxy) ethyl methacrylate EDEGA 2- (2-ethoxyethoxy) ethyl acrylate EEMA 2-ethoxyethyl MEA 2-methoxyethyl MEMA 2-methoxyethyl MMA methyl methacrylate MPEG-MA 300 Poly (ethylene glycol) methyl ether methacrylate, Mn 300 n-BA n-butyl acrylate PM 1-methoxy-2-propanol THFA tetrahydrofurfuryl TISA triisopropylsilyl Tisma Triisopropylsilylmethacrylat Solvesso 100 was acquired by Brenntag.

Determination of the viscosity of the polymer solution

The viscosity of the polymers was determined according to ASTM D2196-15 Test Method A using a Brookfield DV-I Viscometer with LV-2 or LV-4 spindle at 12 rpm. The polymers were tempered to 23.0 ° C ± 0.5 ° C prior to measurements.

Determination of the content of nonvolatile fractions of the polymer solutions

The content of nonvolatile fractions of the polymer solutions was determined according to ISO 3251. To this was taken a test sample of 0.5 g ± 0.1 g and dried in a ventilated oven at 105 ° C for 3 hours. The weight of the remaining material is considered to be nonvolatile (nfA). The content of nonvolatile matter is expressed in weight percent. The value given is the mean of three parallel experiments.

Determination of the average molecular weight distribution of the polymer

The polymers were characterized by gel permeation chromatography (GPC). The molecular weight distribution (MWD) was determined using a Malvern Omnisec Resolve and Reveal system with two Agilent 5-μm mixed-D PL-gel, 5 μm mixed columns. The columns were calibrated by conventional calibration using narrow polystyrene standards.

The samples were prepared by dissolving an amount of the polymer solution and correspond to 25 mg of dry polymer in 5 ml of THF. Before sampling for GPC measurements, the samples were held at room temperature for 3 hours. Prior to analysis, the samples were filtered through 0.45 μm nylon filters. The weight average molecular weight (Mw) and polydispersity index (PDI), expressed as Mw / Mn, are listed.

The following are the analysis conditions: detector RI cell volume 12 μl column assembly Two columns in series, Agilent PL gel, 5 μm, Mixed-D Mobile phase THF flow 1 ml / min injection volume 100 μl Temperature autosampler 25 ° C Column oven temperature 35 ° C Detector Oven Temperature 35 ° C data processing Omnisec 5.1 calibration standards Polystyrene, Medium, EasiVials (4 ml) by Agilent Red, yellow and green

Determination of the glass transition temperature

The glass transition temperature (Tg) is obtained from Differential Scanning Calorimetry (DSC). The DSC measurements were carried out on a TA device DSC Q200. The samples were prepared by means of a test coat on a glass plate with a film puller with a 100 μm gap width. The glass plates were dried for 24 hours at 23 ° C and for 24 hours at 50 ° C in a ventilated oven. About 10 mg of dry polymer material was removed from the glass plates and transferred to aluminum pan with lid. The measurements were carried out by a heating-cooling-heating method (-80 ° C to 120 ° C) at a heating rate of 10 ° C / min and a cooling rate of 10 ° C / min. For reference, an empty crucible is used. The data was processed using TA Instruments Universal Analysis software. The inflection point of the glass transition region on the second heating, as defined in ASTM E1356-08, is reported as the Tg of the polymers.

Determination of the viscosity of the paint using a cone and plate viscometer

The viscosity of the antifouling paint compositions was determined according to ISO 2884-1: 1999 using a digital cone and plate viscometer set at a temperature of 23 ° C, operating at a shear rate of 10,000 s ^-1 and having a viscosity measuring range of 0-5 ° C. 10 P delivered. The result is given as the mean of three measurements.

The results are shown in Table 8-13.

Gravimetric water uptake in fresh water / deionized water

The water uptake in the coating films was determined by a gravimetric method. The paints were applied to pre-weighed and numbered sandblasted glass plates (5.0 x 7.5 cm) using a 300 μm gap film applicator. The films were dried under ambient conditions for at least 1 day, at 50 ° C overnight and then in a desiccator for 24 hours under vacuum. After drying, the coated glass plates were weighed and placed in containers filled with distilled water. At the time of reading, the plates and paint surfaces were rapidly dried using compressed air. The plates were weighed (m _directly ) and then allowed to dry for 2 days under ambient conditions and then placed in a desiccator under vacuum for 24 hours, after which they were weighed again (m _dry ). The weight difference before and after the Drying with respect to the dry weight of the paint film after exposure is expressed as water absorption in percent. $$\text{Amount of water intake}=\left({\text{m}}_{\text{directly}}-{\text{m}}_{\text{dry}}\right)\text{/}\left({\text{m}}_{\text{dry}}-{\text{m}}_{\text{empty plate}}\right)$$

The readings were made after 34 days. The results are shown in Table 8-13.

Calculation of Volatile Organic Compounds (VOC) Content of Antifouling Coating Composition

The volatile organic compound (VOC) content of the antifouling coating composition is calculated according to ASTM D5201.

Determination of incompatibility of the hydrophilic copolymer (i) in binder mixtures of constituents (i), (ii) and (iii).

A mixture of binder components (i), (ii), (iii) and Irgazin Red L 3670 HD was mixed together in 10 ml glass vials. The proportions are given in Table 3-7. The vials were mixed for 3 minutes using a vibrating shaker Collomix Viba. The samples were allowed to stand at room temperature for at least 24 hours, and then the incompatibility was assessed visually. The copolymer (i) is considered incompatible when at least 2 different phases were recognized. Irgazin Rot L 3670 HD was added to make the phase separation more visible. The results are given in Table 3-7 as incompatible (U) or compatible (V). The binder mixtures should have 52-57 wt.% Solids. Xylene: PM should be used at a weight ratio of 85:15 to 95: 5.

Determination of polishing of anti-fouling coating films on a rotating disk in seawater

The polishing was determined by measuring the reduction of the film thickness of a coating film. PVC was used for this test. The coating compositions were applied to the disk as radial strips using a film applicator. The thicknesses of the dry coating films were measured by a stylus instrument. The PVC discs were mounted on an axle and rotated in a container through which seawater flowed. In this case, natural, filtered seawater was used whose temperature was adjusted to 25 ° C ± 2 ° C. The speed of the rotating axle provided a mean simulated speed of 16 knots on the pulley. The PVC disks were taken out to measure the film thickness. Before measuring the film thickness, the disks were rinsed and left to dry at room temperature overnight. The results were reported as film reduction, d. h., as the difference between the initial film thickness and the measured thickness at a given time.

General procedure for the preparation of the copolymer solution P1 to P12 and C1 to C8 (copolymer component (i))

The polymers studied were all prepared in the same manner by charging 28.84 parts xylene and 6.75 parts PM into a thermostated reactor equipped with a stirrer, reflux condenser, nitrogen inlet and feed inlet. The reactor was heated to 95 ° C and held there. A masterbatch of monomers, 6.57 parts xylene, 3.25 parts PM, and initiator was prepared and charged to the reactor at a constant rate over 2 hours and 30 minutes under a nitrogen atmosphere. After an additional hour of reaction, a subsequent addition of a starter accelerating initiator solution and 4.6 parts of xylene was charged to the reactor at a constant rate over 15 minutes. The reactor was held at the reaction temperature for an additional hour and then cooled to room temperature. Exceptions are the polymers P4 and P6, in which the reaction temperatures were 105 ° C and 85 ° C, respectively.

An overview of the various polymers synthesized is given in Tables 1 and 2. The amount of ingredients is given in parts by weight.

Preparation of Acrylic Copolymer Solution A-1 (Polymer Component (iii-2))

19.20 parts of xylene and 7.70 parts of 1-methoxy-2-propanol were charged to a thermostated reactor equipped with a stirrer, reflux condenser, nitrogen inlet and feed inlet. The reactor was heated to 85 ° C and held there. A premix of 53.80 parts of n-butyl acrylate, 3.40 parts of n-butyl methacrylate, 2.40 parts of methyl methacrylate, 0.40 parts of methacrylic acid, 0.93 parts of 2,2'-azobis (2-methylbutyronitrile), and 8.00 Parts of xylene were prepared and loaded into the reactor at a constant rate over 2 hours and 30 minutes under a nitrogen atmosphere. After an additional hour of reaction, a subsequent addition of an accelerating starter solution of 0.20 parts of 2,2'-azobis (2-methylbutyronitrile) and 4.00 parts of xylene was charged to the reactor at a constant rate over 15 minutes. The reactor was held at the reaction temperature for an additional hour and then cooled to room temperature. The amount of ingredients is given in parts by weight. The copolymer solution A-1 had a viscosity of 327 cP, a nonvolatile content of 61.7 wt%, a Mw of 36,200, a PDI of 3.23 and a Tg of -39 ° C.

Preparation of Silyl Ester Acrylic Copolymer Solution A-2 (Polymer Component (iii-1))

35.00 parts of xylene were charged to a thermostated reactor equipped with a stirrer, reflux condenser, nitrogen inlet and feed inlet. The reactor was heated to 85 ° C and held there. A premix of 16.50 parts of methyl methacrylate, 3.50 parts of 2-methoxyethyl acrylate, 30.00 parts of triisopropylsilyl acrylate, 0.50 parts of 2,2'-azobis (2-methylbutyronitrile) and 5.00 parts of xylene was prepared and reacted with a constant Speed charged into the reactor for 2 hours under a nitrogen atmosphere. After an additional hour of reaction, a subsequent addition of an accelerating starter solution of 0.10 parts of 2,2'-azobis (2-methylbutyronitrile) and 5.00 parts of xylene was charged to the reactor at a constant rate over 15 minutes. The reactor was kept at the reaction temperature for a further 2 hours. The temperature of the reactor was raised to 120 ° C and left there for 30 minutes, and then cooled to room temperature. The amount of ingredients is given in parts by weight. The copolymer solution A-2 had a viscosity of 152 cP, a nonvolatile content of 50.5 wt%, a Mw of 28,000, a PDI of 3.61 and a Tg of 35 ° C.

Preparation of Silyl Ester Acrylic Copolymer Solution A-3 (Polymer Component (iii-1))

35.50 parts of xylene were loaded into a thermostated reactor equipped with a stirrer, reflux condenser, nitrogen inlet and feed inlet. The reactor was heated to 85 ° C and held there. A premix of 11.83 parts of methyl methacrylate, 2.96 parts of n-butyl acrylate, 11.83 parts of tetrahydrofurfuryl acrylate, 32.54 parts of triisopropylsilyl methacrylate and 0.71 part of 2,2'-azobis (2-methylbutyronitrile) was prepared and reacted with a constant Speed charged into the reactor for 2 hours under a nitrogen atmosphere. After a further 0.5 hour reaction, a subsequent addition of an accelerating starter solution of 0.12 parts of 2,2'-azobis (2-methylbutyronitrile) and 4.50 parts of xylene was charged to the reactor at a constant rate over 20 minutes. The reactor was kept at the reaction temperature for a further 2 hours. The temperature of the reactor was raised to 110 ° C and left there for 30 minutes, and then cooled to room temperature. The amount of ingredients is given in parts by weight. The copolymer solution A-3 had a viscosity of 1275 cP, a non-volatile content of 60.2 wt%, a Mw of 31,000, a PDI of 3.10 and a Tg of 46 ° C.

General Procedure for the Preparation of Antifouling Coating Compositions

The ingredients were mixed in the proportions indicated in Table 8-13. The mixture was dispersed in the presence of glass beads (about 2 mm diameter) in a 250 ml volume paint can using a vibrating shaker for 15 minutes. Before the test, the glass beads were filtered off.  Table 1 Overview of the polymers of the invention polymer example P1 P2 P3 P4 P5 P6 P7 P8 P9 P10 P11 P12 Wt .-% monomers MEA 19.62 9.80 0 0 0 0 0 0 0 0 0 0 EDEGA 0 0 9.64 9.80 9.83 19.63 0 0 0 0 0 0 MMA 29.42 39.19 28.93 29.41 29,50 29.44 31.97 29,40 19.43 39,15 29.41 19.64 n-BA 0 0 9.64 9.80 9.83 0 5.12 4.90 0 0 0 0 MPEG-MA 300 0 0 0 0 0 0 11.97 0 0 0 0 0 EEMA 0 0 0 0 0 0 0 14.70 0 0 0 0 BDGMA 0 0 0 0 0 0 0 0 29,80 0 0 0 THFA 0 0 0.00 0 0 0 0 0 0 9.78 19.60 29.46 % By weight of xylene (total) 40,00 40,00 40,00 40,00 40,00 40,00 40,00 40,00 40,00 40,00 40,00 40,00 Wt% PM (total) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Wt% ABMN (first addition) 0.79 0.82 1.63 0.83 0.66 0.78 0.78 0.83 0.63 0.89 0.82 0.75 Wt% AMBN (accelerating addition) 0.17 0.18 0.16 0.17 0.17 0.16 0.16 0.17 0.13 0.18 0.16 0.15 Measured nfA: Wt .-% 50.2 52.9 49.2 49.5 49.3 48.9 49.7 50.1 49.1 53.0 50.5 49.8 Viscosity polymer solution: cP 470 1408 125 357 1292 452 655 611 190 1517 595 235 MWD: mw 20709 19016 10700 23578 57992 33005 23119 18902 22612 16590 19608 19863 PDI 2.48 2.23 2.32 2.93 4.04 3.43 2.50 2.25 2.43 2.30 2.68 2.95 Tg (° C) 30 49 18 23 28 20 42 48 9 52 37 27  Table 2 Overview of comparative polymers polymer example C1 C2 C3 C4 C5 C6 C7 C8 Wt .-% monomers MEA 49.18 39.31 0 0 0 9.84 39.34 0 EDEGA 0 0 49.43 9.82 29,50 0 0 3.92 MMA 0 9.83 0 9.82 19.67 0 0 26.45 n-BA 0 0 0 29.46 0 39.34 9.84 18.62 % By weight of xylene (total) 40,00 40,00 40,00 40,00 40,00 40,00 40,00 40,00 Wt% PM (total) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Wt% ABMN (first addition 0.67 0.71 0.46 0.75 0.69 0.68 0.67 0.84 Wt% AMBN (accelerating addition) 0.15 0.16 0.10 0.15 0.14 0.15 0.15 0.17 Measured nfA: Wt .-% 50.1 50.0 48.9 50.0 48.9 50.5 51.2 49.5 Viscosity polymer solution: cP 42 86 30 55 165 27 30 262 MWD: mw 11695 16962 17670 18909 37194 12851 11734 20478 PDI 2.42 2.68 2.84 3.01 4.03 2.46 2.41 3.03 Tg (° C) -36 -21 -54 -34 -16 -47 -39 17  Table 3 Determination of incompatibility (ingredients expressed in grams) example B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 B12 P1 2.48 - - - - - - - - - - - P2 - 2.48 - - - - - - - - - - P3 - - 2.48 - - - - - - - - - P4 - - - 2.48 - - - - - - - - P5 - - - - 2.48 - - - - - - - P6 - - - - - 2.48 - - - - - - P7 - - - - - - 2.48 - - - - - P8 - - - - - - - 2.48 - - - - P9 - - - - - - - - 2.48 - - - P10 - - - - - - - - - 2.48 - - P11 - - - - - - - - - - 2.48 - P12 - - - - - - - - - - - 2.48 A1 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 0.96 Balsam resin solution (60% by weight in xylene) 2.56 2.56 2.56 2.56 2.56 2.56 2.56 2.56 2.56 2.56 2.56 2.56 Irgazin Red L 3670 HD 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 Wt% PM 5.35 5.35 5.35 5.35 5.35 5.35 5.35 5.35 5.35 5.35 5.35 5.35 Wt .-% xylene 38,60 38,60 38,60 38,60 38,60 38,60 38,60 38,60 38,60 38,60 38,60 38,60 Weight% solids 56,05 56,05 56,05 56,05 56,05 56,05 56,05 56,05 56,05 56,05 56,05 56,05 intolerance U U U U U U U U U U U U  Table 4 Determination of incompatibility (ingredients expressed in grams) example B13 B14 B15 B16 B17 B18 B19 C1 2.48 - - - - - - C2 - 2.48 - - - - - C3 - - 2.48 - - - - C4 - - - 2.48 - - - C5 - - - - 2.48 - - C6 - - - - - 2.48 - C7 - - - - - - 2.48 A1 0.96 0.96 0.96 0.96 0.96 0.96 0.96 Balsam resin solution (60% by weight in xylene) 2.56 2.56 2.56 2.56 2.56 2.56 2.56 Irgazin Red L 3670 HD 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 Wt% PM 5.35 5.35 5.35 5.35 5.35 5.35 5.35 Wt .-% xylene 38,60 38,60 38,60 38,60 38,60 38,60 38,60 Weight% solids 56,05 56,05 56,05 56,05 56,05 56,05 56,05 intolerance U U V V U V U  Table 5 Determination of incompatibility (ingredients expressed in grams) example B20 B21 B22 B23 B24 B25 B26 B27 B28 P1 1.94 - - - - - - - - P2 - 1.94 - - - - - - - P3 - - 1.94 - - - - - - P4 - - - 1.94 - - - - - P5 - - - - 1.94 - - - - P7 - - - - - 1.94 - - - P8 - - - - - - 1.94 - - P10 - - - - - - - 1.94 - P11 - - - - - - - - 1.94 A2 2.32 2.32 2.32 2.32 2.32 2.32 2.32 2.32 2.32 A1 0.58 0.58 0.58 0.58 0.58 0.58 0.58 0.58 0.58 Balsam resin solution (60% by weight in xylene) 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 Irgazin Red L 3670 HD 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 Wt% PM 3.97 3.97 3.97 3.97 3.97 3.97 3.97 3.97 3.97 Wt .-% xylene 43.02 43.02 43.02 43.02 43.02 43.02 43.02 43.02 43.02 Weight% solids 53.01 53.01 53.01 53.01 53.01 53.01 53.01 53.01 53.01 intolerance U U U U U U U U U  Table 6 Determination of incompatibility (ingredients expressed in grams) example B29 B30 B31 B32 323 B34 B35 B36 B37 P1 1.94 - - - - - - - - P2 - 1.94 - - - - - - - P3 - - 1.94 - - - - - - P4 - - - 1.94 - - - - - P5 - - - - 1.94 - - - - P7 - - - - - 1.94 - - - P8 - - - - - - 1.94 - - P10 - - - - - - - 1.94 - P11 - - - - - - - - 1.94 A3 2.32 2.32 2.32 2.32 2.32 2.32 2.32 2.32 2.32 A1 0.58 0.58 0.58 0.58 0.58 0.58 0.58 0.58 0.58 Balsam resin solution (60% by weight in xylene) 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 1.16 Irgazin Red L 3670 HD 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 Wt% PM 3.97 3.97 3.97 3.97 3.97 3.97 3.97 3.97 3.97 Wt .-% xylene 43.02 43.02 43.02 43.02 43.02 43.02 43.02 43.02 43.02 Weight% solids 53.01 53.01 53.01 53.01 53.01 53.01 53.01 53.01 53.01 intolerance U U U U U U U U U  Table 7: Determination of incompatibility (ingredients expressed in grams) example B38 B39 B40 B41 B42 B43 B44 C1 1.94 - - - - - - C2 - 1.94 - - - - - C3 - - 1.94 - - - - C4 - - - 1.94 - - - C5 - - - - 1.94 - - C6 - - - - - 1.94 - C7 - - - - - - 1.94 A2 2.32 2.32 2.32 2.32 2.32 2.32 2.32 A1 0.58 0.58 0.58 0.58 0.58 0.58 0.58 Balsam resin solution (60% by weight in xylene) 1.16 1.16 1.16 1.16 1.16 1.16 1.16 Irgazin Red L 3670 HD 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 2 * 10 ^-3 Wt% PM 3.97 3.97 3.97 3.97 3.97 3.97 3.97 Wt .-% xylene 43.02 43.02 43.02 43.02 43.02 43.02 43.02 Weight% solids 53.01 53.01 53.01 53.01 53.01 53.01 53.01 intolerance U U V V U V U  Table 8: Coating compositions (ingredients expressed in weight%) Painting example M1 M2 M3 M4 M5 M6 M7 M8 M9 M10 M11 M12 P1 15.8 - - - - - - - - - - - P2 - 15.8 - - - - - - - - - - P3 - - 15.8 - - - - - - - - - P4 - - - 15.8 - - - - - - - - P5 - - - - 15.8 - - - - - - - P6 - - - - - 15.8 - - - - - - P7 - - - - - - 15.8 - - - - - P8 - - - - - - - 15.8 - - - - P9 - - - - - - - - 15.8 - - - P10 - - - - - - - - - 15.8 - - P11 - - - - - - - - - - 15.8 - P12 - - - - - - - - - - - 15.8 A1 6.05 6.05 6.05 6.05 6.05 6.05 6.05 6.05 6.05 6.05 6.05 6.05 Balsam resin solution (60% by weight in xylene) 16,66 16,66 16,66 16,66 16,66 16,66 16,66 16,66 16,66 16,66 16,66 16,66 Copper (I) oxide 30.23 30.23 30.23 30.23 30.23 30.23 30.23 30.23 30.23 30.23 30.23 30.23 Zineb 7.44 7.44 7.44 7.44 7.44 7.44 7.44 7.44 7.44 7.44 7.44 7.44 zinc oxide 7.17 7.17 7.17 7.17 7.17 7.17 7.17 7.17 7.17 7.17 7.17 7.17 iron oxide 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 Titanium dioxide 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 dolomite 2.94 2.94 2.94 2.94 2.94 2.94 2.94 2.94 2.94 2.94 2.94 2.94 Benton 52 0.92 0.92 0.92 0.92 0.92 0.92 0.92 0.92 0.92 0.92 0.92 0.92 ethanol 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 Solvesso 100 2.05 2.05 2.05 2.05 2.05 2.05 2.05 2.05 2.05 2.05 2.05 2.05 xylene 4.73 4.73 4.73 4.73 4.73 4.73 4.73 4.73 4.73 4.73 4.73 4.73 VOC (g / L) 401 400 399 399 399 400 400 400 400 400 400 400 Vol .-% solids 54.20 54.20 54.20 54.20 54.20 54.20 54.20 54.20 54.2 54.20 54.20 54.20 Cone and plate viscosity (cP) 520 520 350 485 820 675 640 260 260 730 640 440 Water absorption (34 days,% by weight) 2.6 2.2 2.3 2.3 2.4 2.9 2.2 2.7 2.7 2.4 2.3 2.3 Film thickness reduction (14 weeks, μm) 15 15 11 13 15 14 14 10 22 14 14 14  Table 9: Comparative paint compositions (ingredients expressed in weight percent) Painting example CP1 CP2 CP3 CP4 CP5 CP6 CP7 CP18 CP19 C1 15.8 - - - - - - - 32,21 C2 - 15.8 - - - - - - - C3 - - 15.8 - - - - - - C4 - - - 15.8 - - - - - C5 - - - - 15.8 - - - - C6 - - - - - 15.8 - - - C7 - - - - - - 15.8 - - C8 15.8 - A1 6.05 6.05 6.05 6.05 6.05 6.05 6.05 6.05 - Balsam resin solution (60% by weight in xylene) 16,66 16,66 16,66 16,66 16,66 16,66 16,66 16,66 2.98 Copper (I) oxide 30.23 30.23 30.23 30.23 30.23 30.23 30.23 30.23 30.23 Zineb 7.44 7.44 7.44 7.44 7.44 7.44 7.44 7.44 7.44 zinc oxide 7.17 7.17 7.17 7.17 7.17 7.17 7.17 7.17 7.17 iron oxide 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 Titanium dioxide 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 dolomite 2.94 2.94 2.94 2.94 2.94 2.94 2.94 2.94 2.94 Benton 52 0.92 0.92 0.92 0.92 0.92 0.92 0.92 0.92 0.92 ethanol 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 Solvesso 100 2.05 2.05 2.05 2.05 2.05 2.05 2.05 2.05 2.05 xylene 4.73 4.73 4.73 4.73 4.73 4.73 4.73 4.73 4.73 VOC (g / L) 400 400 398 399 399 395 399 395 434 Vol .-% solids 54.20 54.20 54.68 54.44 54.44 54.20 54.4 54.7 50,20 Cone and plate viscosity (cP) 210 260 170 245 360 185 210 413 596 Water absorption (34 days,% by weight) 4.1 3.9 5.3 5.9 3.9 7.6 5.9 3.5 14.5 Film thickness reduction (14 weeks, μm) 16 10 31 27 13 18 20 8th 12  Table 10: Paint compositions (ingredients expressed in weight%) Painting example M13 M14 M15 M16 M17 M18 M19 M20 M21 P1 11.54 - - - - - - - - P2 - 11.54 - - - - - - - P3 - - 11.54 - - - - - - P4 - - - 11.54 - - - - - P5 - - - - 11.54 - - - - P7 - - - - - 11.54 - - - P8 - - - - - - 11.54 - - P10 - - - - - - - 11.54 - P11 - - - - - - - - 11.54 A2 13.83 13.83 13.83 13.83 13.83 13.83 13.83 13.83 13.83 A1 3.43 3.43 3.43 3.43 3.43 3.43 3.43 3.43 3.43 Balsam resin solution (60% by weight in xylene) 6.91 6.91 6.91 6.91 6.91 6.91 6.91 6.91 6.91 Copper (I) oxide 32.79 32.79 32.79 32.79 32.79 32.79 32.79 32.79 32.79 Zineb 4.49 4.49 4.49 4.49 4.49 4.49 4.49 4.49 4.49 copper pyrithione 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 zinc oxide 8.63 8.63 8.63 8.63 8.63 8.63 8.63 8.63 8.63 iron oxide 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 Titanium dioxide 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 dolomite 3.57 3.57 3.57 3.57 3.57 3.57 3.57 3.57 3.57 Disparlon A603-20X 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 tetraethoxysilane 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 Solvesso 100 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 xylene 6.54 6.54 6.54 6.54 6.54 6.54 6.54 6.54 6.54 Vol .-% solids 49.89 49.89 50.25 50.25 50.25 50.25 50.07 50.46 49.88 VOC (g / L) 437 437 435 435 435 435 436 436 436 Cone and plate viscosity (cP) 270 285 210 250 320 285 290 325 300 Water absorption (34 days,% by weight) 3.0 2.1 2.5 3.0 2.6 3.2 1.6 2.3 2.4 Film thickness reduction (14 weeks, μm) 15 12 16 17 16 16 15 10 13  Table 11: Coating compositions (ingredients expressed in weight%) Painting example M22 M23 M24 M25 M26 M27 M28 M29 M30 M31 P1 11.54 - - - - - - - - - P2 - 11.54 - - - - - - 11.54 - P3 - - 11.54 - - - - - - - P4 - - - 11.54 - - - - - 11.54 P5 - - - - 11.54 - - - - - P8 - - - - - 11.54 - - - - P10 - - - - - - 11.54 - - - P11 - - - - - - - 11.54 - - A3 13.83 13.83 13.83 13.83 13.83 13.83 13.83 13.83 13.83 13.83 A1 3.43 3.43 3.43 3.43 3.43 3.43 3.43 3.43 3.43 3.43 Balsam resin solution (60% by weight in xylene) 6.91 6.91 6.91 6.91 6.91 6.91 6.91 6.91 6.91 6.91 Copper (I) oxide 32.79 32.79 32.79 32.79 32.79 32.79 32.79 32.79 32.79 32.79 Zineb 4.49 4.49 4.49 4.49 4.49 4.49 4.49 4.49 4.49 4.49 copper pyrithione 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 Selektope (Mmedetomidine) - - - - - - - - 0.10 0.10 zinc oxide 8.63 8.63 8.63 8.63 8.63 8.63 8.63 8.63 8.63 8.63 iron oxide 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 Titanium dioxide 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 dolomite 3.57 3.57 3.57 3.57 3.57 3.57 3.57 3.57 3.57 3.57 Disparlon A603-20X 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 T etraethoxysilane 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 Solvesso 100 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 xylene 6.54 6.54 6.54 6.54 6.54 6.54 6.54 6.54 6.54 6.54 Vol .-% solids 52.36 52.36 52.70 52.70 52.70 52,50 52,90 52,30 51.8 52.2 VOC (g / L) 415 415 414 414 414 415 415 415 421 419 Cone and plate viscosity (cP) 410 340 360 450 610 510 380 450 595 491 Water absorption (34 days,% by weight) 3.6 2.1 3.0 2.7 2.8 1.9 2.7 3.3 2.3 2.6 Film thickness reduction (14 weeks, μm) 10 14 17 14 11 13 10 11 12 13  Table 12: Comparative coating compositions (ingredients expressed in weight%) Painting example CP8 CP9 CP10 CP11 CP12 CP13 CP14 CP15 CP16 CP17 C1 11.54 - - - - 11.54 - - - - C2 - 11.54 - - - - 11.54 - - - C3 - - 11.54 - - - - 11.54 - - C5 - - - 11.54 - - - - 11.54 - C7 - - - - 11.54 - - - - 11.54 A3 13.83 13.83 13.83 13.83 13.83 A2 13.83 13.83 13.83 13.83 13.83 - - - - - A1 3.43 3.43 3.43 3.43 3.43 3.43 3.43 3.43 3.43 3.43 Balsam resin solution (60% by weight in xylene) 6.91 6.91 6.91 6.91 6.91 6.91 6.91 6.91 6.91 6.91 Copper (I) oxide 32.79 32.79 32.79 32.79 32.79 32.79 32.79 32.79 32.79 32.79 Zineb 4.49 4.49 4.49 4.49 4.49 4.49 4.49 4.49 4.49 4.49 copper pyrithione 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 zinc oxide 8.63 8.63 8.63 8.63 8.63 8.63 8.63 8.63 8.63 8.63 iron oxide 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 1.38 Titanium dioxide 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 dolomite 3.57 3.57 3.57 3.57 3.57 3.57 3.57 3.57 3.57 3.57 Disparlon A603-20X 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 T etraethoxysilane 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 Solvesso 100 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 2.07 xylene 6.54 6.54 6.54 6.54 6.54 6.54 6.54 6.54 6.54 6.54 Vol .-% solids 50.0 50.07 50.44 50.25 50.25 52.53 52.53 52.89 52.70 52.70 VOC (g / L) 436 436 434 435 435 415 415 413 414 414 Cone and plate viscosity (cP) 150 195 125 220 140 221 255 183 320 233 Water absorption (34 days,% by weight) 5.3 4.6 6.6 4.3 4.2 5.9 4.9 7.6 5.4 4.6 Film thickness reduction (14 weeks, μm) 9 10 16 6 12 9 11 5 8th 7

The combination of binder component (i), component (ii) and component (iii) is required to finely adjust the hydrophilic / hydrophobic balance of the coating. The balance affects the coating properties, such as water absorption, polishing speed, crack resistance and ink viscosity. If too little hydrophilic monomer is present (see Comparative Example C8), the polishing is slow. When only the components (i) + (ii) are used in the binder (see Comparative Example CP19), the water absorption is high.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 2128208 [0011]
• WO 03070832 [0012]
• WO 2014175246 [0013]
• WO 9744401 [0014, 0103]
• EP 1288234 [0015]
• WO 2005/005516 [0016]
• WO 2011/131721 [0017]
• WO 2014/175140 [0018]
• EP 3078715 [0019]
• WO 2009/149919 [0020]
• EP 2489710 [0021]
• EP 2161316 [0022]
• US 2011/0166253 [0022]
• WO 0077102 [0155]
• EP 2725073 [0158]

Cited non-patent literature

• ISO 11890-1 [0153]

Claims (20)

A binder for an antifouling coating composition comprising: (i) a hydrophilic copolymer having a glass transition temperature of at least 0 ° C, the hydrophilic copolymer comprising at least 10% by weight of at least one monomer of formula (I)

wherein R ^{1 is} H or CH ₃ and R ^{2 is} a C 3 -C 18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ^{2 is} a poly (alkylene glycol) chain; and at least one monomer of the formula (II),

wherein R ^{1 'is} H or CH ₃ , and R ^{2' is} a C ¹ -C 20 hydrocarbon radical; wherein the hydrophilic copolymer comprises less than 15% by weight of other comonomers than those of formula (I) or (II); (ii) a cyclic monocarboxylic acid such as rosin or a derivative thereof (such as a salt thereof); and (iii) a silyl ester copolymer comprising at least 15% by weight of a silyl ester monomer and / or a non-hydrophilic (meth) acrylic polymer comprising less than 10% by weight of a monomer of formula (I). Binders after Claim 1 wherein component (iii) comprises a silyl ester copolymer in which the monomer is triisopropylsilyl methacrylate (TISMA) or triisopropylsilyl acrylate (TISA). A binder according to any one of the preceding claims, wherein the hydrophilic copolymer (i) comprises (a) 15 to 65% by weight of at least one monomer of formula (I)

wherein R ^{1 is} H or CH ₃ and R ^{2 is} a C 3 -C 18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom, or R ^{2 is} a poly (alkylene glycol) chain; and (b) from 85 to 35% by weight of at least one monomer of the formula (II),

wherein R ^{1 'is} H or CH ₃ , and R ^{2' is} a C ¹ -C 8 hydrocarbon radical; wherein the hydrophilic copolymer comprises less than 15% by weight of other comonomers than those of formula (I) or (II). Binders according to one of Claims 1 to 3 wherein the amount of the component (ii) is in the range of 10 to 70% by weight of the binder (dry matter). A binder according to any one of the preceding claims, wherein component (ii) is a rosin or a derivative thereof (such as a salt thereof). Binders after Claim 1 to 5 wherein R ^{2 is} a group of the formula (CH ₂ CH ₂ O) _n -R ³ wherein R ^{3 is} a C ¹ -C 10 alkyl or C 6 -C 10 aryl substituent and n is an integer ranging from 1 to 6 is. Binder according to one of the preceding claims, wherein the amount of the component (i) in the range of 20 to 60 wt .-% of the binder is (dry matter). A binder according to any one of the preceding claims wherein the monomer of formula (I) is 2-methoxyethyl methacrylate (MEMA), 2-methoxyethyl acrylate (MEA), 2-ethoxyethyl methacrylate (EEMA), 2- (2-ethoxyethoxy) ethyl acrylate (EDEGA) and tetrahydrofurfuryl acrylate ( THFA) is. A binder according to any one of the preceding claims, wherein the monomer of formula (II) is methyl methacrylate (MMA), n-butyl methacrylate (n-BMA), 2-ethylhexyl acrylate (2-EHA) and n-butyl acrylate (n-BA). Binders according to one of Claims 1 to 9 comprising (iii) a silyl ester copolymer comprising at least 15% by weight of a silyl ester monomer and a non-hydrophilic (meth) acrylic polymer comprising less than 10% by weight of a monomer of formula (I). Binders according to one of Claims 1 to 10 comprising a non-hydrophilic (meth) acrylic acid copolymer (iii-2) comprising less than 10% by weight of a monomer of formula (I). Binders according to one of Claims 1 to 11 comprising 10 to 60% by weight of component (iii) (dry substance). Binders according to one of Claims 1 to 10 wherein the Tg of the non-hydrophilic (meth) acrylic polymer (iii-2) is lower than 0 ° C. An antifouling coating composition comprising a binder according to any one of Claims 1 to 13 and at least one antifouling agent. Antifouling coating composition according to Claim 14 wherein the antifouling agent comprises copper (I) oxide and / or copper pyrithione and / or zinc ethylenebis (dithiocarbamate). Antifouling coating composition according to Claim 14 or 15 wherein the binder constitutes 15 to 50% by weight of the antifouling coating composition. A method of protecting an article from fouling, which method comprises coating at least a portion of said fouled article with an antifouling coating composition according to any one of Claims 14 to 16 includes. An article coated with the antifouling coating composition of any one of Claims 14 to 16 , Subject to Claim 18 wherein the article is provided with a corrosion resistant coating layer, a primer layer, and an antifouling coating composition Claim 14 to 16 is coated. Subject to Claim 18 wherein the article is provided with an antifouling coating composition according to Claim 14 to 16 which covers a pre-existing antifouling coating composition on the substrate.