DE112018001119T5 - composition - Google Patents

Abstract

The present invention provides an antifouling coating composition comprising: (i) a silyl (meth) acrylate polymer, (ii) tralopyril, (iii) a polar solvent; and (iv) a nonpolar solvent; wherein the polar solvent has an evaporation rate based on n-butyl acetate of at least 0.1 and a Hansen solubility parameter δH of <17.0 (J / cm), wherein the composition comprises at least 2.5% by weight of polar solvent, based on the total amount of the solvent present in the composition, and the composition has a viscosity of less than 2000 cP.

Description

INTRODUCTION

The present invention relates to an antifouling coating composition comprising a silyl (meth) acrylate polymer, tralopyril and a polar solvent, and to a process for producing the composition. The composition has excellent long-term storage stability. The invention also relates to paint (paint) comprising the composition and to a paint container containing the composition. In addition, the invention relates to an article comprising a coating on at least a portion of the surface thereof, and to a process for coating an article to prevent fouling thereon, comprising coating at least a portion of a surface of the article with the composition ,

BACKGROUND

Surfaces that are immersed in the marine environment are subject to the attachment of fouling organisms such as bacteria, diatoms, algae, pipe worms, barnacles and bivalves. Of all marine organisms that grow on the surface, macro-vegetation (such as barnacles, shells, and worms) is the problem that has the greatest economic consequences. Under the right conditions, macro-growth can grow extremely fast. Barnacles and bivalves are widespread worldwide and are the most commonly encountered fouling organisms in coastal waters.

The risk of fouling and attachment of barnacles and other marsupials to marine vessels is typically greatest during the construction time of newbuilds and vessels with a long berth at anchor or a long rest period during ship operation. Growth can significantly affect the operational efficiency of a watercraft. It causes increased hydrodynamic drag resulting in increased fuel economy, lower speed, and shorter range. A very rough, overgrown hull can increase fuel consumption by up to 40%. There are also additional costs for dry docking. The removal of attached calcareous organisms such as barnacles, mussels and tube worms must be done by mechanical cockroaches. Waterborne vegetation can also cause the spread of non-native species. These are all important economic factors that require the prevention of biofouling.

Anti-fouling paints are used to prevent the colonization and growth of marine organisms. These paints generally consist of polymers that form a film (sometimes referred to as a film-forming binder), anti-fouling agents that control or inhibit fouling, pigments and solvents. In many instances, the paint also includes one or more other compounds such as extenders, desiccants, and thixotropic agents. Tralopyril is an antifouling agent with broad spectrum activity against hard-shelled and soft-bodied animal organisms. It is therefore an attractive antifouling agent which can be incorporated in paint, and more particularly in paint, which has been developed for use on surfaces of submerged vessels such as ships.

However, a problem with the use of tralopyril in paints is that the paint is used in combination with silyl (meth) acrylate polymer during storage and especially during storage for> 1 month, e.g. 6 months, thickened or even gelled. In other words, paints comprising silyl (meth) acrylate polymer and tralopyril tend to increase in viscosity during storage, suggesting that reactions take place in the paint and are not completely stable. That's obviously a practical problem. The viscosity of a paint determines how it can be applied (e.g., whether it can be sprayed) and also influences the finish. For industrial paints, such as antifouling paints, the paint is typically applied to very large surfaces and usually applied by airless spray. The viscosity of the paint must therefore be within a range that allows application with the prior art equipment. A paint can not be thinned and sprayed when gelled.

EP-A-3078715 recognizes the stability problem with paints containing silyl (meth) acrylates and tralopyril. It confirms that such paints tend to thicken during storage. EP-A-3078715 further discloses that the problem can be solved by the addition of a stabilizer selected from carbodiimides and / or silanes.

SUMMARY OF THE INVENTION

• (i) ein Silyl(meth)acrylatpolymer;
• (ii) Tralopyril;
• (iii) polares Lösungsmittel; und
• (iv) unpolares Lösungsmittel;

wobei das polare Lösungsmittel eine Verdampfungsrate bezogen auf n-Butylacetat von mindestens 0,1 und einen Hansen-Löslichkeitsparameter δH von <17,0 (J/cm³)^1/2 aufweist, wobei die Zusammensetzung mindestens 2,5 Gew.-% polares Lösungsmittel, bezogen auf die Gesamtmenge des in der Zusammensetzung vorhandenen Lösungsmittels, umfasst und die Zusammensetzung eine Viskosität von weniger als 2000 cP aufweist.From a first aspect, the present invention provides an antifouling composition comprising:

• (i) a silyl (meth) acrylate polymer;
• (ii) tralopyril;
• (iii) polar solvent; and
• (iv) nonpolar solvent;

wherein the polar solvent has an evaporation rate based on n-butyl acetate of at least 0.1 and a Hansen solubility parameter δH of <17.0 (J / cm ³ ) ^1/2 , the composition being at least 2.5% by weight polar Solvent, based on the total amount of the solvent present in the composition, and the composition has a viscosity of less than 2000 cP.

• (i) eines Silyl(meth)acrylatpolymers;
• (ii) Tralopyrils;
• (iii) eines polaren Lösungsmittels; und
• (iv) eines unpolaren Lösungsmittels.

Viewing a further aspect, the present invention provides a process for the preparation of a composition as described above, comprising mixing:

• (i) a silyl (meth) acrylate polymer;
• (ii) tralopyril;
• (iii) a polar solvent; and
• (iv) a nonpolar solvent.

Viewed from another aspect, the present invention provides a paint comprising a composition as described above.

From another aspect, the present invention provides a paint container having a composition as described above.

Viewing a further aspect, the present invention provides an article comprising (e.g., covered or coated with) a coating on at least a portion of a surface thereof, the coating comprising the composition as described above.

• Beschichten mindestens eines Teils einer Oberfläche des Artikels mit einer Zusammensetzung, wie vorstehend beschrieben; und Trocknen und/oder Aushärten der Beschichtung.

From another aspect, the present invention provides a method for coating an article to prevent fouling thereon, which method comprises:

• Coating at least a portion of a surface of the article with a composition as described above; and drying and / or curing the coating.

From the perspective of a further aspect, the present invention provides the use of a composition as described above to coat at least a portion of a surface of an article to prevent fouling thereon.

DEFINITIONS

As used herein, the term "antifouling coating composition" refers to a composition which, when applied to a surface, prevents or minimizes the growth of marine organisms on a surface.

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

As used herein, the term Hansen solubility parameter, δ H, provides a measure of the hydrogen bonds between molecules in a solvent.

As used herein, the term Hansen solubility parameter, δD, provides a measure of the dispersion forces between molecules in a solvent.

As used herein, the term Hansen solubility parameter, δP, provides a measure of the dipolar intermolecular forces between molecules in a solvent.

All Hansen solubility parameters mentioned herein are from the HSPiP software (Hansen Solubility Parameters in Practice), 4th edition 4.1.07.

As used herein, the term "silyl (meth) acrylate polymer" refers to a polymer comprising repeating units derived from silyl (meth) acrylate monomers. Generally, a silyl (meth) acrylate polymer will comprise at least 5 weight percent, more preferably at least 20 weight percent, and even more preferably at least 40 weight percent repeating units derived from silyl (meth) acrylate monomers, i. Silyl acrylate and / or Silylmethacrylatmonomeren.

As used herein, the term "alkyl" refers to saturated, straight chain, branched or cyclic groups. Alkyl groups may be substituted or unsubstituted.

As used herein, the term "cycloalkyl" refers to a saturated or partially saturated mono- or bicyclic alkyl ring system having from 3 to 10 carbon atoms. Cycloalkyl groups may be substituted or unsubstituted.

As used herein, the term "alkylene" refers to a divalent alkyl group.

As used herein, the term "aryl" refers to a group comprising at least one aromatic ring. The term aryl includes both heteroaryl and fused ring systems wherein one or more aromatic rings is fused to a cycloalkyl ring. Aryl groups may be substituted or unsubstituted. An example of an aryl group is phenyl, ie C ₆ H ₅ . Phenyl groups may be substituted or unsubstituted.

As used herein, the term "substituted" refers to a group wherein one or more, for example up to 6, especially 1, 2, 3, 4, 5 or 6, of the hydrogen atoms in the group are independently represented by the corresponding number of substituted substituents are replaced. The term "optionally substituted" as used herein means substituted or unsubstituted.

As used herein, the term "molecular weight" refers to the weight average molecular weight (Mw) unless otherwise specified.

As used herein, the term "PDI" or polymer dispersion index refers to the ratio Mw / Mn where Mn refers to the number average molecular weight.

As used herein, the term "volatile organic compound (VOC)" refers to a compound having a boiling point of 250 ° C or less at a standard air pressure of 101.3 kPa.

As used herein, the term "rosin" refers to rosin and rosin derivatives.

As used herein, "antifouling agent" refers to a compound or mixture of compounds which prevents the colonization of marine organisms on a surface and / or prevents the growth of marine organisms on a surface and / or the removal of marine organisms from promotes a surface.

As used herein, the term "extender" is used interchangeably with "filler" and refers to a compound that increases the volume or mass of a coating composition.

DETAILED DESCRIPTION OF THE INVENTION

• (i) ein Silyl(meth)acrylatpolymer;
• (ii) Tralopyril;
• (iii) ein polares Lösungsmittel; und
• (iv) ein unpolares Lösungsmittel.

The present invention relates to an antifouling coating composition comprising:

• (i) a silyl (meth) acrylate polymer;
• (ii) tralopyril;
• (iii) a polar solvent; and
• (iv) a nonpolar solvent.

Optionally, the composition further comprises one or more of the following: (v) additional antifouling agent; (vi) carboxylic acid compound and / or derivative thereof; (vii) a binder; (viii) a pigment and / or extender; (ix) a dehydrating agent; and (x) an additive.

In the antifouling coating compositions of the present invention, the combination of a silyl (meth) acrylate polymer, tralopyril, and a polar solvent advantageously provides a composition that has both long-term storage stability and excellent application properties. This means that the antifouling coating composition can be stored for a prolonged period of time (e.g., at least 1 month under uncontrolled temperature conditions) and still has a viscosity of less than 2000 cps which allows it to be applied to a surface, e.g. by spraying. The polar solvent may replace some or all of the conventional solvents (e.g., aromatic hydrocarbon solvents) present in antifouling coating compositions. Preferably, however, the antifouling coating composition comprises a non-polar solvent.

Polar solvent

The polar solvent present in the antifouling coating composition preferably has an evaporation rate based on n-butyl acetate of at least 0.15. Preferably, the polar solvent has an evaporation rate based on n-butyl acetate of 0.15 to 5.0, more preferably 0.2 to 2.5, and even more preferably 0.3 to 2.0. Preferably, the evaporation rate is determined according to ASTM D3539 in an evaporator at a temperature of 25 ° C and a relative humidity less than 5%.

The polar solvent present in the antifouling coating composition preferably has a Hansen solubility parameter δH of <15.0 (J / cm ³ ) ^1/2 . Preferably, the Hansen solubility parameter is δH 2.0 to 14.5 (J / cm ³ ) ^1/2 , more preferably 3.0 to 12.0 (J / cm ³ ) ^1/2 and even more preferably 3.5 to 10.0 (J / cm ³ ) ^1/2 .

The polar solvent present in the antifouling coating composition preferably has a Hansen solubility parameter δP of <10.0 (J / cm ³ ) ^1/2 . Preferably, the Hansen solubility parameter, δP, is 1.5 to 8.5 (J / cm ³ ) ^1/2 , more preferably 2.0 to 8.0 (J / cm ³ ) ^1/2, and even more preferably 2.5 to 7.5 (J / cm ³ ) ^1/2 .

The polar solvent present in the antifouling coating composition preferably has a Hansen solubility parameter δ D of <20.0 (J / cm ³ ) ^1/2 . Preferably, the Hansen solubility parameter is δD 10.0 to 20.0 (J / cm ³ ) ^1/2 , more preferably 12.0 to 18.0 (J / cm ³ ) ^1/2, and even more preferably 14.0 to 16.5 (J / cm ³ ) ^1/2 .

The Hansen solubility parameters δH, δP and δD are available for a variety of solvents, e.g. in the HSPiP (Hansen Solubility Parameters in Practice) Software 4th Edition 4.1.07. The Hansen solubility parameters for some polar solvents suitable for use in the antifouling coating composition of the invention are listed below.

The polar solvent present in the antifouling coating composition preferably has a boiling point of from 75 ° C to 250 ° C, and more preferably has a boiling point of from 110 ° C to 180 ° C.

The polar solvent present in the antifouling coating composition of the invention preferably comprises at least one heteroatom selected from O, N, P, and S, and preferably O. More preferably, the polar solvent present in the composition comprises one or two heteroatoms, and more preferably one or two O. -atoms.

The polar solvent present in the antifouling coating composition of the invention preferably comprises one or more functional groups selected from -O- (ether), -OC (O) - (ester), -C (O) - (ketone) and -C ( OH) - (secondary alcohol). Most preferably, the polar solvent comprises one or more -OC (O) -, - (CO) - and -C (OH) -functional groups. Preferably, the polar solvent present in the composition does not comprise a primary alcohol functional group.

wobei

• jedes R unabhängig ausgewählt ist aus linearen oder verzweigten C_1-8-Alkylgruppen;
• R¹ ausgewählt ist aus linearen oder verzweigten C_1-8-Alkylgruppen, die optional durch eine -O-Gruppe unterbrochen sind; und
• R² ausgewählt ist aus H oder linearen oder verzweigten C_1-8-Alkylgruppen, die optional durch eine -O-Gruppe unterbrochen sind.

The polar solvent present in the antifouling coating composition of the present invention is preferably selected from the formulas (Ia) - (Ic) and more preferably from the formulas (Ib) or (Ic):

in which

• each R is independently selected from C _1-8 linear or branched alkyl groups;
• R ^{1 is} selected from C _1-8 linear or branched alkyl groups optionally interrupted by an -O- group; and
• R ^{2 is} selected from H or linear or branched C _1-8 alkyl groups optionally interrupted by an -O group.

In preferred solvents of formulas (Ia) - (Ic), R is C _1-6 linear or branched alkyl, more preferably C _1-4 alkyl, and more preferably methyl.

Preferably, R is linear.

In preferred solvents of formulas (Ia) - (Ic), R ^{1 is} C _2-8 linear or branched alkyl, and more preferably C _4-5 alkyl. Representative examples of preferred R ¹ groups include n-butyl, n-pentyl, i-butyl and i-pentyl.

In other preferred solvents of formulas (Ia) - (Ic), R ^{1 is} a linear or branched C _1-8 alkyl group interrupted by an -O group. In this case, R ^{1 is} preferably linear or branched C _2-4 alkyl. Representative examples of preferred R ¹ groups include - CH ₂ OCH ₃ and -CH (CH ₃ ) CH ₂ OCH ₃ .

In preferred solvents of formula (Ia), R ^{2 is} H.

Representative examples of solvents of formula (Ia) together with their evaporation rate relative to n-BuAc and their Hansen solubility parameters are listed in the following table. These are preferred solvents of formula (Ia) for the antifouling coating composition of the present invention. 1-methoxy-2-propanol is a preferred solvent of formula (Ia). Surname Evaporation Rate (Evaporation Rate), n-BuAc = 1 δH (J / cm ³ ) ^1/2 δP (J / cm ³ ) ^1/2 δD (J / cm ³ ) ^1/2 1-methoxy-2-propanol 0.6 11.6 6.3 15.6 2-propanol 1.1 16.4 6.1 15.8 2-butanol 0.9 14.5 5.7 15.8 2-methyl-2-butanol 0.9 13.3 6.1 15.3 Methylisobutylcarbinol (4-methyl-2-pentanol) 0.3 12.3 3.3 15.4

Representative examples of solvents of formula (Ib), together with their evaporation rate relative to n-BuAc and their Hansen solubility parameters, are listed in the following table. These are preferred solvents of formula (Ib) for the antifouling coating composition of the present invention. n-butyl acetate, isoamyl acetate and 1-methoxy-2-propyl acetate are preferred solvents of the formula (Ib). Surname Evaporation rate, n-BuAc = 1 δH (J / cm ³ ) ^1/2 δP (J / cm ³ ) ^1/2 δD (J / cm ³ ) ^1/2 n-propyl 2.1 7.6 4.3 15.3 isopropyl 3.5 8.2 4.5 14.9 n-butyl acetate 1.0 6.3 3.7 15.8 isobutyl 1.5 6.3 3.7 15.1 t-butyl 2.8 6.0 3.7 15.0 amyl acetate 0.4 6.1 3.3 15.8 isoamyl 0.5 7.0 3.1 15.3 n-propyl 1.2 5.7 5.8 15.7 butyl propionate 0.5 5.9 5.5 15.7 isobutylisobutyrate 0.4 5.8 2.8 15.1 n-pentyl 0.2 5.7 5.2 15.8 1-methoxy-2-propyl 0.4 9.8 5.6 15.6 Ethyl 3-ethoxypropionate 0.12 8.8 3.3 16.2 Representative examples of solvents of formula (Ic), together with their evaporation rate relative to n-BuAc and their Hansen solubility parameters, are listed in the following table. These are preferred solvents of formula (Ic) for the antifouling coating composition of the present invention. Methyl isoamyl ketone, methyl amyl ketone and methyl isobutyl ketone are preferred solvents of formula (Ic). Surname Evaporation rate, n-BuAc = 1 δH (J / cm ³ ) ^1/2 δP (J / cm ³ ) ^1/2 δD (J / cm ³ ) ^1/2 methyl isoamyl 0.5 4.1 5.7 16.0 methyl amyl ketone 0.4 4.1 5.7 16.2 methyl isobutyl ketone 1.6 4.1 6.1 15.3 diisobutyl 0.2 4.1 3.7 16.0 cyclohexanone 0.3 5.1 8.4 17.8

More preferably, the antifouling coating composition of the present invention comprises a polar solvent selected from 1-methoxy-2-propanol, n-butyl acetate, isoamyl acetate, 1-methoxy-2-propyl acetate, methyl isoamyl ketone, methyl amyl ketone and methyl isobutyl ketone. These solvents have been found to produce antifouling coating compositions that are stable upon long-term storage, i. they do not gel or thicken during long-term storage.

The antifouling coating composition of the present invention preferably comprises at least 3% by weight of polar solvent, based on the total amount of the solvent present in the composition. Preferably, the composition comprises at least 4% by weight of polar solvent, more preferably 5 to 60% by weight and more preferably 7 to 55% by weight of polar solvent, based on the total amount of solvent present in the composition. These levels of polar solvent ensure that the composition is stable upon prolonged storage.

The amount of the polar solvent present in the total antifouling coating composition is preferably 0.5 to 30% by weight, more preferably 1 to 25% by weight, and more preferably 2 to 20% by weight, based on the total weight of the composition.

Non-polar solvent

The antifouling coating composition comprises a nonpolar solvent. Preferably, the nonpolar solvent is organic.

Examples of suitable nonpolar organic solvents are aromatic hydrocarbons such as xylenes, toluene, mesitylene and aliphatic hydrocarbons such as benzine and limonene. Combinations of different non-polar solvents can also be used. Preferably, however, the non-polar solvent is an aromatic hydrocarbon, and more preferably the non-polar solvent is xylene. Suitable non-polar organic solvents are commercially available.

The amount of solvent, and particularly nonpolar solvent, present in the antifouling coating compositions of the present invention is preferably as low as possible, as this minimizes VOC content. Preferably, the composition comprises up to 98% by weight of nonpolar solvent or up to 97.5% by weight of nonpolar solvent, more preferably 40 to 90% by weight and even more preferably 45 to 85% by weight of nonpolar solvent to the total amount of solvent present in the composition. Preferably, a non-polar solvent is present in the compositions of the invention in an amount of 0-35% by weight, preferably 1-30% by weight, and more preferably 1-25% by weight, based on the total weight of the composition ,

Further preferred antifouling coating compositions of the present invention comprise 2.5-60 wt.% Polar solvent and 40-97.5 wt.% Nonpolar solvent, more preferably 5-60 wt.% Polar solvent and 40-95 wt. % non-polar solvent and more preferably 7-55% by weight of polar solvent and 45-93% by weight of non-polar solvent, based on the total amount of solvent present in the composition.

One skilled in the art will understand that the solvent content will vary depending on the other components present.

Silyl (meth) acrylate polymer

The silyl (meth) acrylate polymer present in the antifouling coating composition of the present invention is preferably a copolymer.

wobei

• R⁴ H oder CH₃ ist;
• R⁵ jeweils unabhängig ausgewählt sind aus linearen oder verzweigten C_1-4-Alkylgruppen;
• R⁶ jeweils unabhängig ausgewählt sind aus der Gruppe bestehend aus linearen oder verzweigten C_1-20-Alkylgruppen, C_3-12-Cycloalkylgruppen, gegebenenfalls substituierten C_6-20-Arylgruppen und - OSi(R⁷)₃ Gruppen;
• jedes R⁷ unabhängig voneinander eine lineare oder verzweigte C_1-4-Alkylgruppe ist; Z ein C₁-C₄-Alkylen ist;
• m eine ganze Zahl von 0 bis 1 ist; und
• n eine ganze Zahl von 0 bis 5 ist.

Preferably, the silyl (meth) acrylate polymer present in the antifouling coating composition of the present invention comprises a moiety of at least one silyl (meth) acrylate monomer, and preferably a moiety of at least one silyl (meth) acrylate monomer of formula (II):

in which

• R ^{4 is} H or CH ₃ ;
• R ^{5 are} each independently selected from linear or branched C _1-4 alkyl groups;
• R ^{6 are} each independently selected from the group consisting of linear or branched C _1-20 alkyl groups, C _3-12 cycloalkyl groups, optionally substituted C _6-20 aryl groups, and - OSi (R ⁷ ) ₃ groups;
• each R ^{7 is} independently a linear or branched C _1-4 alkyl group; Z is C ₁ -C ₄ alkylene;
• m is an integer of 0 to 1; and
• n is an integer from 0 to 5.

Examples of substituted aryl groups are 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.

Representative examples of R ⁵ and R ⁷ groups are methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl and t -butyl.

Representative examples of Z include -CH ₂ -, -CH ₂ CH ₂ -, - (CH ₂ ) ₃ -, and - (CH ₂ ) ₄ . There are also provided branched C _3-4 alkylene, for example CH ₂ CH (CH ₃ ) CH ₂ -.

In preferred monomers of the formula (II) m is 0.

In preferred monomers of the formula (II), n is 0.

In preferred monomers of formula (II), R ^{6 are} each independently selected from linear or branched C _1-20 alkyl groups. Still more R ⁶ are each independently selected from linear or branched C _1-8 alkyl groups and more preferably from C _2-6 alkyl groups.

• (Meth)acrylate wie Triisopropylsilyl(meth)acrylat, Tri-n-butylsilyl(meth)acrylat, Triisobutylsilyl(meth)acrylat, Tri-sec-butylsilyl(meth)acrylat, Butyldiisopropylsilyl(meth)acrylat, tert-Butyldimethylsilyl(meth)acrylat, Thexyldimethylsilyl(meth)acrylat, tert-Butyldiphenylsilyl(meth)acrylat, Triisopropylsiloxycarbonylmethyl(meth)acrylat, Triisopropylsiloxycarbonylethyl(meth)acrylat, tert-Butyldiphenylsiloxycarbonylmethyl(meth)acrylat, Nonamethyltetrasiloxy(meth)acrylat, Bis(trimethylsiloxy)methylsilyl(meth)acrylat und Tris(trimethylsiloxy)silyl(meth)acrylat.

Examples of silyl (meth) acrylate monomers, for example as defined by the general formula (II), include:

• (Meth) acrylates such as triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-sec-butylsilyl (meth) acrylate, butyldiisopropylsilyl (meth) acrylate, tert-butyldimethylsilyl (meth) acrylate , Thexyldimethylsilyl (meth) acrylate, tert-butyldiphenylsilyl (meth) acrylate, triisopropylsiloxycarbonylmethyl (meth) acrylate, triisopropylsiloxycarbonylethyl (meth) acrylate, tert-butyldiphenylsiloxycarbonylmethyl (meth) acrylate, nonamethyltetrasiloxy (meth) acrylate, bis (trimethylsiloxy) methylsilyl (meth) acrylate and tris (trimethylsiloxy) silyl (meth) acrylate.

Preferred monomers are alkylsilyl (meth) acrylates and more preferably trialkylsilyl (meth) acrylates wherein one or more of the alkyl group (s) are branched. Particularly preferred monomers are triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, thexyldimethylsilyl (meth) acrylate and tert-butyldiphenylsilyl (meth) acrylate. Particularly preferred are triisopropylsilyl acrylate and triisopropylsilyl methacrylate.

The silyl (meth) acrylate polymer present in the antifouling coating composition of the present invention preferably comprises 1-3 different monomers of formula (II) and more preferably 1 or 2 different monomers of formula (II).

worin R⁸ Wasserstoff oder Methyl ist, R⁹ ein cyclischer Ether ist und X ein C₁-C₄-Alkylen ist; oder

wobei R⁸ Wasserstoff oder Methyl ist und R¹⁰ ein C₃-C₁₈-Substituent mit mindestens einem Sauerstoff- oder Stickstoffatom, vorzugsweise mindestens einem Sauerstoffatom, ist; oder

wobei R⁸ Wasserstoff oder Methyl ist und R¹¹ ein C₁-C₈-Kohlenwasserstoffrest ist.
In bevorzugten Monomeren der Formel (Illa) ist R⁸ Wasserstoff oder Methyl, R⁹ ist ein cyclischer Ether (wie Oxolan, Oxan, Dioxolan, Dioxan, gegebenenfalls alkylsubstituiert) und X ist ein C_1-4-Alkylen, vorzugsweise ein C_1-2-Alkylen. Der zyklische Ether kann ein einzelnes Sauerstoffatom im Ring oder 2 oder 3 Sauerstoffatome im Ring enthalten.
Der zyklische Ether kann einen Ring mit 2 bis 8 Kohlenstoffatomen, wie beispielsweise 3 bis 5 Kohlenstoffatome, enthalten. Der gesamte Ring kann 4 bis 8 Atome umfassen, wie beispielsweise 5 oder 6 Atome.
Der zyklische Etherring kann beispielsweise durch eine oder mehrere, wie beispielsweise eine, C_1-6Alkylgruppe, substituiert sein. Diese Substituentengruppe kann sich an jeglicher Stelle des Rings befinden, einschließlich der Position, die an die X-Gruppe bindet.Preferably, the silyl (meth) acrylate polymer present in the antifouling coating composition of the present invention further comprises a residue of one or more (meth) acrylate monomers. Preferred meth (acrylate) monomers present in the silyl (meth) acrylate polymer are those of formulas (IIIa) - (IIIc):

wherein R ^{8 is} hydrogen or methyl, R ^{9 is} a cyclic ether and X is C ₁ -C ₄ alkylene; or

wherein R ^{8 is} hydrogen or methyl and R ^{10 is} a C ₃ -C ₁₈ substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom; or

wherein R ^{8 is} hydrogen or methyl and R ^{11 is} a C ₁ -C ₈ hydrocarbon radical.
In preferred monomers of formula (IIIa) R ⁸ is hydrogen or methyl, R ⁹ is a cyclic ether (such as oxolane, oxane, dioxolane, dioxane, optionally substituted by alkyl) and X is a C _1-4 alkylene, preferably a C _{1- 2} -alkylene. The cyclic ether may contain a single oxygen atom in the ring or 2 or 3 oxygen atoms in the ring.
The cyclic ether may contain a ring of 2 to 8 carbon atoms, such as 3 to 5 carbon atoms. The entire ring may comprise 4 to 8 atoms, such as 5 or 6 atoms.
The cyclic ether ring may, for example, be substituted by one or more, such as a, C _1-6 alkyl group. This substituent group can be located anywhere in the ring, including the position that binds to the X group.

Suitable monomers of formula (IIIa) include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isopropylideneglycerol methacrylate, glycerol formal methacrylate and trimethylolpropane trimethyl acrylate.

Most preferably, formula (IIIa) represents tetrahydrofurfuryl acrylate having the structure:

In preferred monomers of formula (IIIb), R ^{8 is} hydrogen or methyl, and R ^{10 is} a C _3-18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom.

In preferred monomers of formula (IIIb), R ^{10 is of} the formula - (CH ₂ CH ₂ O) _m -R ¹² wherein R ^{12 is} a C _1-10 hydrocarbyl substituent, preferably a C _1-10 alkyl or a C _{6 -10} -Arlylsubstituent, and m is an integer ranging from 1 to 6, preferably 1 to. 3 Preferably, R ^{10 is of} the formula - (CH ₂ CH ₂ O) _m -R ¹² , wherein R ^{12 is} an alkyl substituent, preferably methyl or ethyl, and m is an integer in the range of 1 to 3, preferably 1 or 2 ,

Preferred monomers of formula (IIIb) include one or more of 2-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate and 2- (2-ethoxyethoxy) ethyl acrylate.

In preferred silyl (meth) acrylate polymers present in the antifouling coating composition of the present invention, it is generally not preferred to have monomers of the two formulas (IIIa) and (IIIb).

In preferred monomers of formula (IIIc), R ^{8 is} hydrogen or methyl and R ¹¹ is a C _1-8 hydrocarbyl substituent, preferably a C _1-8 alkyl substituent, most preferably methyl, ethyl, n-butyl or 2-ethylhexyl.

Preferred monomers of formula (IIIc) include methyl methacrylate and n-butyl acrylate.

Preferred silyl (meth) acrylate polymers present in the antifouling coating composition of the invention comprise at least one monomer of formula (IIIc).

The silyl (meth) acrylate polymer present in the antifouling coating composition of the present invention may optionally comprise other polymerizable monomers. Examples include an alkyl ester of acrylic acid and methacrylic acid such as 3,5,5-trimethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isotridecyl (meth) acrylate, octadecyl (meth) acrylate ; cyclic alkyl esters of acrylic acid and methacrylic acid such as cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate; Aryl esters of acrylic acid and methacrylic acid such as phenyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate; Hydroxyalkyl esters of acrylic acid and methacrylic acid such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, poly (ethylene glycol) (meth) acrylate, poly (propylene glycol) (meth) acrylate; Alkoxyalkyl and poly (alkoxy) alkyl esters of acrylic acid and methacrylic acid, such as poly (ethylene glycol) methyl ether (meth) acrylate, poly (propylene glycol) methyl ether (meth) acrylate, glycidyl (meth) acrylate; other functional monomers of acrylic acid and methacrylic acid, such as methacrylic anhydride; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl dodecanoate, vinyl benzoate, vinyl 4-tert-butyl benzoate, VeoVa ™ 9, VeoVa ™ 10; N-vinyl lactams, N-vinyl amides such as N-vinyl pyrrolidone; Vinyl monomers such as styrene, α-methylstyrene and vinyltoluene.

Preferred silyl (meth) acrylate polymers present in the antifouling coating composition of the present invention have a weight average molecular weight of 5,000 to 80,000, more preferably 10,000 to 70,000 and more preferably 20,000 to 60,000. Preferred silyl (meth) acrylate polymers useful in the antifouling coating composition of the present invention have a number average molecular weight of 3,000 to 20,000, more preferably 5,000 to 15,000, and more preferably 7,000 to 12,000. Preferred silyl (meth) acrylate polymers present in the antifouling coating composition of the present invention have a polydispersity index (PDI ) calculated according to the equation PDI = Mw / Mn from 1.2 to 5 and preferably 2.5 to 4.0. Preferred silyl (meth) acrylate polymers present in the antifouling coating composition of the present invention have a Tg of 10 ° C to 80 ° C, preferably 15 ° C to 70 ° C, and more preferably 20 ° C to 60 ° C.

The antifouling coating composition may comprise one or more (e.g., 1, 2, 3, 4 or 5) silyl (meth) acrylate polymers as described above. Preferred antifouling coating compositions of the present invention comprise 1, 2, 3 or 4 silyl (meth) acrylate polymers, and more preferably 1 or 2 silyl (meth) acrylate polymers.

In preferred silyl (meth) acrylate polymers present in the antifouling coating composition of the present invention, the amount of the monomers of formula (II) is preferably 5 to 80% by weight, preferably 20 to 70% by weight, and more preferably 40% to 65 wt .-%, based on the total weight of the monomers. In preferred silyl (meth) acrylate polymers present in the antifouling coating composition of the present invention, the total amount of the monomers of the formulas (IIIa) and (IIIb) is preferably 1 to 40% by weight, preferably 2 to 30% by weight. and more preferably 5 to 25% by weight, based on the total weight of the monomers. In preferred silyl (meth) acrylate polymers present in the antifouling coating composition of the present invention, the amount of the monomers of formula (IIIc) is preferably 1 to 50% by weight, preferably 2 to 45% by weight, and more preferably 5 to 40 wt .-%, based on the total weight of the monomers. In preferred silyl (meth) acrylate polymers present in the antifouling coating composition of the present invention, the amount of the other monomers is preferably 0 to 20% by weight, more preferably 0 to 15% by weight, and even more preferably 0 to 10 Wt .-%, based on the total weight of the monomers.

Preferably, the total amount of the silyl (meth) acrylate polymer present in the compositions of the invention is 1-50% by weight, more preferably 2-40% by weight and more preferably 5-35% by weight based on the total weight of the composition.

Suitable silyl (meth) acrylate polymers can be prepared by the polymerization techniques known in the art. The silyl (meth) acrylate polymer can be obtained, for example, by polymerizing a monomer mixture in the presence of a polymerization initiator by any of various methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization. For example, controlled polymerization processes can be used. In preparing a coating composition using the silyl (meth) acrylate polymer as described above, the polymer is preferably diluted with solvent to obtain a polymer solution having a suitable viscosity. From this viewpoint, it is desirable to use solution polymerization or bulk polymerization for producing the silyl (meth) acrylate polymer. Examples of suitable polymerization initiators are 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 peroxy pivalate, tert-amyl peroxy-2-ethylhexanoate , 1,1-di (tert-amylperoxy) cyclohexane and dibenzoyl peroxide. These compounds may be used singly or as a mixture of two or more thereof.

Examples of suitable solvents for the polymerization are aromatic hydrocarbons such as xylene, toluene, mesitylene; Ketones such as methyl isobutyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone; Esters such as butyl acetate, amyl acetate, isoamyl acetate, propylene glycol methyl ether acetate; Ethers, such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether; Alcohols such as 2-butanol, benzyl alcohol; Ether alcohols such as 1-methoxy-2-propanol; aliphatic hydrocarbons such as benzine; and optionally a mixture of two or more solvents. These compounds are used alone or as a mixture of two or more thereof.

Alternatively, suitable silyl (meth) acrylate polymers can be purchased commercially.

Tralopyril

The antifouling coating composition of the present invention comprises tralopyril or a salt thereof. This is an antifouling agent capable of preventing or removing marine growth from a surface. The organic biocide tralopyril is marketed by Janssen as Econea®. Tralopyril is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and has the structure shown below:

Tralopyril displays a broad spectrum of activity against various marine organisms such as barnacles, mussels and tube worms. It is also possible to use salts thereof. The term tralopyril will be used below to discuss this biocide. The teaching applies equally to their salts.

Anti-fouling coating compositions of the present invention contain tralopyril in an amount that provides a biocidal effect. Preferred amounts are 0.5 to 10 wt .-% (dry solids), preferably 1 to 7 wt .-%, preferably 2 to 6 wt .-%.

An advantage of using tralopyril is that it has a higher biocidal activity against marine organisms compared to metal biocides so that the amount of metal biocide can be reduced or eliminated. In turn, unwanted effects such as discoloration due to precipitation avoided or reduced by copper salts. A disadvantage of using tralopyril is that it causes instability in silyl (meth) acrylate containing compositions. However, this problem is overcome in the antifouling coating composition herein comprising a polar solvent.

Optionally, the antifouling coating composition comprises one or more additional antifouling agents. The terms antifouling agent, biologically active compounds, antifoulants, biocide, toxicant are used in the industry to describe known compounds which serve to prevent marine growth on a surface. The further antifouling agent present in the compositions of the invention is preferably a marine antifouling agent. The antifouling agent may be inorganic, organometallic or organic. Suitable antifouling agents are commercially available.

Examples of inorganic antifouling agents are copper and copper compounds such as copper oxides, e.g. Cuprous oxide and cupric oxide; Copper alloys, e.g. Copper-nickel alloys; Copper salts, e.g. Copper (I) thiocyanate and copper sulfide.

Examples of organometallic antifouling agents are zinc pyrithione; Organo copper compounds such as copper pyrithione, copper acetate, copper naphthenate, oxine copper, copper nonylphenolsulfonate, copper
Bis (ethylenediamine) bis (dodecylbenzenesulfonate) and copper bis (pentachlorophenolate); Dithiocarbamate compounds such as zinc bis (dimethyldithiocarbamate) [ziram], zinc ethylenebis (dithiocarbamate) [zineb], manganese-ethylenebis (dithiocarbamate) [maneb] and manganese-ethylenebis (dithiocarbamate) complexed with zinc salt [mancozeb].

Examples of organic antifouling agents are 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 [DCOIT], 1,2-benzisothiazolin-3-one, 2- (thiocyanatomethylthio) -1,3-benzothiazole [benthiazole] 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 [TPBP], aminetriphenylborane, 3-iodo-2-propynyl-N-butylcarbamate [iodocarb], 2,4,5,6-tetrachloroisophthalonitrile and p - ((diiodomethyl) sulfonyl) toluene.

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

Preferred further antifouling agents are cuprous oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis (dithiocarbamate) [zineb], 2- (tert-butylamino) -4- (cyclopropylamino) -6- (methylthio) -1,3,5 Triazine [cybutryne], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfamide [dichlofluanide], N- Dichlorofluoromethylthio-N ', N'-dimethyl-Np-tolylsulfamide [tolylfluanid] and 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine].
Particularly preferred further antifouling agents are copper (I) oxide, copper (I) thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis (dithiocarbamate) [zineb], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [ DCOIT] and 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine].

The antifouling agents may be used singly or in mixtures as various antifouling agents act against various marine fouling organisms. Mixtures of antifouling agents are generally preferred. A preferred mixture of antifouling agents is active against marine invertebrates such as barnacles, tube worms, bryozoa and hydroids; and plants such as algae (algae and diatoms); and bacteria.

Some preferred coating compositions of the present invention are free of an inorganic copper scum preventing agent. Such compositions preferably comprise a combination of tralopyril and one or more agents selected from zinc pyrithione, zineb and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.

Other preferred coating compositions include tralopyril, cuprous oxide and / or cuprous thiocyanate and one or more selected from copper pyrithione, zineb and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.

• (i) 1-50 Gew.-%, mehr bevorzugt 2-40 Gew.-% eines Silyl(meth)acrylatpolymers;
• (ii) 0,5-10 Gew.-%, mehr bevorzugt 1-7 Gew.-% Tralopyril;
• (iii) 0,5-30 Gew.-%, mehr bevorzugt 1-25 Gew.-% eines polaren Lösungsmittels; und
• (iv) 0-35 Gew.-%, mehr bevorzugt 1-30 Gew.-% eines unpolaren Lösungsmittels; wobei Gew.-% auf das Gesamtgewicht der Zusammensetzung bezogen sind.

The combined amount of antifouling agents present in the antifouling composition may constitute up to 60% by weight of the coating composition, such as 0.1 to 50% by weight, eg, 0.2 to 45% by weight. based on the total weight of the composition. When inorganic copper compounds are present, a suitable amount of antifouling agent may be 5 to 60% by weight in the coating composition. When inorganic copper compounds are avoided, minor amounts such as 0.1 to 25 wt%, eg, 0.2 to 20 wt% can be used. It will be appreciated that the amount of antifouling agent varies depending on the end-use and antifouling agent used. The use of these antifouling agents is known in antifouling coatings and their use would be known to those skilled in the art. The antifouling agent may be encapsulated or adsorbed on an inert carrier or bound to other materials for controlled release. These percentages are based on the amount of active antifouling agent and not on a carrier used.
Preferred antifouling coating compositions of the invention include:

• (i) 1-50% by weight, more preferably 2-40% by weight of a silyl (meth) acrylate polymer;
• (ii) 0.5-10 wt%, more preferably 1-7 wt% tralopyril;
• (iii) 0.5-30% by weight, more preferably 1-25% by weight of a polar solvent; and
• (iv) 0-35% by weight, more preferably 1-30% by weight of a nonpolar solvent; wherein wt .-% based on the total weight of the composition.

Carboxylic acid compounds and their derivatives

The antifouling coating composition of the present invention preferably comprises one or more compounds comprising a carboxylic acid group and / or its derivatives. Derivatives include metal salts of compounds that include a carboxylic acid group (also referred to as metal carboxylates) and esters of compounds that comprise a carboxylic acid group, preferably methyl esters.

Preferred carboxylic acid compounds are rosin. The antifouling coating composition of the present invention preferably comprises rosin and / or a rosin derivative. Representative examples of rosin include wood rosin, tall oil rosin, and gum rosin. Representative examples of rosin derivatives include hydrogenated and partially hydrogenated rosin, disproportionated rosin, dimerized rosin, polymerized rosin, maleic acid esters, fumaric acid esters and other rosin esters and hydrogenated rosin esters, copper rosin, zinc rosin, calcium rosin, magnesium rosin, and other metal rosin esters of rosin and others as described in U.S. Pat WO 97/44401 described, a. Preferably, the rosin or rosin derivative present in the antifouling coating composition of the present invention is a gum rosin.

Preferably, the present rosin comprises rosin acids selected from abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, secodehydroabietic acid, pimaric acid, isopimaric acid, levopimaric acid, palustric acid, sandaracopimaric acid, municipal acid and their derivatives.

Examples of other carboxylic acid compounds are organic acid compounds such as Versatic ™ acids, isononanoic acid, 2-ethylhexanoic acid, naphthenic acid and other organic acids, as in EP1342756 described; cyclic carboxylic acid compounds such as 1-methyl-3- (4-methyl-3-pentenyl) -3-cyclohexen-1-yl-carboxylic acid, 1-methyl-4- (4-methyl-3-pentenyl) -4-cyclohexene-1 -yl-carboxylic acid, 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-cyclohexen-1-yl-carboxylic acid and others as in EP1695956 and JP2016216651A described.

Preferably, compounds comprising a carboxylic acid group and / or derivatives thereof (eg rosin and / or a derivative thereof) are present in the compositions of the invention in an amount of 0-40% by weight, more preferably 1-35% by weight. and even more preferably 2-25% by weight, based on the Total weight of the composition, present. A mixture of one or more compounds comprising a carboxylic acid group and / or derivatives thereof may also be used.

Compounds comprising a carboxylic acid group and / or derivatives thereof including rosin and rosin derivatives are available commercially. For example, gum rosin, which is preferably included in the coating compositions of the invention, is commercially available.

binder components

• (Meth)acrylpolymere und -copolymere, insbesondere Acrylatbindemittel, wie Poly(n-butylacrylat), Poly(n-butylacrylat-co-isobutylvinylether) und andere wie in WO03/070832 und EP2128208 beschrieben;
• hydrophile Copolymere, wie beispielsweise (Meth)acrylat-Copolymere, wie in GB2152947 beschrieben, und Poly(N-vinylpyrrolidon)-Copolymere und andere Copolymere, wie in EP0526441 beschrieben;
• Vinylether-Polymere und -Copolymere, wie Poly(methylvinylether), Poly(ethylvinylether), Poly(isobutylvinylether), Poly(vinylchlorid-co-isobutylvinylether);
• aliphatische Polyester, wie Poly(milchsäure), Poly(glykolsäure), Poly(2-hydroxybuttersäure), Poly(3-hydroxybuttersäure), Poly(4-hydroxyvaleriansäure), Polycaprolacton und aliphatisches Polyestercopolymer, das zwei oder mehr der aus den oben genannten Einheiten ausgewählten Einheiten enthält;
• Polyoxalate wie in WO2009/100908 beschrieben und andere Kondensationspolymere wie in WO96/14362 beschrieben;
• Alkydharze und modifizierte Alkydharze; und
• Kohlenwasserstoffharz, z.B. wie in WO2011/092143 beschrieben, wie beispielsweise Kohlenwasserstoffharz, 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 Mischungen davon, gebildet wird.
• Besonders geeignete Zusatzbindemittel sind (Meth)acrylpolymere und Copolymere.

In addition to the silyl (meth) acrylate polymer, an additional binder may optionally be used to adjust the properties of the antifouling coating composition. Examples of binders that can be used include:

• (Meth) acrylic polymers and copolymers, especially acrylate binders, such as poly (n-butyl acrylate), poly (n-butyl acrylate-co-isobutyl vinyl ether) and others, as in WO03 / 070832 and EP2128208 described;
• hydrophilic copolymers, such as (meth) acrylate copolymers, as in GB2152947 described, and poly (N-vinylpyrrolidone) copolymers and other copolymers, as in EP0526441 described;
• 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 copolymer, two or more of the above-mentioned units contains selected units;
• Polyoxalates as in WO2009 / 100908 described and other condensation polymers as in WO96 / 14362 described;
• Alkyd resins and modified alkyd resins; and
• Hydrocarbon resin, eg as in WO2011 / 092143 such as hydrocarbon resin 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.
• Particularly suitable auxiliary binders are (meth) acrylic polymers and copolymers.

Extender and pigments

The term extender is used herein for both extenders and fillers. These compounds increase the mass of the composition. Examples of extenders and fillers are minerals such as dolomite, plastorite, calcite, quartz, barite, magnesite, aragonite, silica, wollastonite, talc, chlorite, mica, kaolin and feldspar; synthetic inorganic compounds such as zinc phosphates, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate and silica; Polymeric and inorganic microspheres such as uncoated or coated hollow and solid glass spheres, uncoated or coated hollow and solid ceramic spheres, hollow, porous and compact spheres of polymeric materials such as poly (methyl methacrylate), poly (methyl methacrylate-co-ethylene glycol dimethacrylate), poly ( styrene-co-ethylene glycol dimethacrylate), poly (styrene-co-divinylbenzene), polystyrene and poly (vinyl chloride).

The pigments may be inorganic pigments, organic pigments or a mixture thereof. Preference is given to inorganic pigments. Examples of inorganic pigments include titanium dioxide, iron oxides and zinc oxide. Examples of organic pigments are naphthol red, phthalocyanine compounds, azo pigments and carbon black.

Preferably, the total amount of extenders, fillers and / or pigments in the compositions of the invention is 0-70% by weight, more preferably 1-60% by weight and even more preferably 2-50% by weight, based on the total weight the composition. One skilled in the art will understand that the extender and pigment content can vary depending on the other components 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 separator 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 by removing moisture resulting from raw materials such as pigments and solvents, or water resulting from reaction between carboxylic acid compounds and di- and tri-valent metal compounds 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, often referred to as a desiccant. 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 are 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 trimethoxymethyl-silane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane and ethyl polysilicate.

Preferred dehydrating agents are those which chemically react with water. Particularly preferred dehydrating agents are organosilanes. Organosilanes are particularly preferred in antifouling coating compositions containing inorganic copper antifouling agent. More preferably, organosilanes contained in antifouling coating compositions comprise cuprous oxide.

Preferably, the dehydrating agent in the compositions of the invention is present in an amount of 0-5 wt.%, More preferably 0.5-2.5 wt.% And even more preferably 1.0-2.0 wt.%, based on the total weight of the composition.

Preferably, the antifouling coating compositions of the present invention do not comprise a carbodiimide compound. In particular, the antifouling coating composition of the present invention preferably does not comprise a compound containing a functional group of the formula [-N = C = N-].

Other components

The antifouling coating composition of the present invention preferably comprises one or more other components. Examples of other components which can be added to the antifouling coating composition are reinforcing agents, thixotropic agents, thickeners, anti-settling agents, dispersants, wetting agents and plasticizers.

Examples of reinforcing agents are flakes and fibers. The 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; Metal fibers; natural and synthetic organic fibers such as cellulose fibers, rubber fibers, acrylic fibers, polyamide fibers, polyimide fibers, 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 2000 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. Preferred in the compositions of the invention are reinforcing agents in an amount of 0-50 microns. 20 wt%, more preferably 0.5-15 wt%, and even more preferably 1-10 wt%, based on the total weight of the composition.

Examples of thixotropic agents, thickeners and anti-settling agents are silicic acids such as fumed silicas, organically modified clays, amide waxes, polyamide waxes, amide derivatives, polyethylene waxes, oxidized polyethylene waxes, hydrogenated castor oil wax, ethyl cellulose, aluminum stearates and mixtures thereof. Preferred are thixotropic agents, thickeners and anti-settling agents in the composition of Invention in each case in an amount of 0-10 wt .-%, more preferably 0.5-6 wt .-% and even more preferably 1.0-3.0 wt .-%, based on the total weight of the composition present.

Examples of plasticizers are chlorinated paraffins, phthalates, phosphate esters, sulfonamides, adipates and epoxidized vegetable oils. Preferably, in the compositions of the invention, plasticizers are present in an amount of 0-20% by weight, more preferably 1-15% by weight and even more preferably 1-10% by weight, based on the total weight of the composition.

Composition and painting

The present invention also relates to a process for preparing the composition as described above, wherein the components present in the composition are mixed. In a preferred method of the invention, tralopyril is premixed with polar solvent and mixed with silyl (meth) acrylate polymer and nonpolar solvent and other optional ingredients. Any conventional production method can be used. In a preferred method of the invention, silyl (meth) acrylate polymer and nonpolar solvent and other optional ingredients are dispersed and ground and cooled before adding tralopyril or a mixture comprising tralopyril and polar solvent.

The composition described herein may be used at a suitable concentration for use, e.g. when spraying. In this case, the composition itself is a paint. Alternatively, the composition may also be a paint-conditioning concentrate. In this case, another solvent is added to the composition described herein to form the paint. Preferred solvents are as described above with respect to the composition.

After mixing, and optionally after addition of solvent, the antifouling coating composition or antifouling paint is preferably filled into a container. Suitable containers include cans, barrels and tanks.

The antifouling coating composition is preferably supplied as a single pack. Therefore, the composition is preferably supplied in a ready-mixed or ready-to-use form. Optionally, the single pack product may be diluted with solvents before use.

The antifouling coating composition and the antifouling paint of the invention preferably have a solids content of 40-80% by volume, more preferably 45-70% by volume, and still more preferably 50-65% by volume.

Preferably, the antifouling coating composition and the antifouling paint of the invention have a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, even more preferably 100-900 cP and even more preferably 150-800 cP. The viscosity measurement is preferably carried out with a "Cone and Plate Viscometer" ( ISO 2884-1: 1999 ), as described in the examples.

Preferably, the antifouling coating composition and antifouling paint of the invention have a viscosity of from 50 to 2000 cps, more preferably 50-1000 cps, even more preferably 100-900 cps and even more preferably 150-800 cps after 1 week storage at 52 ° C ASTM D1849-95 (2014). Preferably, the antifouling coating composition and the antifouling paint of the invention have a viscosity of 50 to 2000 cP, more preferably 50-1000 cP, even more preferably 100-900 cP and even more preferably 150-800 cP after being at 52 for 2 weeks ° C according to ASTM D1849-95 (2014). Preferably, the antifouling coating composition and the antifouling paint of the invention have a viscosity of from 50 to 2000 cps, more preferably 50-1000 cps, even more preferably 100-900 cps and even more preferably 150-800 cps after being at 52 for 4 weeks ° C according to ASTM D1849-95 (2014). Preferably, the antifouling coating composition of the invention does not gel during storage for 4 weeks at 52 ° C according to ASTM D1849-95 (2014). The viscosity measurement is preferably carried out with a "cone and plate viscometer" (ISO 2884-1: 1999), as described in the examples.

Preferably, the antifouling coating composition and the antifouling paint of the invention have a VOC of from 50 to 500 g / L, preferably 50 to 420 g / L, eg 50 to 390 g / L. The VOC content can be calculated (ASTM D5201-01) or measured (EPA, Method 24).

Preferably, the antifouling coating composition and the antifouling paint of the invention have a viscosity of 50-1000 cP and a VOC content of 50-500 g / L, more preferably a viscosity of 100-900 cP and a VOC content of 50-420 g / L and more preferably has a viscosity of 150-800 cP and a VOC content of 50 to 390 g / L.

The antifouling coating composition and the antifouling paint of the invention may be applied in whole or in part to any article surface which is subject to fouling. The surface may be permanent or intermittent underwater (e.g., by tides, different charges or swellings). The surface of the article is typically the hull of a watercraft or the surface of a solid marine object, such as an oil rig or buoy. The application of the coating composition and the paint may be by any means, e.g. by painting (e.g., by brush or roller) or more preferably by spraying the coating onto the article. Typically, the surface must be separated from the seawater to allow for coating. The application of the coating can be carried out as is customary in the art. After application of the coating, this is preferably dried.

The invention will now be described by the following non-limiting examples, wherein:

EXAMPLES

Production and characterization of polymers

Determination of the viscosity of the polymer solution

The viscosity of the polymer solutions was determined according to ASTM D2196-15 Test Method A with 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 solids content of the polymer solutions

The solids content of the polymer solutions was determined according to ISO 3251: 2008. A sample of 0.4 g ± 0.1 g was taken and dried for 30 minutes in a ventilated oven at 150 ° C. The weight of the residual material is considered a nonvolatile substance (NVM). The content of non-volatile substance is given in percent by weight. The result is the average of three parallels.

Determination of the distribution of the average molecular weights of polymers

The polymers were characterized by gel permeation chromatography (GPC) measurement. The molecular weight distribution (MWD) was determined using a Agilent "Malvern Omnisec Resolve and Reveal System" with two PLgel 5 μm Agilent Mixed-D columns. The columns were calibrated by conventional calibration with narrow polystyrene standards. The analysis conditions were as shown in the following table. detector RI cell volume 12 μl Column set Agilent PLgel 5 μm Mixed-D, 2 columns in series Mobile phase THF flow 1 ml / min injection volume 100 μl Autosampler temperature 25 ° C Column oven temperature 35 ° C Detector cabinet temperature 35 ° C data processing Omnisec 5.1 calibration Standards Agilent Polystyrene Medium EasiVials (4 ml) Red, yellow and green

The samples were prepared by dissolving an amount of polymer solution corresponding to 25 mg dry polymer in 5 mL THF. Samples were stored for at least 3 hours at room temperature prior to sampling for GPC measurements. 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 reported.

Determination of the glass transition temperature

The glass transition temperature (Tg) was determined by Differential Scanning Calorimetry (DSC) measurements. The DSC measurements were performed on a TA Instrument DSC Q200. Dry polymer samples were prepared by lowering onto a glass sheet with a film applicator of 100 μm gap size. The glass sheets were dried for at least 24 hours at room temperature and then dried at 50 ° C for 24 hours. About 10 mg of dry polymer material was collected from the glass sheets and transferred to an aluminum pan. The measurements were made in open aluminum pans with an empty pan as reference. The scans were recorded at a heating rate of 10 ° C / min and a cooling rate of 10 ° C / min in a temperature range of -50 ° C to 120 ° C. The data was processed using the Universal Analysis Software from TA Instruments. The inflection point of the glass transition region, as defined in ASTM E1356-08, of the second heating is reported as the Tg of the polymers.

General procedure for the preparation of the copolymer solution S-1 to S-9

A quantity of solvent was charged to a temperature controlled reaction vessel equipped with a stirrer, a condenser, a nitrogen inlet and an inlet. The reaction vessel was heated and maintained at the reaction temperature of 85 ° C. A premix of monomers, initiator and solvent was prepared. The masterbatch was fed to the reaction vessel at a constant rate over 2 hours under a nitrogen atmosphere. After 1 more hour, a boost initiator solution was added later. The reaction vessel was maintained at the reaction temperature of 85 ° C for an additional 2 hours. The temperature was then increased to 110 ° C and held for a further 30 minutes. The diluting solvent was added to the reactor and the copolymer solution was then cooled to room temperature.

The components of the compositions, expressed as parts by weight, and the properties of the copolymer solutions are shown in Table 1. Table 1 S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 reactor charge solvent xylene 60.0 60.0 30.0 - - 60.0 60.0 60.0 60.0 methyl isoamyl - - - 60.0 - - - - - butyl - - 30.0 - 60.0 - - - - Vormischladung monomers Triisopropylsilylmethacrylat 55.0 55.0 55.0 55.0 55.0 - 50.0 50.0 - - - - - - - 56.0 - - 55.0 2- (2-ethoxyethoxy) ethyl acrylate 10.0 10.0 10.0 10.0 10.0 - - - - 2-methoxyethyl - - - - - - 30.0 - - tetrahydrofurfuryl - - - - - - - 20.0 5.0 n-butyl acrylate 5.0 5.0 5.0 5.0 5.0 6.0 10.0 5.0 5.0 methyl methacrylate 30.0 30.0 30.0 30.0 30.0 38.0 10.0 25.0 35.0 initiator 2,2'-azobis (2-methylbutyronitrile) 1.20 1.20 1.20 1.20 1.20 1.20 1,00 1.20 1.20 booster charge initiator 2,2'-azobis (2-methylbutyronitrile) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 solvent xylene 7.5 7.6 7.5 - - 7.6 7.5 7.6 7.6 methyl isoamyl - - - 7.5 - - - - - butyl - - - - 7.5 - - - - thinner solvent xylene 15.5 - - - - - - - - methyl isoamyl - - - 15.5 - - - - - butyl - - 15.5 - 15.5 - - - - characteristics Measured NVM% by weight 54.3 59.5 55.3 56.3 54.9 60.0 59.6 60.2 60.0 Brookfield viscosity (cP) 646 1835 732 800 722 1312 1330 1940 1427 Mw (x1000) 33.7 35.1 33.5 31.9 33.2 32.2 34.9 35.2 36.3 Mn (x1000) 10.3 11.2 11.0 10.8 10.7 9.0 11.6 11.2 9.2 PDI (Mw / Mn) 3.3 3.1 3.1 3.0 3.1 3.6 3.0 3.1 3.9 Tg (° C) 46 46 44 44 48 42 35 43 38

Production and testing of anti-hindering coating formulations

Determination of the coating viscosity with the "cone and plate" viscometer

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

Determination of the paint consistency with the Stormer viscometer

The consistency of the antifouling paint compositions was determined according to ASTM D562-10 (2014) Method B with a Stormer digital viscometer. The measurement was carried out on samples in a 500 mL container at 23 ° C.

Determination of VOCs

The VOC (g / L) of the antifouling coating compositions was calculated according to ASTM D5201-01.

Accelerated storage stability testing of paints

The storage stability of the antifouling coating compositions was determined under the conditions described in ASTM D1849-95 (2014). Samples were included in 250 mL containers Stored at 52 ° C. After storage, the samples were cooled to room temperature before the containers were opened. The consistency of the paints was evaluated. Liquid samples were stirred in homogeneous quality and the viscosities were recorded with a cone and plate viscometer. Storage for 1 month at 52 ° C simulates some of the effects of storage for 6 months to 1 year at 23 ° C.

General procedure for the preparation of antifouling coating compositions

The components were mixed in the proportions shown in Tables 3-1 to 3-3 and Table 4. The quantities are given in parts by weight. Table 4 describes comparative compositions. The mixture was dispersed in the presence of an appropriate amount of glass beads (3-4 mm in diameter) in a 1 liter container with a vibratory paint shaker for 15 minutes. The color was transferred to 250 mL containers to test storage stability.

The properties of the polar solvents used in the antifouling coating compositions are summarized in Table 2 below. The Hansen solubility properties were taken from the HSPiP software (Hansen Solubility Parameters in Practice) 4th Edition 4.1.07.  Table 2 Evaporation rate based on n-BuAc = 1 Hansen solubility parameter Surface tension (dynes / cm at 20 ° C) δH (J / cm ³ ) ^1/2 δP (J / cm ³ ) ^1/2 δD (J / cm ³ ) ^1/2 methyl isoamyl 0.5 4.1 5.7 16.0 25.8 methyl amyl ketone 0.4 4.1 5.7 16.2 26.1 methyl isobutyl ketone 1.6 4.1 6.1 15.3 24.0 n-butyl acetate 1.0 6.3 3.7 15.8 25.3 1-methoxy-2-propyl acetate 0.4 9.8 5.6 15.6 26.4 1-methoxy-2-propanol 0.6 11.6 6.3 15.6 27.7  Table 3-1 PA-1 PA-2 PA-3 PA-4 PA-5 PA-6 PA-7 PA-8 PA-9 PA-10 Silyl copolymer S-1 26.5 26.5 - 26.5 26.5 - - - - - S-2 - - 24.3 - - 24.3 24.3 24.3 12.0 - S-4 - - - - - - - - - 26.5 S-6 - - - - - - - - 12.0 - S-7 - - - - - - - - - - S-8 - - - - - - - - - - Co-binder Gum rosin 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 Poly (n-butyl acrylate) - - - - - - - - - - biocides Copper (I) oxide 35.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0 Copper (I) thiocyanate - - - - - - - - - - Copper pyrithione 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Zinc pyrithione - - - - - - - - - - Tralopyril 3.0 3.0 3.0 3.0 3.0 3.0 3.0 2.0 3.0 3.0 Pigments and extenders Naphtol red - - - - - - - - - - iron oxide 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Titanium dioxide 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 talc 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 feldspar - - - - - - - - - - zinc oxide 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 additives Polyamide wax (20% in xylene) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Oxidized poly (ethylene oxide) wax (25% in xylene) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 tetraethoxysilane 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Calcium sulfate hemihydrate - - - - - - - - - - Sylosive A4 - - - - - - - - - - Polar solvents Methyl isoamyl ketone 5.0 10.0 15.0 - - - - 10.0 10.0 - methyl amyl ketone - - - 5.0 10.0 15.0 - - - - methyl isobutyl ketone - - - - - - 10.0 - - - Other solvents xylene 6.0 1.0 - 6.0 1.0 - 3.2 3.2 2.5 11.0 total 100.0 100.0 101.8 100.0 100.0 101.8 100.0 99.0 99.0 100.0 % By weight polar solvent of the total solvent 21% 41% 58% 21% 41% 58% 42% 42% 42% 49% Calculated VOC (g / L) 404 401 414 404 402 414 399 405 393 392 Storage stability; Cone and plate viscosity (cP); ("Cone & Plate viscosity (cP)") begin 353 416 229 377 362 258 440 324 338 415 1 week 376 446 261 384 388 242 475 340 404 484 2 weeks 412 459 337 423 464 287 516 370 603 593 3 weeks 447 597 449 500 596 378 702 434 856 768 4 weeks 516 783 647 600 840 489 977 466 992 986  Table 3-1 Continued PA-11 PA-12 PA-13 PA-14 PA-15 PA-16 PA-17 Silyl copolymer S-1 26.5 26.5 - - - - - S-2 - - 24.3 - - - - S-4 - - - - - - - S-6 - - - - - - - S-7 - - - 28.0 28.0 - - S-8 - - - - - 20.0 20.0 Co-binder Gum rosin 4.5 4.5 4.5 6.0 6.0 8.0 8.0 Poly (n-butyl acrylate) - - - - - 2.0 2.0 biocides Copper (I) oxide 35.0 35.0 35.0 - - - - Copper (I) thiocyanate - - - - - 25.0 25.0 Copper pyrithione 3.0 3.0 3.0 - - - - Zinc pyrithione - - - 3.0 3.0 5.0 5.0 Tralopyril 3.0 3.0 3.0 5.0 5.0 3.0 3.0 Pigments and fillers Naphtol red - - - 0.5 0.5 - - iron oxide 2.0 2.0 2.0 0.5 0.5 5.0 5.0 Titanium dioxide 1.0 1.0 1.0 - - - - talc 6.0 6.0 6.0 6.0 6.0 3.0 3.0 feldspar - - - 10.0 10.0 - - zinc oxide 6.0 6.0 6.0 23.0 23.0 7.0 7.0 additives Polyamide wax (20% in xylene) 1.0 1.0 1.0 0.5 0.5 2.0 2.0 Oxidized poly (ethylene oxide) wax (25% in xylene) 0.5 0.5 0.5 0.5 0.5 - - tetraethoxysilane - - - 1.0 1.0 1.0 1.0 Calcium sulfate hemihydrate - 1.0 1.0 - - - - Sylosive A4 1.0 - - - - - - Polar solvents Methyl isoamyl ketone 5.0 5.0 2.5 5.0 10.0 5.0 10.0 methyl amyl ketone - - - - - - - methyl isobutyl ketone - - - - - - - Other solvents xylene 6.0 6.0 10.7 10.0 5.0 14.0 9.0 total 100.5 100.5 100.5 99.5 99.5 100.0 100.0 % By weight polar solvent of the total solvent 21% 21% 10% 18% 35% 17% 34% Calculated VOC (g / L) 405 405 406 391 389 397 395 Storage stability; Cone and Plate Viscosity (cP) ("cone & plate viscosity (cP)") begin 371 341 362 302 267 201 182 1 week 435 415 399 337 316 240 245 2 weeks 545 507 431 362 348 258 270 3 weeks 749 668 447 405 372 299 302 4 weeks 972 933 468 518 545 338 379  Table 3-2 PB-1 PB-2 PB-3 PB-4 PB-5 PB-6 PB-7 PB-8 PB-9 PB-10 Silyl copolymer S-1 26.5 26.5 - 26.5 26.5 - - - - - S-2 - - 24.3 - - 24.3 - - 24.3 - S-3 - - - - - - 26.5 - - - S-5 - - - - - - - 26.5 - - S-7 - - - - - - - - - 28.0 S-8 - - - - - - - - - - Co-binder Gum rosin 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 6.0 Poly (n-butyl acrylate) - - - - - - - - - - biocides Copper (I) oxide 35.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0 35.0 - Copper (I) thiocyanate - - - - - - - - - - Copper pyrithione 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 - Zinc pyrithione - - - - - - - - - 3.0 Tralopyril 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 5.0 Pigments and extenders Naphtol red - - - - - - - - - 0.5 iron oxide 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 1.0 Titanium dioxide 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 - talc 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 feldspar - - - - - - - - - 10.0 10.0 zinc oxide 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 23.0 additives Polyamide wax (20% in xylene) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.5 Oxidized poly (ethylene oxide) wax (25% in xylene) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 tetraethoxysilane 0.5 0.5 0.5 0.5 - - 0.5 0.5 0.5 1.0 Calcium sulfate hemihydrate - - - - 1.0 - - - - - Sylosive A4 - - - - - 1.0 - - - - Polar solvents butyl 5.0 10.0 15.0 - 5.0 5.0 - - 1.0 5.0 1-methoxy-2-propyl - - - 5.0 - - - - - - Other solvents xylene 6.0 1.0 - 6.0 6.0 8.2 11.0 11.0 12.2 10.0 total 100.0 100.0 101.8 100.0 100.5 100.5 100.0 100.0 100.0 99.5 % By weight of the total solvent 21% 41% 58% 21% 21% 21% 27% 49% 4% 18% Calculated VOC (g / L) 407 408 423 411 409 407 403 405 400 394 Storage stability; Cone and Plate Viscosity (cP) ("cone & plate viscosity (cP)") begin 441 385 284 438 362 423 450 418 423 322 1 week 477 416 367 486 431 473 501 528 432 338 2 weeks 548 516 378 518 543 596 543 606 447 347 3 weeks 652 666 536 593 695 794 650 819 472 375 4 weeks 773 971 864 695 938 975 852 992 501 528  Table 3-2 (continued) PB-11 PB-12 PB-13 Silyl copolymer S-1 - - - S-2 - - - S-3 - - - S-5 - - - S-7 28.0 - - S-8 - 20.0 20.0 Co-binder Gum rosin 6.0 8.0 8.0 Poly (n-butyl acrylate) - 2.0 2.0 biocides Copper (I) oxide - - - Copper (I) thiocyanate - 25.0 25.0 Copper pyrithione - - - Zinc pyrithione 3.0 5.0 5.0 Tralopyril 5.0 3.0 3.0 Pigments and extenders Naphtol red 0.5 - - iron oxide 1.0 5.0 5.0 Titanium dioxide - - - talc 6.0 3.0 3.0 feldspar 10.0 - - zinc oxide 23.0 7.0 7.0 additives Polyamide wax (20% in xylene) 0.5 2.0 2.0 Oxidized poly (ethylene oxide) wax (25% in xylene) 0.5 - - tetraethoxysilane 1.0 1.0 1.0 Calcium sulfate hemihydrate - - - Sylosive A4 - - - Polar solvents butyl 10.0 10.0 15.0 1-methoxy-2-propyl Other solvents xylene 10.0 9.0 4.0 total 99.5 100.0 100.0 % By weight polar solvent of the total solvent 18% 34% 51% Calculated VOC (g / L) 394 400 400 Storage stability; Cone and plate viscosity (cP) begin 285 197 189 1 week 321 247 258 2 weeks 352 275 309 3 weeks 368 319 367 4 weeks 523 407 462  Table 3-3 PC-1 PC-2 PC-3 PC-4 Silyl copolymer S-1 26.5 - - 26.5 S-2 - 24.3 - - S-7 - - - - S-8 - - 20.0 - S-9 - - - - Co-binder Gum rosin 4.5 4.5 8.0 4.5 Poly (n-butyl acrylate) - - 2.0 - biocides Copper (I) oxide 35.0 35.0 - 35.0 Copper (I) thiocyanate - - 25.0 - Copper pyrithione 3.0 3.0 5.0 3.0 Zinc pyrithione - - - - Zineb - - - - Tralopyril 3.0 3.0 3.0 3.0 Pigments and extenders iron oxide 2.0 2.0 5.0 2.0 Titanium dioxide 1.0 1.0 - 1.0 talc 6.0 6.0 3.0 6.0 dolomite - - - - zinc oxide 6.0 6.0 7.0 6.0 additives Polyamide wax (20% in xylene) 1.0 1.0 2.0 1.0 Oxidized poly (ethylene oxide) wax (25% in xylene) 0.5 0.5 - 0.5 tetraethoxysilane 0.5 0.5 1.0 0.5 Polar solvents 1-methoxy-2-propanol 5.0 1.0 5.0 - 1,3-dioxolane - - - 5.0 Other solvents xylene 6.0 12.2 14.0 6.0 total 100.0 100.0 100.0 100.0 % By weight polar solvent of the total solvent 21% 4% 17% 21% Calculated VOC (g / L) 409 406 401 414 Storage stability; Cone and plate viscosity (cP) begin 392 449 259 467 1 week 403 505 350 499 2 weeks 458 541 461 525 3 weeks 515 540 684 557 4 weeks 552 569 945 623  Table 4 C-1 C-2 C-3 Silyl copolymer S-1 26.5 - - S-2 - 24.3 24.3 Co-binder Gum rosin 4.5 4.5 4.5 biocides Copper (I) oxide 35.0 35.0 35.0 Copper pyrithione 3.0 3.0 3.0 Tralopyril 3.0 - 3.0 Pigments and extenders iron oxide 2.0 2.0 2.0 Titanium dioxide 1.0 1.0 1.0 talc 6.0 6.0 6.0 zinc oxide 6.0 6.0 6.0 additives Polyamide wax (20% in xylene) 1.0 1.0 1.0 Oxidized poly (ethylene oxide) wax (25% in xylene) 0.5 0.5 0.5 tetraethoxysilane 0.5 0.5 0.5 Polar solvent 1-methoxy-2-propanol - - 0.5 Other solvents xylene 11.0 13.2 12.7 total 100.0 97.0 100.0 % By weight polar solvent of the total solvent 0% 0% 2% Calculated VOC (g / L) 407 418 418 Storage stability; Cone and plate viscosity (cP) begin 398 303 422 1 week gel 318 gel 2 weeks - 332 - 3 weeks - 345 - 4 weeks - 359 -

The antifouling coating compositions PA1-PA17, PB1-13 and PC1-4 all comprise a silyl (meth) acrylate, tralopyril and at least 2.5% by weight polar solvent (either ketone, ester or secondary alcohol). All of these coating compositions are storage stable. Thus, even after storage for 4 weeks under accelerated storage conditions, the compositions have not formed a gel, indicating that they can still be applied to a surface by spraying. In contrast, Comparative Example C-1 comprising silyl (meth) acrylate and tralopyril but containing no polar solvent forms a gel after 1 week of storage. This shows that it is the addition of the polar solvent to the composition that ensures storage stability.

Also Comparative Example C-3, which comprises silyl (meth) acrylate, tralopyril and only 2% by weight of polar solvent, based on the total weight of the solvent, forms a gel after 1 week storage under accelerated conditions. In contrast, PC-2 and PC-3, which comprise 4% by weight and 9% by weight of polar solvent, based on the total weight of the solvent, are storage stable.

Comparative Example C-2, which comprises silyl (meth) acrylate but lacks tralopyril and polar solvent, is stable during storage. This shows that it is the combination of tralopyril and silyl (meth) acrylate that leads to instability in antifouling compositions during storage.

Preparation of an antifouling coating composition

An antifouling coating composition was prepared using a dissolver. 120 g of copper pyrithione, 500 g of silyl (meth) acrylate polymer solution S-2, 300 g of gum rosin solution (60% in xylene) and 120 g of methyl isoamyl ketone were mixed in a 3 L paint tank. There were added 1400 g of cuprous oxide, 240 g of talc, 240 g of zinc oxide, 80 g of iron oxide red, 40 g of titanium dioxide, 20 g of oxidized polyether wax (25% in xylene) and 20 g of tetraethoxysilane. The mixture was dispersed at high speed until the mill bottom had a fineness of 40 μm and a temperature of 55 ° C. With stirring, 470 g of silyl (meth) acrylate polymer solution S-2, 40 g of polyamide wax (20% in xylene) and 170 g of xylene were added. The mixture was cooled and a premix of 120 g tralopyril and 120 g methyl isoamyl ketone added. The paint was cooled to room temperature and transferred to smaller containers for viscosity measurements and storage stability tests. The viscosity was measured the next day.

The paint composition had a calculated VOC of 403 g / L and a measured Stormer viscosity of 86 KU and a cone and plate viscosity of 369 cP.

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 3078715A [0006]
• WO 9744401 [0103]
• EP 1342756 [0105]
• EP 1695956 [0105]
• JP 2016216651 A [0105]
• WO 03/070832 [0108]
• EP 2128208 [0108]
• GB 2152947 [0108]
• EP 0526441 [0108]
• WO 2009/100908 [0108]
• WO 9614362 [0108]
• WO 2011/092143 [0108]
• WO 0077102 [0118]

Cited non-patent literature

• ISO 2884-1: 1999 [0126]

Claims (28)

Anti-fouling coating composition comprising: (i) a silyl (meth) acrylate polymer; (ii) tralopyril; (iii) a polar solvent; and (iv) a nonpolar solvent; wherein the polar solvent has an evaporation rate based on n-butyl acetate of at least 0.1 and a Hansen solubility parameter δH of <17.0 (J / cm ³ ) ^1/2 , the composition is at least 2.5% by weight polar solvent based on the total amount of the solvent present in the composition, and the composition has a viscosity of less than 2000 cP. Composition as in Claim 1 wherein the polar solvent has an evaporation rate based on n-butyl acetate of at least 0.2. Composition as in Claim 1 or 2 wherein the polar solvent has a Hansen solubility parameter δH of 2.0 to 14.5 (J / cm ³ ) ^1/2 . Composition like in one of Claims 1 to 3 wherein the polar solvent has a Hansen solubility parameter δP of <10.0 (J / cm ³ ) ^1/2 . A composition as claimed in any preceding claim, wherein the polar solvent has a Hansen solubility parameter ΔD of <20.0 (J / cm ³ ) ^1/2 . A composition as claimed in any preceding claim wherein the polar solvent comprises at least one heteroatom selected from O, N, P and S, preferably O. A composition as claimed in any preceding claim wherein the polar solvent does not comprise a primary alcohol functional group. A composition as claimed in any preceding claim wherein the polar solvent comprises a functional group selected from -O-, -OC (O) -, -C (O) - and -C (OH) -. Composition as in Claim 1 to 7 wherein the polar solvent is selected from the formulas (Ia) - (Ic):

wherein each R is independently selected from C _3-8 linear or branched alkyl groups; R ^{1 is} selected from C _1-8 linear or branched alkyl groups optionally interrupted by an -O- group; and R ^{2 is} selected from H or linear or branched C _1-8 alkyl groups optionally interrupted by an -O group. Composition as in Claim 9 wherein R is linear or branched C _3-6 alkyl. Composition as in Claim 9 or 10 wherein the polar solvent is selected from formula Ib or Ic. A composition as claimed in any preceding claim, wherein the polar solvent is selected from 1-methoxy-2-propanol, n-butyl acetate, 1-methoxy-2-propyl acetate, methyl isoamyl ketone, methyl amyl ketone and methyl isobutyl ketone. A composition as claimed in any preceding claim, wherein the composition comprises at least 3% by weight of polar solvent, based on the total amount of solvent present in the composition. A composition as claimed in any preceding claim, wherein the non-polar solvent is an aromatic hydrocarbon. A composition as claimed in any preceding claim, wherein the silyl (meth) acrylate polymer is a copolymer. A composition as claimed in any preceding claim wherein the silyl (meth) acrylate polymer comprises a residue of at least one monomer of formula (II):

wherein R ^{4 is} H or CH ₃ ; R ^{6 are} each independently selected from linear or branched C _1-4 alkyl groups; R ^{6 are} each independently selected from the group consisting of linear or branched C _1-20 alkyl groups, C _3-12 cycloalkyl groups, optionally substituted C _6-20 aryl groups, and -OSi (R ⁷ ) ₃ groups; each R ^{7 is} independently a linear or branched C _1-4 alkyl group; Z is C ₁ -C ₄ alkylene; m is an integer of 0 to 1; and n is an integer from 0 to 5. A composition as claimed in any preceding claim wherein the silyl (meth) acrylate polymer further comprises (meth) acrylate monomers. Composition as in Claim 17 wherein the (meth) acrylate monomer has the formula (IIIa) - (IIIc):

wherein R ^{8 is} hydrogen or methyl, R ^{9 is} a cyclic ether (such as oxolane, oxane, dioxolane, dioxane, optionally alkyl-substituted) and X is C ₁ -C ₄ alkylene;

wherein R ^{8 is} hydrogen or methyl and R ^{10 is} a C ₃ -C ₁₈ substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom;

wherein R ^{8 is} hydrogen or methyl, and R ^{11 is} a C ₁ -C ₈ hydrocarbon radical. A composition as claimed in any preceding claim, wherein the composition comprises 0.5-10% by weight of tralopyril. A composition as claimed in any preceding claim, comprising: (i) 1-50% by weight of a silyl (meth) acrylate polymer; (ii) 0.5-10% by weight of tralopyril; (iii) 0.5-30% by weight of a polar solvent; and (iv) 0-35% by weight of a nonpolar solvent; A composition as claimed in any preceding claim, wherein the composition has a viscosity of 50 to 2000 cps after 1 week storage at 52 ° C. A composition as claimed in any preceding claim, wherein the composition does not gel during storage for 4 weeks at 52 ° C. Process for the preparation of a composition as in any of Claims 1 to 22 comprising mixing: (i) a silyl (meth) acrylate polymer; (ii) tralopyril; (iii) a polar solvent; and (iv) a nonpolar solvent. A paint comprising a composition as in any of Claims 1 to 22 claimed. Paint container having a composition as in any of the Claims 1 to 22 contains claimed. An article comprising (eg, covered with or coated with) a coating on at least a portion of a surface thereof, said coating having the composition as in any of Claims 1 to 22 comprises claimed. A method of coating an article to prevent fouling thereof, the method comprising: coating at least a portion of a surface of the article with a composition as in any of Claims 1 to 22 claimed; and drying and / or curing the coating. Use of a composition as in any of Claims 1 to 22 claimed for coating at least a portion of a surface of an article to prevent fouling thereon.